The aim of the present study was to compare the surface morphology alterations, mineral content, and surface roughness of eroded enamel surface versus eroded enamel surface which was preceded by Bioactive Glass 45S5 (BAG45S5) application in both primary and permanent human dentitions.Fifty-two primary teeth and fifty-two permanent teeth were selected. Teeth were randomly divided into 4 groups of twenty-six teeth each. Groups A1 and B1 underwent erosion with 1% citric acid, while groups A2 and B2 were subjected to application of BAG45S5 powder followed by the same erosive conditions as A1 and B1. Measurements were performed by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and surface profilometry. They were used to examine the surface morphology alterations, mineral content, and surface roughness, respectively.p < 0.005) in both human dentitions. Erosion-only groups showed significantly less surface roughness in permanent teeth (p < 0.045). A marked decrease in surface roughness was observed in surfaces receiving BAG45S5, primary teeth (p < 0.001), and permanent teeth (p < 0.001).SEM of enamel which received BAG45S5 showed smoother surface in primary teeth post erosion. EDX analysis showed that enamel exhibited crucial resistance to mineral loss in the group which received BAG45S5 prior to inducing erosion as compared to the induced erosion-only group. This was significant (Bioactive Glass 45S5 proved successful against erosive conditions in both primary and permanent teeth with better performance in the permanent teeth so it can be regarded as a means of prevention.Bioactive Glass 45S5 powder could be used not only to remove stains but also as a prophylactic preventive measure against the multiple episodes of acidic food and beverage consumption in children. Dental erosion is the chronic and progressive, irreversible loss of dental hard tissues caused by a chemical process without any bacterial involvement. It has become a significant clinical challenge in the recent years. This is due to the major lifestyle changes that have led to an increase in the amount and frequency of consumption of acid-containing foods and beverages . Owing tErosion could have dramatic effect on the dental tissues and would result in alterations in surface roughness, changes in surface morphology, and even mineral loss of dental tissues –7. TheseBioactive glasses are biocompatible silicate-based materials, containing calcium and phosphate in an amorphous matrix. They undergo a unique biological reaction at the interface stimulating the formation of a chemical bond between living structures and the material itself . These sA study by Dionysopoulos et al. revealed that surface pre-treatment using air abrasion with BAG45S5 may help to prevent enamel surface erosion induced by an acidic drink in bovine teeth . In addiThe current study is a cross-sectional in vitro study, which was conducted in the Pediatric Dentistry and the Oral Biology Departments, Faculty of Dentistry, Pharos University in Alexandria, Alexandria, Egypt. Ethical approval was obtained from the Research Ethics Committee—Pharos University in Alexandria in adherence to the tenets of the Declaration of Helsinki 1964 and its later amendments (# PUA02202207243036) . ParticiSample size was based on 95% confidence level to detect differences in surface roughness and mineral content between eroded enamel surface as opposed to eroded enamel surface preceded by BAG45S5 application. Dionysopoulos et al. reported mean ± SD difference in surface roughness of eroded enamel pre-treated with Bioactive Glass = 0.002 ± 0.001, whereas it was 0.006 ± 0.01 for eroded enamel . The calAge group 6–20 years; normally shed or serially extracted teeth ; sound labial/buccal enamel surface.Labial/buccal enamel surface with cracks; developmental defects; caries; erosion; fillings.Group A1: twenty-six primary teeth undergoing erosion induction only. Subgroups: two teeth assigned for scanning electron microscopy (SEM) (A1-SEM); twelve teeth for energy-dispersive X-ray spectroscopy (EDX) (A1-EDX); twelve teeth for profilometry (A1-Pro)Group A2: twenty-six primary teeth receiving BAG45S5 followed by erosion induction. Subgroups: two teeth assigned for SEM (A2-SEM); twelve teeth for EDX (A2-EDX); twelve teeth for profilometry (A2-Pro)Group B1: twenty-six permanent teeth undergoing erosion induction only. Subgroups: two teeth assigned for SEM (B1-SEM); twelve teeth for EDX (B1-EDX); twelve teeth for profilometry (B1-Pro)Group B2: twenty-six permanent teeth receiving BAG45S5 followed by erosion induction. Subgroups: two teeth assigned for SEM (B2-SEM); twelve teeth for EDX (B2-EDX); twelve teeth for profilometry (B2-Pro)  Fig. Fifty-two primary teeth were randomly and equally divided into 2 groups A1 and A2. Fifty-two permanent teeth were also randomly and equally divided into the other 2 groups B1, B2. Randomization was completed using a computer-generated list of random numbers using RAND and RANK functions-Excel (MS Office 365). A serial number was given to each tooth indicating its allocation.Collected teeth were kept in 10% formaldehyde solution at 4 °C for 7 days for sterilization . Teeth w(BAG45S5) in the form of Sylc® powder  with particle size ranging from 25 to 120 µm  for 3 min, rinsed with distilled water, and stored in artificial saliva (storage medium) for 65–80 min between the 6 cycles for remineralization iii.Surface roughnessThe outcomes of the current study included:Assessment of outcomes was performed at baseline and post erosion for all groups.Scanning electron microscopy (SEM) JSM-IT200 InTouchScope™ Scanning Electron Microscope  was used for this purpose. Two teeth from each group were sectioned into buccal and lingual specimens using a double-sided fine grit water-cooled diamond disc yielding 4 specimens. One specimen of each tooth was randomly selected for baseline assessment of ultra-structure surface morphology alterations, while the other one was used for post erosion assessment. All specimens were dehydrated at the time of evaluation by passed through series of 50%, 70%, and 95% ethyl alcohol for 10 min each and then in absolute alcohol for two changes of 1-h period each. This was followed by drying in vacuum desiccator for 1 h . The assEnergy-dispersive X-ray spectroscopy (EDX) JSM-IT200 InTouchScope™ Scanning Electron Microscope  was used for this purpose. Assigned teeth were well-polished using diamond paste (1-μm size). Then, they were washed out under running water, dehydrated, and air dried . After dProfilometry using linear scanning stylus; MarSurf PS 10  ISO 16610–21, Lt = 1.5 mm (0.25 × 5), parameters Ra and Rz was used for this purpose. Twelve teeth from each group were assessed for their surface roughness at baseline and then post erosion. Teeth were firstly polished using 1200-grit abrasive sandpaper to smoothen out any irregularities on the enamel surface. Then, they were stored in artificial saliva for 1 h. For each tooth, three measurements were taken, and an average reading for those three measurements was obtained.. . Qualitative data were described using number and percent. The Kolmogorov–Smirnov test was used to verify the normality of distribution. Quantitative data were described using range mean, standard deviation. Significance of the obtained results was judged at the 5% level. The used tests: Student t-test for normally distributed quantitative variables to compare between two groups and paired t-test for normally distributed quantitative variables to compare between two periods.Data were analysed using IBM SPSS software package version 20.0Group A1-SEM micrograph demonstrated generalized smooth surface architecture of the enamel surface (× 500) Fig. . Group BGroup A2-SEM micrograph was showing microscopic roughness and irregularities in some areas on the enamel surface (× 1500) Fig. . Group Bp < 0.001). Carbon (C) (mean ± SD) showed an increase post erosion = 51.48 ± 2.38 than baseline = 12.15 ± 2.65 which was statistically significant (p < 0.001). Oxygen (O2) (mean ± SD) showed a decrease post erosion = 43.47 ± 1.54 than baseline = 48.60 ± 1.75 which was statistically significant (p < 0.001). Fluoride (F) (mean ± SD) showed a negligible amount at baseline and post erosion with no significant difference (p = 0.275).The (mean ± SD) was at baseline for calcium (Ca) and phosphorus (P) = 24.29 ± 1.24 and 14.30 ± 0.81 respectively which decreased post erosion to = 3.20 ± 1.99 and 1.43 ± 0.88 for Ca and P, respectively. This was statistically significant (p < 0.001). C (mean ± SD) showed an increase post erosion = 10.85 ± 1.26 than baseline = 9.59 ± 2.50 which was statistically non-significant (p = 0.182). O2 (mean ± SD) showed an increase post erosion = 53.01 ± 1.68 than baseline = 48.96 ± 2.97 which was statistically significant (p < 0.001). Fluoride (F) (mean ± SD) showed a negligible amount at baseline and post erosion with no significant difference (p = 0.156) (Table The (mean ± SD) was at baseline for Ca and P = 26.09 ± 1.57 and 14.82 ± 0.77 respectively which decreased post erosion to = 22.45 ± 1.27 and 12.95 ± 0.57 for Ca and P, respectively. This was statistically significant (p = 0.335). Also, for P, (mean ± SD) was comparable between baseline and post erosion = 16.36 ± 0.56 and 16.15 ± 0.72, respectively. This was non-significant (p = 0.520). C (mean ± SD) showed a decrease post erosion = 10.27 ± 3.56 than baseline = 13.18 ± 1.92 which was non-significant (p = 0.085). O2 (mean ± SD) showed an increase post erosion = 35.23 ± 4.30 than baseline = 32.69 ± 3.17 which was non-significant (p = 0.067). F (mean ± SD) showed an increase post erosion than baseline = 0.61 ± 0.26 and = 0.37 ± 0.22, respectively. This was statistically significant (p = 0.004).The (mean ± SD) was comparable for Ca between baseline and post erosion = 37.32 ± 2.65 and 37.92 ± 4.48, respectively. This was non-significant (p = 0.255). Also, for P, (mean ± SD) was comparable between baseline and post erosion = 16.78 ± 0.61 and 17.29 ± 0.70, respectively. This was non-significant (p = 0.064). C (mean ± SD) showed a decrease post erosion = 5.83 ± 1.68 than baseline = 10.55 ± 1.63 which was statistically significant (p < 0.001). O2 (mean ± SD) showed an increase post erosion = 36.59 ± 5.24 than baseline = 33.93 ± 2.94 which was statistically significant (p = 0.049). F (mean ± SD) showed a negligible amount at baseline and post erosion with no significant difference (p = 0.352) (Table The (mean ± SD) was comparable for Ca between baseline and post erosion = 38.19 ± 2.99 and 39.49 ± 5.26, respectively. This was non-significant (p < 0.001). The (mean ± SD) of P content change decreased in A1-EDX than that of B1-EDX =  − 12.87 ± 0.47 and − 1.87 ± 0.53, respectively. This change was statistically significant (p < 0.001). The (mean ± SD) of O2 content change decreased in A1-EDX than that of B1-EDX =  − 5.13 ± 2.01 and 4.06 ± 2.94, respectively. This change was statistically significant (p < 0.001). The (mean ± SD) of F content change decreased in A1-EDX than that of B1-EDX =  − 0.11 ± 0.34 and 0.20 ± 0.45, respectively. This change was non-significant (p = 0.115). The (mean ± SD) of C content change increased in A1-EDX than that of B1-EDX = 39.33 ± 2.17 and 1.25 ± 3.05, respectively. This change was statistically significant (p < 0.001).Post erosion, the (mean ± SD) of Ca content change decreased in A1-EDX than that of B1-EDX =  − 21.09 ± 1.15 and − 3.64 ± 0.98, respectively. This change was statistically significant (p = 0.476). The (mean ± SD) of P content change decreased in A1-EDX than that of B1-EDX =  − 0.22 ± 1.14 and 0.51 ± 0.86, respectively. This change was non-significant (p = 0.159). The (mean ± SD) of O2 content change showed comparable change in A1-EDX and B1-EDX = 2.55 ± 4.35 and 2.66 ± 4.18, respectively. This change was non-significant (p = 