In this study, a porous Ni-MOF formulated as {(H2NMe2)[Ni3(μ3OH)(TPT)(TZB)3](H2O)6(DMA)7}n (TZB = 4-(1H-tetrazol-5-yl)benzoate, TPT = 2,4,6-tri(4-pyridyl)-1,3,5-triazine, and DMA = N,N-dimethylacetamide) was prepared and its C2H2 and CO2 adsorption performances were systemically studied both experimentally and computationally. The structural analysis by single crystal X-ray diffraction studies reveals that the prepared Ni-MOF crystallizes in the space group P63mc and features a porous pacs-type network composed of trigonal bipyramidal and octahedral cages. The activated Ni-MOF (Ni-MOF-a) shows a high C2H2 uptake capacity of 157 cm3/g with a moderate C2H2/CO2 IAST selectivity of 3.3 at 298 K and 1 bar. More importantly, Ni-MOF-a shows a low adsorption heat for C2H2 ranging from 24.6 to 27.1 kJ/mol at 298 K with a high separation potential of 2.85 mol/kg. In the computational simulation section, six sets of point charge derived from different approaches (Qeq, Mulliken, PACMOF, mCBAC, Mepoml, PACMAN) and two different force-fields (UFF and Dreiding) were used to calculate the C2H2 and CO2 adsorption isotherms and then compared with the experimental values. Our results reveal that great care should be taken in the selection of point charges and force fields, and the unsuitable combinations might result in an inappropriate C2H2/CO2 selectivity which is against the experimental results.
{"title":"Experimental and computational study on a dual structural cage-based Ni-MOF for efficient C2H2/CO2 separation","authors":"Di-Ming Chen, Han-Dong Qiao, Pei-Feng Wang, Zi-Jun Zhao, Shao-Ming Fang","doi":"10.1016/j.molstruc.2025.142042","DOIUrl":"10.1016/j.molstruc.2025.142042","url":null,"abstract":"<div><div>In this study, a porous Ni-MOF formulated as {(H<sub>2</sub>NMe<sub>2</sub>)[Ni<sub>3</sub>(μ<sub>3<img></sub>OH)(TPT)(TZB)<sub>3</sub>](H<sub>2</sub>O)<sub>6</sub>(DMA)<sub>7</sub>}<sub>n</sub> (TZB = 4-(1H-tetrazol-5-yl)benzoate, TPT = 2,4,6-tri(4-pyridyl)-1,3,5-triazine, and DMA = N,N-dimethylacetamide) was prepared and its C<sub>2</sub>H<sub>2</sub> and CO<sub>2</sub> adsorption performances were systemically studied both experimentally and computationally. The structural analysis by single crystal X-ray diffraction studies reveals that the prepared Ni-MOF crystallizes in the space group P6<sub>3</sub>mc and features a porous <strong><em>pacs</em></strong>-type network composed of trigonal bipyramidal and