0.947). The (mean ± SD) of F content showed comparable change in A1-EDX and B1-EDX = 0.24 ± 0.23 and 0.16 ± 0.59, respectively. This change was non-significant (p = 0.716). The (mean ± SD) of C content change increased in A1-EDX than that of B1-EDX =  − 2.90 ± 5.31 and − 4.72 ± 2.04, respectively. This change was non-significant (p = 0.340)  of Ca content change decreased in A2-EDX than that of B2-EDX = 0.60 ± 2.06 and 1.31 ± 3.76, respectively. This change was non-significant p = 0.76. The (P = 16.15 ± 0.72 and 1.43 ± 0.88 respectively (p < 0.001). The mineral content change of C and O2 significantly decreased in A2-EDX than A1-EDX as C = 10.27 ± 3.56 and 51.48 ± 2.38 respectively (p < 0.001) and O2 = 35.23 ± 4.30 and 43.47 ± 1.54 respectively (p < 0.001). F content change was comparable between groups A2-EDX and A1-EDX = 0.61 ± 0.26 and 0.54 ± 0.18 respectively which was non-significant (p = 0.454).The mineral content change of Ca and P significantly increased in A2-EDX than A1-EDX as Ca = 37.92 ± 4.48 and 3.20 ± 1.99 respectively (p < 0.001) and p < 0.001), and P = 17.29 ± 0.70 and 12.95 ± 0.57 respectively (p < 0.001).The mineral content change of Ca and P significantly increased in B2-EDX than B1-EDX as Ca = 39.49 ± 5.26 and 22.45 ± 1.27 respectively (2 significantly decreased in B2-EDX than B1-EDX as C = 5.83 ± 1.68 and 10.85 ± 1.26 respectively (p < 0.001) and O2 = 36.59 ± 5.24 and 53.01 ± 1.68 respectively (p < 0.001). F content change was comparable between groups B2-EDX and B1-EDX = 0.67 ± 0.45 and 0.79 ± 0.48 respectively which was non-significant (p = 0.537) . (Mean ± SD) of B1-Pro readings at baseline was = 0.56 ± 0.16, while for post erosion, it was decreased to = 0.28 ± 0.06, and this was statistically significant (p0 < 0.001). (Mean ± SD) of A2-Pro readings at baseline was = 0.58 ± 0.07, while for post erosion, it was decreased to = 0.27 ± 0.09, and this was statistically significant (p0 < 0.001). (Mean ± SD) of B2-Pro readings at baseline was = 0.61 ± 0.12, while for post erosion, it was decreased to = 0.28 ± 0.10, and this was statistically significant (p0 < 0.001). The change in surface roughness from baseline to post erosion significantly decreased in B1-Pro than that of A1-Pro = 0.56 ± 0.16/0.28 ± 0.06 and = 0.58 ± 0.16/0.57 ± 0.42 respectively (p1 = 0.045). The change in surface roughness from baseline to post erosion was similarly decreased in A2-Pro and B2-Pro = 0.58 ± 0.07/0.27 ± 0.09 and = 0.61 ± 0.12/0.28 ± 0.10 respectively (p1 = 0.563). The change in surface roughness, post erosion, between group A1-Pro = 0.57 ± 0.42, and A2-Pro = 0.27 ± 0.09 was significantly less in group A2-Pro (p = 0.026). The change in surface roughness, post erosion, between group B1-Pro = 0.28 ± 0.06, and B2-Pro = 0.28 ± 0.10 was not significant (p = 0.960) (Table (Mean ± SD) of A1-Pro readings at baseline was = 0.58 ± 0.16, while for post erosion, it was = 0.57 ± 0.42 which was not statistically significant p0 = 0.55.  on both human primary and permanent dentitions. To overcome the lack of reliability in the use of bovine teeth instead of human ones, teeth were used from both human dentitions instead of bovine teeth for more favourable clinically applicable results. In a review of literature conducted by Yassen et al.  and baseDissolution of the enamel usually occurs when it is exposed to undersaturated solutions at a pH less than the critical pH, which is thought to be 5.5 . TherefoBAG45S5 has been widely studied for its effectiveness on enamel remineralization. It improved the microhardness of the subsurface-eroded enamel surface . A fluorChanges in surface roughness commonly occur after the interaction of acidic solutions with tooth structures. While the effect of erosive solutions on the surface roughness depends on the thickness of the aprismatic layer, the non-treated permanent enamel with its thin aprismatic surface layer demonstrated a notable roughness after exposure to the erosive acid, whereas the non-treated primary enamel with its generally uniform and thicker aprismatic layer presenting a more stable surface texture was not as affected by the erosive agent . On the Moreover, the results of the current study revealed that both human dentitions were showing significant loss of calcium and phosphate ions post the erosive challenge. The dissolution was expected to occur due to the weak constitution of the calcium-deficient carbonated hydroxyapatite crystals present in the enamel layer causing a distorted lattice conformation that is more soluble in acidic environments. The primary dentition presented greater mineral loss and surface distortion, because of the higher number of carbonate molecules in the hydroxyapatite crystals in the primary enamel as well as the presence of copious organic content specific to primary enamel . This isOn the contrary, enamel surface that was pre-treated by BAG45S5 before the erosive challenge showed decreased rates of carbon ions when compared to the baseline. Moreover, there was no significant change in calcium or phosphate content after erosion also compared to baseline. The effect of BAG45S5 on enamel lessened the effect of erosion on either primary or permanent enamel compared to enamel of erosion-only surfaces. BAG45S5 was suggested to be able to restore early erosive enamel lesions with complete loss of hydroxyapatite crystal content . In the On demineralized enamel surface, BAG45S5 acted in some way differently as suggested by several studies. Abbassy et al. , in theiThroughout the comparison between both dentitions, the permanent dentition which received BAG45S5 showed slightly better response following exposure to induced erosive challenge. Permanent enamel has better consolidation with particles of BAG45S5 due to the intrinsically higher inorganic content as well as morphological differences, indicating that the permanent enamel allows better integration of Bioactive Glass with the inherent calcium and phosphate ions to form more hydroxycarbonate apatite crystals . Since tIt can be concluded that applying Bioactive Glass 45S5 (BAG45S5) to the enamel surface prior to inducing erosion showed better results than inducing erosion alone in both primary and permanent dentitions. Consequently, BAG45S5 can limit or even prevent dental erosion in both primary and permanent dentitions by protecting the enamel surface from acid dissolution, with better performance on the permanent enamel. This means that BAG45S5 could be considered a promising method of erosion prevention. It could be implemented as a part of the preventive program tailored to children who show high consumption of juice and acidic beverages. Further clinical trials on children are needed to assess the effect on teeth sensitivity of using BAG45S5 prior to the repeated episodes of acidic food and beverage intake.Being dependant on collecting human teeth, difficulty was encountered in collecting the required number of teeth which led to compensating this through teeth sectioning.


Correction to: Acta Neuropathologica (2019) 138:251–273 10.1007/s00401-019-02013-zIn this article author would like to make few changes in the article text. The corrections are given below.1. In Materials and methods section for Immunofluorescence of human sections:In the sentence:goat serum blocking with 0.1 M KPBS and 0.025% Triton-X) for at least 1 h with gentle agitation.”“The sections were then washed (3 × 15 min) in 0.1 M KPBS, after which they were incubated in blocking buffer  and TNF-α (627–0.153 pg/mL). The Aβ40 detection range was 15,100–3.69 pg/mL, and the Aβ42 detection range was 2280–0.557 pg/mL. ELISA plates from R&D (DY008 and DY1197-05) were used to measure the levels of gal3 (detection range 1000–15.6 pg/mL) in culture media.”“The detection ranges of the different cytokines measured were as follows: IL1β (1670–0.408 pg/mL), IL4 (1660–0.405 pg/mL), IL12 , IL10 (3410–0.833 pg/mL), IFN-γ (938–0.229 pg/mL), IL2 (2630–0.642 pg/mL), IL5 (967–0.236 pg/mL), IL6 (5720–1.40 pg/mL), Action: Write “IL8 regarded as human functional homolog to rodent KC” between brackets next to KC/GRO.


Analysis of the Hirshfeld surface shows structure-defining interactions for bromomethylalcohol 1, resulting in intermolecular hydrogen bonds between the hydroxyl groups along the a-axis direction.Trimethyl({tris[(phenylsulfanyl)methyl]silyl}methoxy)silane ( 3), C26H32OS3Si, is a new ligand for transition-metal coordination chemistry derived from 3-bromo-2,2-bis(bromomethyl)propan-1-ol (1), C5H9Br3O, through silylation and following exchange of bromine groups with NaSPh. Silylated thioether ligand 3 crystallizes in the centrosymmetric space group C2/c. Bromomethylalcohol 1 crystallizes in the space group P1, resulting in intermolecular hydrogen bonds between the hydroxyl groups along the a-axis direction.Trimethyl({tris[(phenylsulfanyl)methyl]silyl}methoxy)silane ( As a result of the soft property of thioethers, they coordinate to transition metals . The molecular structure of bromomethylalcohol 1 is shown in Fig. 1Bromomethylalcohol et al., 1987The bond lengths to be expected for a C–Br bond are in the range 1.880–1.940 Å % for O1/Si1/C24–C26 and 49.1 (3)% for O1′/Si1′/C24′–C26′. The disorder at the TMSO group also shows a shorter O1—C23 [1.384 (15) Å] bond length than O1′—C23 [1.479 (14) Å]. The expected bond length for a C—O—Si bond is between 1.365 and 1.467 Å  bonds are of comparable lengths to each other and correspond to the expected bond lengths for alkyl–sulfur bonds  Å]. Moreover, the angles are approximately linear at 175 (4)° (O3—H3⋯O4) and 168 (4)° (O1—H1⋯O2). These hydrogen bonds can be assigned the graph-set symbol D11(2). This means that a hydrogen bond between two adjacent hydroxyl groups, O1—H1⋯O2, is established. The contact between O4—H4⋯O1 is created via the symmetry operation (i) x − 1, y, z.The crystal packing of bromomethylalcohol CrystalExplorer21 , which is due to the spatial arrangement of the bromine substituents in relation to the hydroxyl group.To gain further insight into the supramolecular packing interactions, a Hirshfeld surface analysis was performed propoxy]benzene-1,2-dicarbonitrile silane]dibromomercury(II)] silane-S,S′]mercury(II) -2-[(phenylthio)methyl]propan-2-ol yielded no hits in the WebCSD. By replacing the quaternary carbon with a silicon atom, the comparable structural motif of 2I2 rhomboids  was dropped into diethyl ether (50 mL) at 273.15 K to 1 (15.39 mmol). The solution was stirred for 1 h at room temperature and then chlorotrimethylsilane (16.93 mmol) was added at 273.15 K. It was stirred again for 1 h at room temperature, then the reaction solution was quenched with water. The aqueous phase was extracted three times with dichloromethane and the combined organic layers were dried over magnesium sulfate. The volatiles were removed to give compound 2 crude.Methyllithium  δ = 3.33 , 3.18 , 0.03 3) ppm.1H}13C NMR  δ = 61.6 , 44.3 , 34.6 , −0.7  ppm.{2 in DMF (10 mL) at 273.15 K and stirred for 10 minutes. The reaction solution was irradiated with microwaves  and then quenched with water. The aqueous phase was extracted three times with dichloromethane, the combined organic layers were dried over magnesium sulfate and the volatiles were removed. The residue was separated by fractional distillation under reduced pressure. Crystallization from diethyl ether at 243.15 K provided silylated thioether ligand 3 as clear and colourless blocks.Thiophenol (5.83 mmol) was then added to sodium hydride (5.83 mmol) in DMF (5 mL) at 273.15 K and stirred for 10 minutes. The NaSPh solution was added to 1H NMR  δ = 7.38–7.34 , 7.30–7.23 , 7.19–7.15 , 3.60 , 3.22 , 0.04  ppm.1H}13C NMR  δ = 137.2 , 129.8 , 128.9 , 126.2 , 64.1 , 46.0 4), 38.7 , −0.6  ppm.{6.Uiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso(H) = 1.5Ueq(C) for CH3 hydrogen atoms. Hydrogen atoms H1, H2, H3 and H4 for compound 1 were refined independently. The TMSO group in 3 is disordered with occupancies converging to 50.9 (3)% for O1/Si1/C24–C26 and 49.1 (3)% for O1′/Si1′/C24′–C26′.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S205698902300227X/vm2278sup1.cifCrystal structure: contains datablock(s) 1, 3, global. DOI: 10.1107/S205698902300227X/vm22781sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S205698902300227X/vm22783sup3.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S205698902300227X/vm22781sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S205698902300227X/vm22783sup5.cmlSupporting information file. DOI: 2247226, 2247225CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title carbazole derivative, the dihedral angle between the carbazole ring system and the pendant phenyl ring is 56.78 (8)°. 19H15NO, the dihedral angle between the benzene rings of the carbazole moiety is 1.73 (12)° and the methoxy-substituted phenyl ring deviates from the mean plane of the carbazole grouping (r.m.s. deviation = 0.020 Å) by 56.78 (8)°. In the crystal, weak C—H⋯π interactions link the molecules. The two-dimensional fingerprint plots derived from the Hirshfeld surface indicate that H⋯H (51.2%) and C⋯H/H⋯C (39.9%) contacts dominate the packing.In the title compound, C The crystal structure is consolidated by weak C—H⋯π interactions  = 2.71 Å; symmetry code: 1 − x, −y, z; C17—H17⋯Cg(C7–C12) = 2.92 Å; symmetry code: x, 1 + y, z]. The crystal packing viewed along the a-axis direction is shown in Fig. 3The title compound crystallizes in the orthorhombic space group it Fig. 1. As expens Fig. 2 [C9—H9⋯Cet al., 2017dnorm within the range −0.05 to 1.63 a.u. shows a few red spots in the locales of D⋯A  interactions, consistent with the presence of weak C—H⋯π interactions , which were uniformly dispersed in 35 ml of dimethylformamide (DMF) and the mixture was dissolved homogeneously under an N2 atm. To the mixture, K2CO3 , CuI  and 1,10-phenanthroline  was added and the mixture was refluxed for 12 h under N2. The progress of the reaction was monitored by TLC. After the completion of the reaction, the reaction was quenched in ice–water and the solid product was dissolved in ethyl acetate and washed with brine solution. The obtained solvent was removed under reduced pressure and the obtained residue was further purified using column chromatography (100–200 mesh silica gel) to afford the title compound as shown in Fig. 6A 100 ml round-bottom flask was charged with 4-iodoanisole 1.78 g , 9Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2414314623006740/hb4441sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314623006740/hb4441Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314623006740/hb4441Isup3.cmlSupporting information file. DOI: 2280833CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structures of two benzothiophene derivatives are described and the intermolecular contacts in the crystals analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots. 22H16FNO2S2 (I) and C26H20FNO2S2 (II), the benzothiophene rings are essentially planar with maximum deviations of 0.009 (1) and 0.001 (1) Å for the carbon and sulfur atom in compounds I and II, respectively. In I, the thiophene ring system is almost orthogonal to the phenyl ring attached to the sulfonyl group, with a dihedral angle of 77.7 (1)°. In compound I, the molecular structure is stabilized by weak C—H⋯O intramolecular interactions formed by the sulfone oxygen atoms, which generate two S(5) ring motifs. In the crystal of I, N—H⋯O hydrogen bonds link the molecules into R22(8) rings, which are connected into a C(10) chain via C—H⋯F hydrogen bonds. Intermolecular C—H⋯π interactions are also observed. In compound II, the molecules are linked via C—H⋯O and C—H⋯F hydrogen bonding, generating infinite C(11) and C(13) chains running parallel to [010].In the title compounds, C Thiophene derivatives possess pharmacological and biological activities including antibacterial benzenesulfonamide (C7–C22/N1/S2/O1/O2/F1) while compound II, C26H20FNO2S2 benzenesulfonamide (C9–C15/N1/S2/O1/O2). In both compounds, the benzothiophene ring systems (S1/C1–C8) are essentially planar with maximum deviations of 0.009 (1) and 0.001 (1) Å for atom C8 and S1 in compounds I and II, respectively. The mean planes of the thiophene ring system in I make dihedral angles of 1.2 (2), 2.3 (2), 77.7 (2)° with the C1–C6, C11–C16 and C17–C22 phenyl rings. The mean planes of the thiophene ring system in II make dihedral angles of 0.3 (2), 33.3 (2), 25.2 (2)°, respectively, with the C1–C6, C11–C16 and C17–C22 phenyl rings, The benzothiophene ring system in I is almost orthogonal to the C17–C22 ring attached to sulfonyl group with dihedral angle of 77.7 (1)° in I. For both compounds, the bond lengths and angles are close to those observed for similar structures ° in II], with a simultaneous decrease in the N1—S2—C17 angle [106.35 (9) in I and 108.3 (2)° in II] from the ideal tetrahedral value (109.5°) are attributed to the Thorpe–Ingold effect  and N1—C16 = 1.450 (5) Å bond lengths in the molecule are longer than the mean Nsp2—Csp2 bond-length value of 1.355 (14) Å   interactions, where the Cg1 is the centroid of the C1–C6 ring  were performed with CrystalExplorer17  through white to blue . The dnorm surface was mapped over a fixed colour scale of −0.434 (red) to 1.449 (blue) for compound I and −0.119 (red) to 1.765 (blue) for compound II, where the red spots indicate the intermolecular contacts involved in the hydrogen bonding. The electrostatic potential was also mapped on the Hirshfeld surface using a STO-3G basis set and the Hartee–Fock level of theory . Areas on the Hirshfeld surface with high curvedness tend to divide the surface into contact patches with each neighbouring molecule. The coordination number in the crystal is defined by the curvedness of the Hirshfeld surface . The nearest neighbour coordination environment of a molecule is identified from the colour patches on the Hirshfeld surface depending on their closeness to adjacent molecules .The Hirshfeld surfaces of compounds I, they reveal that the principal intermolecular contacts are H⋯H contacts at 36.9% , H⋯C/C⋯H contacts at 26.1% , O⋯H/H⋯O at 15.1% , F⋯H/H⋯F at 9.2% , C⋯C at 6.7% , S⋯C/C⋯S at 2.2% , S⋯H/H⋯S contacts at 0.9% , F⋯C/C⋯F at 0.8% , N⋯C/C⋯N at 0.7%  and N⋯H/H⋯N contacts at 0.3% .The fingerprint plots are given in Figs. 89% Fig. 8b, H⋯C/C1% Fig. 8c, O⋯H/H1% Fig. 8d, F⋯H/H2% Fig. 8e, C⋯C a7% Fig. 8f, S⋯C/C2% Fig. 8g, S⋯H/H9% Fig. 8i, F⋯C/C8% Fig. 8j, N⋯C/C7% Fig. 8k and N⋯3% Fig. 8l.II, they reveal a similar trend, with the principal intermolecular contacts being H⋯H/H⋯H at 41.4% , H⋯C/C⋯H contacts at 25.1% , O⋯H/H⋯O at 12.1% , F⋯H/H⋯F at 8.1% C⋯C at 4.6% , C⋯·C at 4.7% , S⋯H/H⋯S contacts at 4.5% , S⋯C/C⋯S contacts at 2.1% , C⋯O/O⋯C contacts at 1.0% , F⋯S/S⋯F at 0.9%  and O⋯O contacts at 0.3 . In both compounds, the H⋯H intermolecular contacts predominate, followed by the C⋯H/H⋯C and O⋯H/H⋯O contacts.For compound 4% Fig. 9b, H⋯C/C1% Fig. 9c, O⋯H/H6% Fig. 9e, C⋯·C 7% Fig. 9f, S⋯H/H5% Fig. 9g, S⋯C/C1% Fig. 9h, C⋯O/O0% Fig. 9i, F⋯S/S9% Fig. 9j and O⋯.3 Fig. 9k. In bo5.I: To a solution of (E)-2-(2-(benzo[b]thiophen-2-yl)vinyl)-5-fluorobenzenaminium chloride  in dry DCM (10 mL), pyridine  and PhSO2Cl  were added and stirred at room temperature for 12 h. After completion of the reaction (monitored by TLC), it was poured into crushed ice (50 g) containing conc. HCl (5 mL), extracted with DCM (2 × 20 mL) then washed with water (2 × 20 mL) and dried (Na2SO4). Removal of solvent in vacuo followed by crystallization from diethylether (4 mL) afforded (E)-N-{2-[2-(benzo[b]thiophen-2-yl)ethenyl]-5-fluorophenyl}benzenesulfonamide as a white solid.Compound II: To a solution of (E)-N-{2-[2-(benzo[b]thiophen-2-yl)vinyl]-5-fluorophenyl}benzenesulfonamide  in CH3CN (10 mL), K2CO3  and 1-bromobut-2-yne  were added and stirred at room temperature for 12 h. After completion of the reaction (monitored by TLC), it was poured into crushed ice (50 g) containing conc. HCl (5 mL), extracted with ethyl acetate (2 × 20 mL) then washed with water (2 × 20 mL) and dried (Na2SO4). Removal of solvent in vacuo followed by crystallization from methanol (4 mL) afforded (E)-N-{2-[2-(benzo[b]thiophen-2-yl)ethenyl]-5-fluorophenyl}-N-(but-2-yn-1-yl)benzenesulfonamide as a white solid.Compound 6.I, the NH H atoms were located in difference-Fourier maps and freely refined. For compound II, they were included in calculated positions and refined as riding: N—H = 0.93 Å with Uiso(H) = 1.2Ueq(N). All C-bound H atoms were positioned geometrically and constrained to ride on their parent atoms: C–H = 0.93–0.97 Å with Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. In compound I, the thiophene ring is disordered over two positions with a refined occupancy ratio of 0.756 (4):0.244 (3). The geometries were regularized using soft restraints.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989023006096/zn2029sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989023006096/zn2029Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989023006096/zn2029IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989023006096/zn2029Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023006096/zn2029IIsup5.cmlSupporting information file. DOI: 2280606, 2280605CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


It crystallizes isotypically with H-La2[Si2O7]. The four crystallographically distinct CeIII cations form distorted square antiprisms, capped square antiprisms, and bicapped square antiprisms as coordination polyhedra consisting of oxygen atoms. Four crystallographically different silicon atoms recruit the centers of two different isolated [Si2O7]6– units.The title compound, dicerium(III) oxidodisilicate, Ce H-type Ce2[Si2O7], like H-La2[Si2O7]  cover an interval from 2.366 (4) to 2.817 (4) Å (Table 1plus 3.11 (4)–3.34 (4) Å to most caps. All oxygen atoms belong to pyroanionic oxidodisilicate anions [Si2O7]6–  = 1.588 (4)–1.676 (4) Å   as reaction vessel at a temperature of 1023 K, taking advantage of the presumed mineralizers Sb2O3 and CeCl3. The transparent, colorless crystals exhibit a platelet-like habit.Single crystals of Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314623005916/wm4192sup1.cifCrystal structure: contains datablock(s) I, 1R. DOI: 10.1107/S2414314623005916/wm4192Isup2.hklStructure factors: contains datablock(s) I. DOI: 2222660CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Araucaria araucana is an ancient conifer, native to the mountain ranges in Chile and Argentina. These trees host a large number of organisms, mainly insects, strongly or even exclusively associated with them. The recent emergence of a novel canker disease on A. araucana has emphasised the importance of fungi associated with these iconic trees and has resulted in the discovery of various new species. In this study, we considered the identity of an unknown calicioid fungus consistently found on resin on the branches of A. araucana. Preliminary phylogenetic analyses placed isolates in the recently described sub-class Cryptocaliciomycetidae, closest to Cryptocalicium blascoi. However, the morphology of the ascomata and its occurrence in a unique niche suggested that the closest relative could be Resinogalea humboldtensis , a fungus with similar sporing structures found on resin of Araucaria humboldtensis in New Caledonia. There are no living cultures or sequence data available for either R. humboldtensis or its supposed closest relative, Bruceomyces castoris, precluding sequence-based comparisons. Morphological comparisons of the sporing structures on A. araucana confirmed that the ascomatal morphology of our unknown calicioid fungus and R. humboldtensis are almost identical and resemble each other more so than B. castoris or Cr. blascoi. A phylogenetic analysis based on the small subunit (SSU), internal transcribed spacer (ITS) and large subunit (LSU) rDNA regions resolved our strains into two clades with Cr. blascoi as its closest relative. Further analyses applying the Genealogical Concordance Phylogenetic Species Recognition (GCPSR) based on ITS, mini chromosome maintenance protein complex (MCM7), RNA polymerase II second largest subunit (RPB2) and translation elongation factor 1-alpha (TEF) gene regions, confirmed that strains represent two new species. Based on our morphological observations and phylogenetic analyses, we introduce two new Resinogalea species, R. araucana and R. tapulicola, and reclassify the genus in the subclass Cryptocaliciomycetidae.The online version contains supplementary material available at 10.1186/s43008-023-00122-9. Araucaria araucana (Araucariaceae), commonly known as Araucaria, pewén or the monkey puzzle tree, is an ancient species native to the mountain ranges of Chile and Argentina. The species is one of only two in the genus and family found in South America, with the remainder distributed in the Southeast Asia–Oceania region     to accommodate both genera, Resinogalea and Bruceomyces, each containing a single species  or 2% malt extract agar  in Petri dishes. Plates were incubated for 14 d at 20–25 °C. Fungal colonies of interest were transferred to new MEA plates in order to produce pure cultures. Isolates were further purified by transferring them to 2% water-agar  and allowing these to grow for 2–4 d before transferring single hyphal tips to new MEA plates. Direct isolations from ascomata were made by collecting ascospores with a sterile needle, spreading these onto WA and after 2–4 days, transferring germinating single spores to new MEA plates.All relevant isolates used in this study were deposited into the culture collection (CMW) housed at the Forestry and Agricultural Biotechnology Institute . Representative strains for each species were subsequently deposited into the CMW-IA culture collection  and to the culture collection (CBS) of the Westerdijk Fungal Biodiversity Institute . Specimens were deposited in the PREM fungarium of the South African National Collections of Fungi housed at the Agricultural Research Council .DNA extractions were performed using the Prepman® Ultra Sample Preparation Reagent kit  following the manufacturer’s protocols. For some strains, DNA was extracted using a phenol–chloroform method. For the latter approach, strains were grown on MEA for 21 d, after which mycelium was collected in 2 mL Eppendorf tubes and freeze dried overnight. Mycelia was ground by adding metal beads and shaking this in a mixer mill  and then following the protocol described by Barnes et al.  and modiRPB2) with primers RPB2-5f2 & RPB2-7cR  with primers Cer-MCM7F & Cer-MCM7R  large intron with primers EF1-782F & EF-2  of each primer (10 µM), 0.3 µL MyTaq™ DNA Polymerase and 17.7 µL (16.7 µL for MCM7) sterile deionized water. The thermal cycling conditions included an initial denaturation step of 95 ˚C for 3 min, followed by 35 cycles of denaturing at 95 ˚C for 30 s, annealing at 56 ˚C (52 ˚C for TEF1 and MCM7) for 30 s and elongation at 72 ˚C for 45 s, followed by a final elongation step at 72 ˚C for 4 min. Successful amplifications were confirmed by staining PCR amplicons with GelRed® (2 µL per 4 µL of PCR product) and electrophoresing the product on a 1% agarose gel for 12 min at 110 V.Six gene regions were amplified through PCR, which included: (i) the internal transcribed spacer 5.8S rDNA (ITS) with primers ITS1 & ITS4 .PCR amplicons were cleaned from excess primers and unincorporated nucleotides either by sodium acetate precipitation  approach  and edited using Affinity Designer v.1.10.5.1342 (Serif (Europe), Nottingham, UK). Aligned datasets and IQ-TREE outputs were uploaded to the University of Pretoria’s research data repository hosted on Figshare and can be accessed at https://doi.org/10.25403/UPresearchdata.21640298.Each dataset was aligned using the MAFFT v.7 online service selecting the L-INS-i algorithm . Microscopic slides were prepared from 28 d old colonies using 10% lactic acid as mountant. Structures collected directly from samples were first sectioned using a Leica CM1520 cryostat  before a microscope specimen was prepared. Characters were observed and photographed using a Zeiss AXIO Zoom.V16 dissection and AXIO Imager.A2 compound microscopes both equipped with a Zeiss AxioCaM 512 colour camera driven by Zen Blue v.3.2 software . For dissection microscope images, extended depth of field analyses were performed using Helicon Focus v.7.5.4 . Up to 50 measurements were made for each character where available, and boxplot graphs were constructed with measurements of each character to visualize data distribution. Photographic plates were prepared in Affinity Designer v.1.10.5.1342 (Serif (Europe) Ltd, Nottingham, UK). Attempts were made at the time of the study to obtain specimens for R. humboldtensis but these were unsuccessful. Morphological comparisons were thus based on the description published in Rikkinen et al.  using a micropipette and allowed to dry for 10 min before plates were sealed with Parafilm® and incubated upside down. Plates were incubated at temperature gradient of 5 °C intervals from 5–35 °C for 21 d and colony diameters measured every 3–4 d. The colony area was measured from images taken on day 21 using ImageJ v.1.52  and Trongol Alto .Isolations made from surface disinfested n = 23), and from single spore isolates from five fruiting bodies (n = 5). A preliminary phylogenetic analysis , 39 gaps (6%)), followed by Penicillium scabrosum , 35 gaps (5%)), P. hirayamae , 28 gaps (4%)), P. copticola , 16 gaps (3%)), and P. terrigenum , 27 gaps (4%)). Six strains were selected from each of the two ITS clades and five additional gene regions sequenced for them to continue further analyses.DNA extraction and ITS sequencing was performed for all strains originating from plant tissue , ITS  and LSU  were concatenated resulting in a matrix containing 62 taxa that was 5770 bp long. The most suitable nucleotide substitution models according to the Bayesian information criterion (BIC) for SSU, ITS and LSU were TNe + I + G4, GTR + F + I + G4, and TN + F + I + G4 respectively. ML and BI analyses resolved strains, with high bootstrap support, into two clades in the subclass Cryptocaliciomycetidae with Cr. blascoi as its closest relative  in Cr. blascoi and the outgroup Caliciopsis pinea. Substitution models for the aligned ITS , MCM7 , RPB2 , and TEF1 , datasets were, respectively, TNe + G4, K2P + I, TNe + I and TNe + G4. All gene regions resolved the strains in two concordant well-supported clades, and with the exception of SSU, all regions resolved them in a clade separate from Cr. blascoi. Similarities between isolates from the two clades containing our isolates were low; the SSU differed by three or more substitutions, the LSU differed by eight or more substitutions, the ITS differed by 20 or more substitutions, the MCM7 differed by 99 or more substitutions, the TEF1 differed by 102 or more substitutions, and the RPB2 differed by 99 or more substitutions.Single gene phylogenies were subsequently calculated to assess the phylogenetic relationships between our strains by applying GCPSR Fig. . For theR. humboldtensis  and distinctive characters such as the shape of the ascomata and ascospore ornamentation  were observed only on branch samples, never in culture, and all strains obtained from them resided in a single clade based on DNA sequence comparisons. The ascomata on the samples emerged directly from resin or the plant tissue that surrounded it Fig. . Ascomaties Fig. a, b. TheRikkinen ; Table 2Cryptocalicium blascoi, the closest phylogenetic relative to our species, shares broad morphological and niche features with our fungus and R. humboldtensis . Furthermore, morphological characteristics, colony growth rate and optimal growth temperature data revealed minor but consistent differences between two species which we describe below : Conguillío National Park sector Los Paraguas: -38.697836°, -71.817216°, from ascomata on branches of A. araucana, 02 May 2018, F. Balocchi .Description: In nature — Ascomata emerging from dry resin patches in branches of A. araucana, stipitate, capitate, (556–)766–1070(–1540) µm tall (excluding mazaedium); stipe cylindrical, subulate or rarely dumbbell-shaped, bent wholly or at the base, rarely straight, black, rugose, covered with a granular orange to reddish-brown mineral pruina, (257–)364–598(–1069) × (70–)92–214(–275) µm; stipe medulla composed of textura intricata-porrecta, brownish pigmentation; stipe outermost layer composed of 15–20 layers of textura prismatica-porrecta, long parallel hyphae, cylindrical, septate, slightly thick walled, hyaline inner layers becoming dematiaceous towards outer layers, hyphae 2–3 µm wide; strongly melanized mycelium emerging from the base of the stipe, hyphae darkly pigmentated and thick walled, (3–)6–9(–13.5) × 3–5(–7.5) µm; capitulum spherical when immature, ampulliform or urceolate when mature, (204–)293–394(–467) µm wide, (121–)230–344(–500) µm tall (not including mazaedium), black, rugose, sometimes covered with white to yellowish white resin; margins at the apical opening discrete, irregular, sometimes crenate-like, light brown; mazaedium well-developed in mature ascomata, reddish-brown, irregularly shaped or in some cases columnar, up to 290 µm in length; ectal excipulum poorly differentiated from the medullary excipulum, both combined consisting of 8–14 layers of textura prismatica–porrecta, hyphae periclinally arranged, darkly pigmented in the outer layers and becoming hyaline in the inner, (8–)11–17(–32) × 3–6(–9) µm; subhymenium hyaline or with very slight yellowish pigmentation, composed of textura angularis-intricata. Asci clavate, hyaline, pedicellate, bitunicate, evanescent, eight-spored, often with biseriately arranged spores, sporiferous part (15.5–)19–23(–30) × 4–6 µm, pedicel 6–18.5(–32) × 1.5–3 µm. Ascospores non-septate, hyaline when immature, becoming brownish with age, smooth to finely roughened, broadly ellipsoidal, some globose or ellipsoidal, some erythrocyte-like, 4–5.5(–6.5) × (3.5–)4–5.5 µm, (x̅ = 5.25 ± 0.6 × 4.34 ± 0.49), average length/width 1.22 ± 0.12 (n = 50). Paraphyses hyaline, filiform, obtuse, non-branched, 1–5 septate, 64–121(–172) × 2–3 µm. Phialide-like structures sporadically found inside the capitulum, potentially emerging from walls, hyaline, single-celled, subglobose, ellipsoidal or ampulliform, guttulate, (3–)4.5–7.5(–8.5) × 2–3(–4) µm, bearing single conidia-like structures, globose to obovoid, sometimes lobsided, hyaline when immature, becoming brownish with age, smooth or finely roughened, 4–6(–7) × 3.5–5.5 µm (x̅ = 5.54 ± 0.67 × 4.47 ± 0.59), average length/width = 1.25 ± 0.19 (n = 37).In culture — colony diameters: (mm after 14 d (after 21 d)): MEA at 5 °C microcolonies (3–5), at 10 °C 6–9 (13–15), at 15 °C 13–21 (17–28), at 20 °C 19–26 (29–35), at 25 °C 18–24 (29–37); PDA at 5 °C microcolonies (3–4), at 10 °C 8–11 (13–17), at 15 °C 15–18 (21–26), at 20 °C 20–24 (28–35), at 25 °C 19–27 (27–40), at 30 °C 6–15 (8–21), at 35 °C no growth; WA at 5 °C microcolonies (2–5), at 10 °C 5–8 (10–13), at 15 °C 10–14 (15–20), at 20 °C 14–19 (22–27), at 25 °C 14–23 (25–36); OA at 20 °C 18–24 (30–36).Colony characters: MEA 25 °C 21 d: Colonies velvety, concentric darkening or without pattern, umbonate, margins entire to slightly irregular, subsurface, obverse greyish yellow to dark yellow (4B4–C8), aerial mycelium yellowish white to orange white (4A2–5A2) at margins, pale to light yellow (4A3–5) centrally, reverse beige to blond (4C3–4) orange yellow to dark yellow (4B8–C7) centrally. MEA 20 °C 21 d: Colonies slimy, glabrous and sulcate, rarely dry and fluffy, umbonate, with full or slightly crenate margins, obverse greyish yellow to dark yellow (4B3–C8), aerial mycelium yellowish white to orange white (4A2–5A2) at margins, yellowish white to light yellow (4A2–5) centrally, reverse beige to blond (4C3–4) at margins, orange yellow to dark yellow (4B8–C7) centrally. MEA 20–25 °C 6 wks or older: Colonies slimy, glabrous, sulcate, irregular margins, producing sporodochia as mucilaginous spore masses on the surface, in concentric halos or with no pattern, dark brown to brownish black (6F4–H8). PDA 25 °C 21 d: Colonies velvety, glabrous, some cultures slimy only at centres, concentric or slightly petaloid pattern, umbonate, with full or slightly crenate margins, obverse yellowish grey to orange white (4B2–5A2), margins sunken in the medium, aerial mycelium greyish yellow to pale orange (4B4–5A3) at margins, becoming slightly darker or sometimes grey (4B1–D1) towards the centre, reverse yellowish white to yellowish grey (4A2–B2) at margins, pale yellow to olive (2D4–4A3) at centre, sometimes olive (2F7).Microscopic characters: Somatic hyphae at colony periphery hyaline, smooth, thin-walled, branched, transversely septate, 1.5–4.5 µm diam, anastomosing and developing coils, becoming inflated and melanized with age. Conidiomata most commonly absent, sporodochial with age, composed of pseudostromatic thick-walled melanized hyphae, setae absent. Conidiophores reduced, unbranched, rarely single branched or stromatic. Conidiogenous cells monophialidic or undifferentiated, then acropleurogenous; denticles sometimes present, up to 3 µm in length; terminal conidiogenous loci 13.5–25 (–35) µm in length from septa; phialides ampulliform, curved or straight and tapering towards the apex, collarette distinct, (5.5–)7–10(–15) × 2.5–3(–4) µm. Conidia produced in slimy heads, hyaline, sometimes dematiaceous with age, aseptate, smooth walled, distinct hilum mostly present, globose to broadly ellipsoidal, larger conidia on PDA and WA typically ellipsoidal to ovoid, variable in size, from MEA (3–)3.5–4.5(–6.5) × 3–3.5(–4) µm (x̅ = 3.83 ± 0.46 × 3.41 ± 0.26), average length/width = 1.13 ± 0.17 (n = 228), from PDA 3.5–6(–8) × (3–)3.5–5 µm, (x̅ = 5.06 ± 1.11 × 3.82 ± 0.46), average length/width = 1.32 ± 0.26 (n = 56), from WA (3–)3.5–5(–6.5) × (2.5–)3–3.5 (–4.5) µm (x̅ = 4.39 ± 0.82 × 3.3 ± 0.38), average length/width = 1.34 ± 0.26 (n = 62).Habitat/host: Resinogalea araucana produces ascomata on dry resin patches on damaged tissues in A. araucana branches. It was isolated directly from resin or plant tissues covered with resin. The type of damage inducing the exudated resin in which this fungus was found varied between samples, and included cankers caused by pathogenic fungi or insect feeding. This suggests that the presence of this fungus is merely associated with the presence of dry resin and has no role in causing resin to be produced. Strains originated from all collection sites in the Andes and Coastal range, suggesting that its distribution overlaps that of A. araucana.Material examined:Chile:Araucanía (IX): Conguillío National Park (sector Los Paraguas), -38.697836°, -71.817216°, from branches of A. araucana, 2 May 2018, F. Balocchi ; ibid, -38.697836°, -71.817216°, from branches of A. araucana (isolates from plant tissue covered in resin), 11 Dec. 2017, (culture CMW 53536 = AR023); — Villarrica National Park sector Puesco, -39.572706°, -71.499235°, branches of A. araucana (isolates from plant tissue covered in resin), 13 Dec. 2017, F. Balocchi . — Biobío (VIII), Ralco Natural Reserve, -37.962620°, -71.327679°, cankers on branches on A. araucana (isolates from plant tissue covered in resin), 27 Dec. 2017, F. Balocchi (culture CMW 53543 = AR224); — Nahuelbuta mountain range, Trongol Alto, -37.564893°, -73.205764°, branches of A. araucana (isolates from plant tissue covered in resin), 21 Dec. 2017, F. Balocchi ; — -37.553434°, -73.188438°, ascomata on branches of A. araucana, 5 Dec. 2019, F. Balocchi .Distinguishing characters: See below.MycoBank: MB 846746.Etymology: Latin, ‘tapulicola’, named after the Mapudungun (indigenous Chilean and Argentinian Mapuche language) word ‘tapül’ meaning the leaves of a tree, and the Latin '-cola' meaning an inhabitant, inhabitant of leaves of a tree.Diagnosis: ITS barcode: OP508126. Alternative identification markers: LSU = OP508138, MCM7 = OP524462, RPB2 = OP524476, SSU = OP508114, TEF1 = OP524488.Type:Chile:Araucanía (IX): Conguillío National Park sector Los Paraguas, -38.697836°, -71.817216°, branches of A. araucana (isolates from plant tissue covered in resin), 11 Dec. 2017, F. Balocchi .Description: Only known in culture. Colony diameters: (mm after 14 d (after 21 d)): MEA at 5 °C microcolonies (3–4), at 10 °C 9–10 (15–17), at 15 °C 15–18 (24–26), at 20 °C 22–27 (33–39), at 25 °C 23–31 (33–47); PDA at 5 °C microcolonies (3–5), 10 °C 9–12 (16–19), 15 °C 17–20 (25–30), 20 °C 21–29 (32–44), at 25 °C 27–34 (39–49), 30 °C 11–19 (15–27), 35 °C no growth; WA at 5 °C microcolonies (3–5), at 10 °C 7–9 (10–16), at 15 °C 13–16 (17–24), at 20 °C 15–23 (22–34), at 25 °C 17–24 (29–36); OA at 20 °C 20–24 (29–37).Colony characters: MEA 25 °C 21 d: Colonies velvety to tomentose, mycelium growth in a rosaceous and/or concentric pattern, umbonate, margins irregular, obverse dark yellow to greyish yellow (4B4–C8) at margins, aerial mycelium yellowish white to orange grey (4A2–5B2) at margins, pale to light yellow (4A3–5) centrally, reverse greyish yellow to blond (4B3–C4) at margins, becoming dark yellow to brownish yellow (4B8–5C7) centrally. MEA 20–25 °C 6 wks or older: slimy, glabrous, rarely velvety, umbonate, mycelium growing in a rosaceous and/or concentric pattern, margins irregular, soluble pigments golden brown to reddish brown (5D7–8E6), obverse orange grey to light brown (6B2–D4), aerial mycelium sometimes present, white to greyish red (3A1–7B4), reverse brownish orange to brown (5C3–F6), sporodochia appear as mucilaginous spore masses on the surface, in concentric halos or with no pattern, light brown to dark brown (6D6–F8). PDA 25 °C 21 d: slimy, glabrous to tomentose, mycelium growing in a rosaceous or stellate pattern, margins irregular, obverse edges sunken in the medium, yellowish grey (2B2–4B2), aerial mycelium white to pale yellow (3A1–3) at margins, becoming olive to dark grey (1F1–3E8) centrally, reverse pale grey to yellowish grey (3B1–3) at margins, becoming dull yellow to olive (3B4–E5) centrally, sometimes darker (3F7).Microscopic characters: Somatic hyphae at colony periphery hyaline, smooth, thin-walled, branched, transversely septate, 1.5–4 µm diam, anastomosing, often developing coils, becoming inflated and melanized with age. Conidiomata most commonly absent, sporodochial with age, composed of interwoven thick-walled melanized hyphae, setae absent. Conidiophores reduced, unbranched, single branched, becoming monoverticillate to richly branched. Conidiogenous cells monophialidic or undifferentiated, then acropleurogenous; denticles sometimes present, up to 4.5 µm in length; terminal conidiogenous loci (10.5–)19–28(–52) µm in length from septa; phialides ampulliform, sometimes constricted at the middle, curved or straight and tapering towards the apex, with distinct collarette, (6–)8–12(–16) × (2–)2.5–3.5(–4) µm. Conidia produced in slimy heads, hyaline and thin-walled when young or on nutrient poor media, thick-walled and/or dematiaceous with age, aseptate, smooth walled, distinct hilum mostly present, on MEA globose to broadly ellipsoidal, rarely ellipsoidal, 3.5–4.5(–6) × 3–4.5 µm (x̅ = 4.28 ± 0.49 × 3.91 ± 0.32), average length/width = 1.09 ± 0.09 (n = 114), on PDA and WA subglobose to ellipsoidal, rarely globose, on PDA (3.5–)4–5(–6) × 3–4(–4.5) (x̅ = 4.66 ± 0.66 × 3.55 ± 0.38), average length/width = 1.32 ± 0.21 (n = 58), on WA (3–)4–5(–7.5) × (3–)3.5–4(–4.5) (x̅ = 4.31 ± 0.93 × 3.62 ± 0.38), average length/width = 1.19 ± 0.19 (n = 50).Habitat /host: A sexual morph of this fungus has not been observed, and is only known from cultures isolated from plant tissues that had resin on them. Strains originate from collection sites in the Andes and Coastal range suggesting that its distribution overlaps that of A. araucana. Its occurrence on other tree species has not been explored and a broader geographical distribution may thus exist.Material examined:Chile:Araucanía (IX): Conguillío National Park sector Los Paraguas, -38.697836°, -71.817216°, branches of A. araucana (isolates from plant tissue covered in resin), 11 Dec. 2017, F. Balocchi . — Villarrica National Park sector Puesco, -39.575582°, -71.493489°, branches of A. araucana (isolates from plant tissue covered in resin), 13 Dec. 2017, F. Balocchi ; — Biobío (VIII), Nahuelbuta mountain range, Trongol Alto, -37.564893°, -73.205764°, branches of A. araucana (isolates from plant tissue covered in resin), 15 Jan. 2019, F. Balocchi .Distinguishing characters: The general morphology of the ascomata produced by R. araucana closely resembles those of R. humboldtensis, and to a lesser extent Cr. blascoi. Ascomata were not observed for R. tapulicola. Comparing ascomata of R. araucana with those reported for R. humboldtensis 92–214(–275) µm vs 80–140 µm), and the mineral pruina covering it was orange to darker red as oppose to yellowish brown. Ascospores of R. araucana were on average slightly larger (4–5.5(–6.5) × (3.5–)4–5.5 µm vs (3–)3.6–4.7(–5.8) × (2.7–)3.3–4.3(–4.6) µm) and asci were thinner (4–6 µm vs 6–9 µm) with commonly shorter pedicels (6–18.5(–32) µm vs 22–43 µm). Cryptocalicium blascoi produces smaller ascomata (150–360 µm vs (556–)766–1070(–1540) µm), generally smaller microscopic features, and is characterized by a greenish mazaedium, contrasting with the reddish brown mazaedium of R. araucana.R. araucana and R. tapulicola resemble each other and could easily be confused. Resinogalea tapulicola grows faster than R. araucana  originating from them was confirmed by sequencing. This difference in results between isolates from R. araucana and R. humboldtensis may be an outcome of different ages and/or preservation status of the specimens at their time of collection and/or processing. The erythrocyte-like shape of ascospores in R. humboldtensis observed by Rikkinen et al.  alongside B. castoris  with Cryptocalicium, the only other genus in the family. However, we consider Bruceomyces (B. castoris) to be morphologically sufficiently distinct from Resinogalea and Cryptocalicium to merit retention as the monotypic genus of Bruceomycetaceae. Furthermore, we emphasise that DNA sequence data will be needed to determine its relationship with other fungi.The results of our analyses using DNA sequence data generated from Cryptocalicium, Prieto et al. . As a consequence, R. humboldtensis has remained taxonomically obscure and its relationship to the specimen we found on A. araucana was initially only suspected based on the hosts and substrate. This situation has been highlighted by numerous authors who note that a large number of old fungal names remain unsequenced , had no reference DNA sequence data available and had not been classified within the ascomycetes (incertae sedis). Morphological and ecological data supports our conclusions that the fungi collected in this study on A. araucana are most closely related to R. humboldtensis, and phylogenetic analyses showed that they reside in the recently described subclass Cryptocaliciomycetidae. The genus Resinogalea has consequently been re-classified in the Cryptocaliciaceae  together with the two new species R. araucana and R. tapulicola described here from A. araucana in Chile.This study combines morphological, ecological, and phylogenetic data to describe two novel Additional file 1. Maximum likelihood tree for the ITS gene region for 28 isolates obtained from branches of Araucaria araucana.


DFT analysis at M06/6-311G  level was accomplished to explore the photonic behavior of PCMD1–D9 compounds. Various kind of analysis like; UV–Vis, density of state (DOS), natural bond orbitals (NBOs), transition density matrix (TDM) and frontier molecular orbitals (FMOs) analyses were accomplished to understand the NLO properties of said chromophores. The configuration change led to considerable charge distribution over highest occupied and lowest unoccupied molecular orbitals with minimum band difference. The energy gap trend for all the entitled compounds was observed as; PCMD8 < PCMD5 = PCMD9 < PCMD6 < PCMD7 < PCMD4 < PCMD3 < PCMD2 < PCMD1 with the least band gap of 2.048 eV in PCMD8 among all the compounds. The UV–Visible spectrum of the entitled chromophores manifested high values of λmax in derivatives contrary to PCMR. Additionally, NBO findings explored effective intramolecular charge transfer and maximum energy of stabilization  for PCMD8 chromophore. The highest linear polarizability (<α>) and dipole moment (µtot) values were exhibited by PCMD5 at 2.712 × 10–22. and 1.995 × 10–17 esu, respectively. PCMD8 push–pull configured molecular entity exhibited highest first hyper-polarizability (βtot) at 4.747 × 10–27 esu and second hyper-polarizability at 6.867 × 10–32 esu. Overall, all the formulated chromophores exhibited significant NLO results contrary to PCMR. Hence, through this structural tailoring via various acceptors, effective NLO materials were obtained for optoelectronic applications.In opto-electronics, non-fullerene (NF) derivatives are regarded as efficient non-linear optical (NLO) materials. The present investigation was based on designing NF naphthalene-based derivatives (PCMD1–D9) with D-π One particularly fascinating aspect of NLO is Second Harmonic Generation (SHG), a process that transforms incoming light waves into waves with double their initial frequency. This phenomenon has garnered extensive attention for its practical applications, particularly in advanced technologies like photovoltaics and optoelectronics2.In the past few decades, non-linear optics (NLO) has emerged as a rapidly expanding field of scientific exploration. It delves into the intricate relationship between light interacts with matter, especially when subjected to external electric fields, this phenomenon referred to as ‘nonlinear optical phenomena’ due to the non-trivial relationship between the response of matter and the strength of the applied electric field3. Each material possesses unique attributes that may make it well-suited for one application while less relevant for others. The performance of materials becomes notably significant when they exhibit a high degree of nonlinearity, demonstrates promising potential for crystal growth, and possesses a high damage threshold, among other qualities. The continuous development of novel materials with exceptional characteristics plays a pivotal role in advancing leading-edge technologies6. The strength of optical parallelism and fast speed will progressively generate optoelectronic systems where more functions could be executed optically. Nevertheless, the technological evolution of photonics dependent on formulating novel compounds with enhanced performance7.When an electric field interacts with dielectric materials, it induces a rearrangement of the spatial distribution of electrons around the nucleus. This distortion leads to the establishment of electric dipoles within the material, resulting from these electron–nucleus distortions. The choice of a suitable crystal for a specific application in nonlinear optics depends on several factors, including the nonlinear phenomenon being employed, the characteristics of the pump laser, and the desired properties of the device8. Due to D–π–A architecture increased conjugation and these are utilized in number of fields causing organic compound having excellent NLO properties9. Conjugated polymers are considered the most comprehensive researched materials for nonlinear optics and among the organics. Having a quality of existence of a delocalized π-electron system making it quick response giving and substantial third-order nonlinear optical characteristics11. They can also be created in many geometries, such as waveguides, films, fibers, and single crystals and they can be utilized by molecular engineering. So, polymers with the π-conjugated structures are considered as top applicants for succeeding optical photonic technologies.Different NLO substances have been attained by many scientific efforts during current years to bring out synthetic resins, molecular dyes, organic and inorganic semiconductor diodes. Low dielectric constants, low cost, high photoelectric coefficients, accessibility, the contribution of π-bonding system and electronic displacement besides facile formulation made the organic compounds should be selected in preferences. Intra-molecular charge transfer (ICT) is an important phenomenon in NLO response. The NLO substances demonstrating “push–pull” system due to donor-π-acceptor framework is the reason for development of ICT13, reduced ground state dipole interaction, chirality15, and organometallic complex18, however physical and chemical methods have been successful in attaining non-centro symmetric organic compounds.Due to electronic delocalization, particularly conjugation present in organic materials, they exhibit distinctive optoelectronic characteristics such as photocatalytic, photovoltaic and photoconductive behavior. High second order nonlinear optical response is present in organic compounds demonstrating intramolecular charge transfer (ICT). Charge spread asymmetrically in the p electron structure in organic materials having electron deficient (acceptor) and rich (donor) motifs and hence exhibit enhanced NLO behavior. The conditions of chemical and mechanical stability, large damage threshold, and high phase matchable NLO coefficient must be present in NLO crystals. Molecular properties based on a few of the above conditions can be fulfilled through molecular formulation. By choosing appropriate acceptor and donor combinations, the molecular ICT can be regulated. Various approaches have been presented to develop organic compounds with non-centro symmetric structures like hydrogen bondingβ values) and high nonlinear optical coefficients. Due to their expanded aromatic rings in structure, they have an extremely conjugated π-electron system. This conjugation gives rise to efficient electron delocalization and charge transfer, which are important for generating nonlinear optical responses. Having highly linear planar structure and having strong molecular packing makes the octacyclic naphthalene-based organic scaffolds (NITT) selection as π-spacer for current study. Yang et al. inserted a terminal end group i.e., IC-2F with NITT core, namely NITTBF to further explore nonlinear properties19. NITT-BF compound showed red shifted absorption along with higher electron mobility because of enhanced intermolecular π–π stacking. Its blend film gives increased exciton dissociation and charge collection properties. NITT-BF delivers higher electron mobility and stronger intermolecular π–π stacking, which account for the higher exciton dissociation and charge collection efficiency in NITT-BF-based device. In addition, NITT-BF has an optical energy gap of 1.25 eV which corresponds to higher nonlinearity.A large and delocalized π-electron system of octacyclic naphthalene-based organic compounds which leads to exceptional hyperpolarizabilities  configured PCMD1–D9 organic chromophores by substituting acceptor motif in the reference PCMR having acceptor–π–acceptor (A–π–A) configuration from parent NITT-BF. The reference compound has been obtained by substituting R1 (3-ethylheptane) and R2 (1-hexyl-4-methylbenzene) with methyl group to reduce computational cost and time of investigation. However, in PCMD9 the one side acceptor is replaced with donor motif which remained constant in the rest of the compounds. But from PCMD1–D9 the end capped acceptor group was substituted by variant acceptor groups to study their molecular nonlinearity and impact on ICT. The analyses were performed at M06/6-311G functional. The TD-DFT and DFT calculations would be executed to interpret the effect of variant acceptors on intramolecular charge transmission, band gap, nonlinear response and absorption spectra. Therefore, various analysis such as FMO, NLO, NBO, UV–Vis, TDM and DOS were performed. We hope these theoretically engineered molecules will lead to more advancements in leading optical technology.20. Complete investigation of the present research were accomplished utilizing M0621/6-311G22 theory level. Transition density matrix (TDM) as well as natural bond orbital (NBO) analyzed charge transition interactions through Multiwfn 3.723 and NBO package 3.124. The energies of frontier molecular orbitals (FMOs) and orbital diagrams were obtained through Avogadro25. The Ultraviolet–Visible (UV–Vis) study was executed utilizing GaussSum26 and the spectral diagram was depicted via Origin 8.027. However, the density of states illustrations were obtained through PyMOlyze28. The dipole moment (µtot)29 and nonlinear optical parameters like linear polarizability (<α>)30 as well as nonlinear hyperpolarizability (βtot and γtot)31 were also computed at the same level M06/6-311G through Eqs.  and PCMD1–D9 having donor-π-acceptor (D–π–A) system) were calculated employing density functional theory (DFT) via Gaussian 09 programσ), chemical potential (μ)32, ionization potential (IP)33, electronegativity (X)34, global hardness (η)35, electron affinity (EA) and global electrophilicity index (ω)36.Equations –11) wer wer11) w19 was utilized. The structural modification of NITT-BF into three parts; 2- malononitrile two acceptor groups on either side and NITT core. The R1 (3-ethylheptane) and R2 (1-hexyl-4-methylbenzene) groups in NITT core were replaced by methyl groups to convert NITT-BF to reference PCMR with A–π–A configuration  energy gap is directly influenced by above mentioned factors. These orbitals determine intra-molecular charge transference efficiency42. However, their energy difference (ΔE) is efficient to know molecular chemical reactivity as well as dynamic stability Less ΔE value corresponds to high polarizability which in turn lead to exceptional NLO behavior43. On the other hand, high ΔE value corresponds to molecular stability and hardness leading to less reactivity and chemical alteration. Table NLO characteristics of molecule’s electronic structure is determine by frontier molecular investigationFrom the above table, the reference organic molecule (PCMR) possesses − 5.941 and − 3.505 eV of HOMO and LUMO energies, which are comparable to the experimental values of − 5.75 and − 4.15 eV, respectively, indicating the accurateness in the selection of functional group for the present analysis. The achieved values of HOMO for all the derivatives (PCMD1–D9) are higher than the reference compound at − 5.658, − 5.637, − 5.649, − 5.657, − 5.697, − 5.682, − 5.659, − 5.696 and − 5.693 eV, respectively. However, the obtained LUMO values for PCMD1–D4 and PCMD7 are higher than the reference i.e., − 3.362, − 3.352, − 3.402, − 3.445 and − 3.459 eV, correspondingly but on the other hand PCMD5, PCMD6, PCMD8 and PCMD9 exhibit less values than PCMR at − 3.623, − 3.525, 3.648 and − 3.619 eV, respectively. Hence, the high HOMO and less LUMO values result in less band gap in PCMD5, PCMD6, PCMD8 and PCMD9 showing high charge transmission probability in these molecules.The highest band gap is exhibited by PCMR at 2.436 eV. This largest energy difference is attributed to the presence of 2-malononitrile as a acceptor motifs with A–π–A configuration. Because moving from PCMR to PCMD1 the one end capped acceptor group is substituted with 9-phenyl-9H-carbazole which significantly reduces the band gap to 2.296 eV in PCMD1.Conversely, the least band gap value of 2.048 eV is present in PCMD8, that might be owing to the presence of high electronegative nitro functional groups at 6 and 7 positioning of 1-(dicyanomethylene)-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalene (DMP) acceptor group. The second lowest energy gap value is exhibited by PCMD5 and PCMD9 at 2.074 eV because of the presence of sulfonic acid groups and cyano groups at 6 and 7 positioning of DMP acceptor moiety rendering high electron withdrawing tendency. However, PCMD6 possess 2.157 eV energy gap resulted from the 6, 7 positioning of trifluoromethyl functional group in DMP. The presence of acetate, chloro and fluoro groups at 6, 7 positioning of DMP acceptor group in PCMD7, PCMD4 and PCMD3 corresponds to band gap of 2.200, 2.212 and 2.247 eV, respectively. 2.285 eV of energy gap is present in PCMD2 in relation to the absence of any electron withdrawing functional groups in DMP. The ascending order of energy difference (HOMO/LUMO) for the derivatives is PCMD8 < PCMD5 = PCMD9 < PCMD6 < PCMD7 < PCMD4 < PCMD3 < PCMD2 < PCMD1. Figure 44. In DOS pictographs, the HOMO signifies valence band showing negative values while the positive values are represented by the conduction band (LUMO)45. The analysis was performed at the same DFT functional for PCMR and PCMD1–D9. DOS indicates the contribution of each fragment of molecule in charge transfer. For determining the density of states (DOS), we split our studied molecules into se98parate fragments. The PCMR1 was divided into two fragments i.e., donor (D) and acceptor (A) while, the derivatives (PCMD1–D9) were divided into three segments i.e., donor, π-spacer, and acceptor. From Fig. The DOS analysis verify the results shown by the FMOs diagrams and explain the electronic distribution in frontier molecular orbitals47. Franck–Condon principle relates spectral highest absorption maxima (λmax) to vertical excitation. The information about oscillator strength (fos), absorption maxima (λmax), excitation energy (E), along with molecular orbital (MO) contribution in transition are given in Table λmax) in ultraviolet visible region for PCMR and PCMD1–D9 is presented in Fig. The ultraviolet visible computation in gaseous form for PCMR and PCMD1–D9 were performed at M06/6-311G to apprehend oscillator strength as well as excitation energy with relation to important electronic transitionsλmax) value for reference (PCMR) i.e., 606.899 nm is lowest among all the compounds with transition energy of 2.043 eV, 2.956 oscillator strength and molecular orbital contribution from HOMO to LUMO of 95%, however, from HOMO-1 to LUMO-1 it is 3%. Hence, it is observed that absorption maxima are significantly impacted by highly electron rich donor and electron withdrawing acceptor end capped groups as well as molecular configuration (reference (A–π–A)λmax value of reference compound resulted from two electron withdrawing acceptor groups on either side of the π-linker. However, the highest λmax value of 701.541 nm is exhibited by PCMD8 among all the chromophores because of high electronegative nitro functional groups present in DMP acceptor group, results in 1.767 eV energy of transition and oscillator strength of 1.299. The molecular orbital contribution exhibited by PCMD8 compound is 96% from HOMO to LUMO and 3% HOMO-1 to LUMO. The second highest λmax of 696.849 nm is present in PCMD5 due to the presence of sulfonic acid groups in DMP with 1.779 eV of transition energy, 1.779 fos and MO contribution of 95 and 3% from HOMO to LUMO and HOMO-1 to LUMO, respectively. However, the third highest λmax of 695.442 nm is shown by PCMD9 because of cyano groups presence in DMP with transition energy and fos values of 1.783 eV and 1.362, respectively. However, the molecular orbital contributions in PCMD9 corresponds to 95% from HOMO to LUMO and 3% from HOMO-1 to LUMO. Owing to the presence of trifluoromethyl groups in PCMD6, the λmax reduces to 663.580 nm with E 1.868 eV, 1.504 fos and MO contributions of 95 and 3% from HOMO to LUMO and HOMO-1 to LUMO, respectively. Substituting trifluoromethyl groups by chloro groups result in λmax of 641.238 nm in PCMD4 with E 1.934 eV, 1.687 fos and MO contributions of 95 and 3% from HOMO to LUMO and HOMO-1 to LUMO, respectively. The overall decreasing trend for PCMD1–D9 as; PCMD8 > PCMD5 > PCMD9 > PCMD6 > PCMD4 >  > PCMD3 > PCMD1 > PCMD2 with chief molecular orbital contribution is from HOMO to LUMO of 94–96%. The compounds with lower Eg showed wider absorption spectrum as the decreasing trend of λmax is almost similar with the increasing trend of energy gap. All fabricated molecules showed bathochromic shift 49. σ → σ*, π → π*, LP → σ* and LP → π* orbital overlapping lead to hyper conjugation. The π-conjugation present in the computed derivatives having D–π–A configuration lead to π → π* transitions, hence result in efficient nonlinear optical substances. Weak σ → σ* transitions are also present because of poor donor and acceptor interactions. Table Here, Molecular orbitals for PCMR and PCMD1–D9 involve in consistent π → π* transitions are π(C18–C19) → π*(C22–C23) corresponds to stabilization energies of 31.57, 32.39, 31.82, 32.24, 32.6, 34.13, 33.46, 32.84, 34.31 and 34.06 kcal/mol, respectively. The lowest π → π* transitions exhibited by PCMR and PCMD1–D9 corresponds to π(C61–C62) → π*(C61–C62), π(C34–O35) → π*(C28–C29), π(C107–C108) → π*(C107–C108), π(C80–C83) → π*(C80–C83), π(C105–C106) → π*(C105–C106), π(C39–N40) → π*(C37–N38), π(C95–C96) → π*(C95–C96), π(C95–C96) → π*(C95–C96), π(C39–N40) → π*(C37–N38) and π(C37–N38) → π*(C39–N40) at 0.65, 4.16, 0.67, 0.51, 0.67, 0.8, 0.67, 0.67, 0.81 and 0.79 kcal/mol stabilization energy, respectively.Likewise, orbitals involved in σ → σ* transitions in PCMR and PCMD1–D9 are σ(C22–H24) → σ*(C18–S20), σ(C22–H24) → σ*(C18–S20), σ(C22–H24) → σ*(C18–S20), σ(C22–H24) → σ*(C18–S20), σ(C22–H24) → σ*(C18–S20), σ(C12–C13) → σ*(C13–C19), σ(C3–C4) → σ*(C4–C5), σ(C22–H24) → σ*(C18–S20), σ(C3–C4) → σ*(C4–C5) and σ(C62–C64) → σ*(C66–C84) at highest energy of stabilization of 10.27, 10.36, 10.42, 10.43, 10.48, 4.92, 4.99, 10.54, 4.99 and 4.99 kcal/mol, respectively. Whereas, the lowest stabilization energy for σ → σ* transitions involve σ(C37–N38) → σ*(C33–C36), σ(C65–C66) → σ*(C6–C15), σ(C62–C64) → σ*(C62–S63), σ(C61–C62) → σ*(C6–C59), σ(C61–C62) → σ*(C6–C59), σ(C62–C64) → σ*(C62–S63), σ(C62–C64) → σ*(C62–S63), σ(C61–C62) → σ*(C6–C59), σ(C37–N38) → σ*(C33–C36) and σ(C61–C62) → σ*(C6–C59) at 0.51 kcal/mol in PCMR and 0.5 kcal/mol in PCMD1–D9 chromophores.LP → π* and LP → σ* transitions are also observed conforming to resonance. LP → π* transitions involve LP(1)(C68) → π*(C64–C66), LP(1)(N82) → π*(C83–C85), LP(1)(N96) → π*(C107–C108), LP(2)(S20) → π*(C12–C13), LP(2)(S20) → π*(C12–C13), LP(1)(C3) → π*(C9–C57), LP(1)(N94) → π*(C95–C96), LP(2)(O120) → π*(C118–O119), LP(3)(O117) → π*(N115–O116) and LP(1)(N94) → π*(C105–C106) orbitals having 72.81, 35.44, 35.42, 29.54, 29.56, 69.77, 35.34, 47.48, 194.76 and 35.4 kcal/mol in PCMR and PCMD1–D9 chromophores, correspondingly. All the same, LP(1)(O35) → σ*(C29–C34), LP(1)(O35) → σ*(C29–C34), LP(1)(O35) → σ*(C29–C34), LP(1)(O35) → σ*(C23–C34), LP(3)(O119) → σ*(S118–O122), LP(1)(O35) → σ*(C29–C34), LP(1)(O116) → σ*(C115–O117), LP(1)(O35) → σ*(C29–C34) and LP(1)(O35) → σ*(C29–C34) at 21.25, 21.3, 20.67, 20.8, 18.57, 29.05, 21.11, 33.38, 21.35 and 21.24 kcal/mol in PCMR and PCMD1–D9 chromophores, correspondingly. Hence, this analysis reveals that their stabilization is significantly influenced by extended hyperconjugation and strong intramolecular charge transfer. These factors underscore the importance of their charge transfer properties, which are pivotal for their nonlinear optical (NLO) characteristics.σ), chemical potential (μ)32, ionization potential (IP)33, electronegativity (X)34, global hardness (η)35, electron affinity (EA) and global electrophilicity index (ω)36 that impart knowledge about molecular stability and its reactivity. Ionization potential (IP) is the principal parameter which defines energy needed to eliminate electron out of MO. From Table IP value is present in PCMD1 i.e. 5.64 eV. The trend for IP value is; PCMD9 > PCMD4 = PCMD7 > PCMD8 > PCMD5 > PCMD3 = PCMR > PCMD2 > PCMD1. Conversely, energy liberates on electronic insertion in valence shell is termed as electron affinity (EA). The highest EA is exhibited by PCMD7 at 3.65 eV while 3.35 eV is the least energy released upon electronic addition in PCMD1. Knowledge about polarization of electronic cloud is collected from global softness (σ) and global hardness (η) values. High polarization of electronic cloud is demonstrated by softer molecules while least is associated with harder compounds. The highest η value is present in PCMD9 at 1.22 eV that reduces to 1.02 eV in PCMD7. The values of global softness (σ) are lesser than their respective global hardness (η) and global electrophilicity index (ω) values. PCMD7 manifests highest softness at 4.88 eV−1 with 0.436 eV−1 being the least softness among all compounds present in PCMD1. Hence all the fabricated chromophores exhibited the higher value of softness which supported the greater charge transference in them than reference chromophore which in result would express good NLO response. The highest value of global electrophilicity index (ω) is possessed by PCMD4 at 10.47 eV. While the lowest of 8.86 eV is present in PCMR. Chemical potential (μ) is inversely related to Electronegativity (X) value. Where, chemical potential describes affinity of electron removal while electronegativity reveals affinity to accept electrons. PCMD9 with highest electronegativity and lowest chemical potential at 4.72 and − 4.72 eV, correspondingly, manifests highest electron transmission in turn possess highest nonlinearity.Global reactivity parameters (GRPs) encompass multiple descriptors i.e. global softness  demonstrate density of transition which is the estimation of excitations involving charge transmission. Whereas, local excitations corresponds to transition density demonstrated by equivalent basis functions (correspondent to same atomic centers)51.Transition density matrices (TDMs) is employed for visualizing and investigating optical nature of each electronic transition in a molecular system during excited state charge dispersion and electron–hole mobilityThe current inquiry of PCMR and PCMD1–D9 has been executed at M06/6-311G via Multiwfn 3.7 . While atomic and molecular nonlinearity subject to extensive nonlinear optical phenomenon is hyperpolarizability . The first order hyperpolarizability (βtot), second order hyperpolarizability (γtot), linear polarizability (<α>) and dipole moment (µtot) values including tensors for PCMR and PCMD1–D9 are presented in Tables NLO is an eminent discipline of current investigations due to its importance in managing primary tasks of optical memory, telecommunications, signal processing, frequency shifting, optical interconnections, optical logic, optical switching and optical modulationµ) is greatly affected by difference of electronegativity that could be categorically the product of charge magnitude and distance among them, where high electronegativity corresponds to large µ55. Besides, molecular µ, polarity is crucial in improving molecular nonlinearity. The µtot characterize average dipole moment, whereas, tensors contributes to µtot along x, y and z-orientations are µx, µy and µz56. The highest µtot values are detected in all the derivatives (PCMD1–D9) in 0.981–1.995 × 10–17 esu range contrary to reference (PCMR) at 0.308 × 10–17esu. The descending order of µtot is; PCMD5 > PCMD8 = PCMD9 > PCMD6 > PCMD7 > PCMD4 > PCMD1 > PCMD3 > PCMD2 > PCMR. The findings indicate major contribution by x-axis in the overall µtot 57, a standard molecule for investigating the NLO properties, these compounds exhibit 0.06, 0.23, 0.20, 0.22, 0.24, 0.40, 0.29, 0.24, and 0.37 times greater µ values. Similarly, when compared to CPTR158, similar analog to our compounds, 0.8, 3.0, 2.6, 3.0, 3.2, 5.4, 3.8, 3.2, and 5.0 the times greater values are found in our fabricated chromophores.The dipole polarizability (ot Table . The PCMα>) values of PCMR and PCMD1–D9 along with polarizability contributing tensors and their values. The <α> value of 2.712 × 10–22 esu is the highest polarizability value among all the chromophores exhibited by PCMD5. However, the least <α> value of 2.310 × 10–22 esu corresponds to PCMD1. The <α> values for the rest of the compounds PCMR, PCMD2-D4, PCMD6-D9 are 2.499, 2.495, 2.506, 2.608, 2.588, 2.670, 2.686 and 2.695 × 10–22 esu, respectively. The investigation extends to the realm of linear polarizability, where a comparison is drawn between our computed compounds (PCMR and PCMD1–D9) and the standard pNA57 and CPTR158. Notably, the linear polarizability values of pNA57 and CPTR158 stand at 1.178 × 10–23 and 1.370 × 10–22 esu, respectively. In contrast, our designed derivatives exhibit intriguing linear polarizability values in relation to pNA and CPTR1. Correspondingly, the comprehensive analysis of their contributing tensors indicates major contribution by αxx towards the overall <α> in all the compounds. The formulated chromophores have shown comparable <α> values with given descending order; PCMD5 > PCMD9 > PCMD8 > PCMD7 > PCMD4 > PCMD6 > PCMD3 > PCMR > PCMD2 > PCMD1.Table βtot) value which increases in strongly push–pull configured molecular systems because of extended conjugation. The nine tensors i.e., βxxx, βxxy, βxyy, βyyy, βxxz, βyyz, βxzz, βyzz, βzzz are used to determine hyperpolarizability values. Table βtot) values are tabulated in Table βtot highest of 4.747 × 10–27 esu is exhibited by PCMD8, whereas the least hyperpolarizability is present in PCMR at 0.099 × 10–27 esu. The same trend for second hyperpolarizability values has been observed, where the highest γtot of 6.867 × 10–32 esu is exhibited by PCMD8, but the least γtot is present in PCMD1 at 3.517 × 10–32 esu. Where the major contribution towards βtot is exhibited by βxxx tensor and γtot in is by γx tensor. Comparative analysis with pNA and CPTR1 our compounds illustrated higher values for β and γtot50. In conclusion, the changing configuration from A-D-A to D–π–A and variant acceptor groups indicates substantial ICT besides bathochromic shift which in turn enhances the optical nonlinearity in all the designed chromophores. The high values of hyperpolarizability and polarizability manifest designed compounds as potential candidate for technologically advanced optical devices.Compound’s nonlinearity is calculated by first hyper-polarizability  with greater red shift (701.541 nm) is examined in PCMD8 than that of other molecules. From all the devised NLO compounds, PCMD8 demonstrated relatively high first hyperpolarizability and second hyperpolarizability of 4.747 × 10–27 esu and 6.867 × 10–32 esu, respectively. Nevertheless, PCMD5 manifested high dipole moment and linear polarizability value of 1.995 × 10–17 esu and 2.712 × 10–22 esu, respectively. So, PCMD8 and PCMD5 possessed high optoelectronic (linear and nonlinear) behavior resulted from the induction of nitro and sulfonic acid groups in the acceptor moiety. However, all the formulated compounds have shown higher nonlinearity on comparison with pNA as a standard molecule from the literature. Subsequently, PCMD8 chromophores is approved to be proficient NLO candidates for technologically advanced nonlinear optical devices.In current report, we devised novel octacyclic naphthalene-based PCMD1–D9 nonlinear organic compounds by substituting one end acceptor moiety in PCMR with donor (9-phenyl-9H-carbazole) in derivatives and altering acceptor group in each successive derivative. Quantum chemical calculation were applied to investigate the NLO behavior of fabricated chromophores. The NBO study revealed a hyper conjugative interaction played significant role in stabilizing the molecule. An efficient charge transference from donor to acceptor through spacer has been studied by FMO findings which were further also supported by DOS and TDM analysis. A lower band gap (2.048 eVSupplementary Information.


N,N′-bidentate ligands [4-(2-aminoethyl)morpholine] and two trans-located acetate molecules. The Cd atom is located on a centre of inversion, whereas the morpholine and four water molecules are adjacent to the acetate moieties. In the crystal, neighboring metal complexes and uncoordinated water molecules are linked via N—H⋯O and O—H⋯O hydrogen-bonding interactions.In the title coordination compound, the Cd atom is octahedrally coordinated by two  2H3O2)2(C6H14N2O)2]·4H2O, was synthesized by mixing 2 moles of 4-(2-aminoethyl)morpholine and 1 mole of cadmium acetate in double-distilled water. The Cd atom is octahedrally coordinated by two N,N′-bidentate ligands [4-(2-aminoethyl)morpholine] and two trans-located acetate molecules. The Cd atom is located on a center of inversion, whereas the 4-(2-aminoethyl)morpholine and four water molecules are adjacent to the acetate molecules. The chair conformation of the morpholine molecules is confirmed. In the crystal, adjacent metal complexes and uncoordinated water molecules are linked via N—H⋯O and O—H⋯O hydrogen-bonding interactions, generating R22(6), R66(16), R66(20) and S11(6) motifs and forming a three-dimensional network. A Hirshfeld surface analysis indicated the contributions of various contacts: H⋯H (71.8%), O⋯H/H⋯O (27.1%), and C⋯H/H⋯C (1.0%).The title coordination compound, [Cd(C The coordination polyhedron around the metal atom may be best described as a distorted octahedron. The four nitrogen atoms of the diamine ligands define the equatorial plane, and two oxygen atoms from the acetate anions coordinate in the trans-axial positions. The coordination of the morpholine ligands creates two five-membered chelate rings  by varying the M—N distances and N—M—N angles. Many articles and reviews have reported that an important factor for metal-ion selection is the chelate ring size, in which five-membered chelate rings promote selectivity for large metal ions with an ionic radius (r+) close to 1.0 Å. Theoretical calculations show that for five-membered N–C–C–N–M chelate rings, the ideal values for the N—M distance and N—M—N angle are 2.5 Å and 69°, respectively  and 2.2788 (15) Å (Cd—N2 and Cd—N2i), are in good agreement with the values reported in the literature  −x + 1, −y, −z + 1] and the cis-angles of the octahedron involving O2 and O2i are close to the ideal value of 90°. The morpholine rings adopt a chair conformation. The acetate group is disordered over two positions of equal occupancy and in both of the crystallographically independent water molecules, one of the protons is equally disordered over two positions. Finally, water atom O5 from the water molecules is disordered over two positions in a 75 (3):25 (3) ratio.The title compound Fig. 1 crystallgs Fig. 2. Upon co3.et al., 1995et al., 2000a-axis direction indicated by cyan dashed lines. In the crystal, the molecules are linked by numerous N—H⋯O and O—H⋯O interactions  are the most significant, contributing 71.8% to the total crystal packing. This major contribution may be due to van der Waals interactions . Fig. 9d shows the C⋯H/H⋯C interactions, which contribute 1.0% to the Hirshfeld surface.A Hirshfeld surface analysis was performed for the complex alone (excluding the water molecules) and the two-dimensional (2D) fingerprint plots were created with 4.et al., 2016catena-[bis-[4-(2-aminoethyl)morpholine]]nickel(II) morpholine]bis(nitrito)nickel(II) bisnickel(II) copper(II) monohydrate bis[4-(2-aminoethyl)morpholine]dicopper(II) morpholine-2κ-N,N′]nickel(II) dichloride morpholine.A search in the Cambridge Structural Database : 3301 , 2887 , 1549 , 1411 , 1342 , 1192 , 960 , 653  and 594 .As shown in the reaction scheme Fig. 10, the tit6.Uiso(H) = 1.2–1.5Ueq(C), while the N—H and O—H protons were located in residual electron-density maps and refined with distance restraints (DFIX and SADI) and with Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O). The acetate group was refined as disordered over two positions (ratio 50:50%) with distance, geometry and ijU restraints . H4 and H6 are disordered over two positions in a 50:50 ratio due to symmetry-related hydrogen bonds. O5 is disordered over two positions in a 75 (3):25 (3) ratio. As both positions have the same distance to H5, H6 and H6′, only one set of the hydrogen atoms was refined for both O5 and O5B.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989023008782/jq2030sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023008782/jq2030Isup4.hklStructure factors: contains datablock(s) I. DOI: 2299387CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, molecules with the same absolute configuration are linked into infinite chains along the b-axis direction by O—H⋯O hydrogen bonds between the hydroxy substituent and the carbonyl O atom of the adjacent molecule.The title compound,which is produced by the oxidation of 1-(4- 5H5)(C21H24NO2)], which is produced by the oxidation of 1-(4-tert-butylphenyl)-2-ethyl-3-ferrocenylpyrrole, crystallizes as a racemic mixture in the centrosymmetric space group P21/n. The central heterocyclic pyrrole ring system subtends dihedral angles of 13.7 (2)° with respect to the attached cyclopentadienyl ring and of 43.6 (7)° with the major component of the disordered phenyl group bound to the N atom. The 4-tert-butylphenyl group, as well as the non-substituted Cp ring are disordered with s.o.f. values of 0.589 (16) and 0.411 (16), respectively. In the crystal, molecules with the same absolute configuration are linked into infinite chains along the b-axis direction by O—H⋯O hydrogen bonds between the hydroxy substituent and the carbonyl O atom of the adjacent molecule.The title compound, [Fe(C Therefore, a new centre of chirality is created at C1, which used to be an sp2 carbon atom in the starting compound. Since no chiral reaction conditions were applied, a racemate of the title compound is produced. The title compound also crystallizes as a racemic mixture in the centrosymmetric space group P21/n. The molecular structure of the S-enantiomer is shown in Fig. 1tert-butylphenyl group, as well as the non-substituted Cp ring, are disordered with s.o.f. values of 0.589 (16) and 0.411 (16). Bond lengths and angles are of expected values with the C2—C3 bond length of 1.336 (5) Å, clearly indicating a double bond. In addition, the N1—C4 bond [1.366 (5) Å] is shortened with respect to the other nitrogen carbon bonds, as is typical for amides.The title compound, 3.b-axis direction by O—H⋯O hydrogen bonds of the C(6) type -one CSD -2-ethyl-3-ferrocenylpyrrole were treated with 5 mol% p-toluene sulfonic acid and were dissolved in 1.0 mL of anhydrous ethanol. The solution was placed in a 10 mL screw-cap vessel closed with parafilm. The process of the oxidation reaction was followed by thin layer chromatography and it could be observed that the reaction was finished after approximately 8 days. The reaction mixture was transferred to a Schlenk tube, the solvent was removed in vacuo and the remaining oily residue was purified by column chromatography  using CH2Cl2 as the eluent. Slow evaporation of the solvent at ambient temperature led to the formation of crystalline material of the title compound . 1H NMR : (ppm) = 0.55 ; 1.31 ; 1.92 ; 2.84 ; 4.17 ; 4.44–4.50 ; 4.72–4.73 ; 6.24 ; 7.37–7.43 ; 7.48–7.52 . 13C NMR : (ppm) = 7.80 (CH3); 26.37 (CH2); 31.32 (CH3); 34.50 (C); 68.03 (CpR); 68.85 (CpR); 70.03 (Cp); 72.96 (CpR); 95.55 (C); 118.48 (=CH); 125.44 (CHPh); 125.86 (CHPh); 135.19 (CPh); 149.21 (CPh); 160.63 (C); 169.10 (C=O). MS (DEI): m/z (%) = 443 (96) [M+]; 427 (76) [M+ − O]; 426 (40) [M+ − OH]; 425 (75) [M+ − H2O]; 398 (22) [M+ − 3CH3]; 360 (98) [M+ − C5H5 − H2O]; 322 (48) [M+ − C5H5Fe]; 305 (58) [M+ − C5H5Fe − OH]; 294 (64) [M+ − C5H5Fe − CO].0.5 mmol (200 mg) of 1-(4-6.O2) was located in a difference-Fourier map and refined freely. All carbon-bound hydrogen atoms were placed in idealized positions and refined using a riding model with isotropic displacement parameters Uiso(H) = 1.2eqU(C) for methylene and aromatic hydrogen atoms and H3 and Uiso(H) = 1.5eqU(C) for methyl groups. The p-tBuC6H4 and Cp groups are disordered over two positions and were found to refine well with only one free variable. The proportion of the two positions is 58.94:41.06%. SIMU, RIGU, SAME, SADI and FLAT instructions were used to restrain the geometry and displacement parameters of the disordered moieties.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989023001858/jq2026sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989023001858/jq2026Isup2.hklStructure factors: contains datablock(s) I. DOI: 961575CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: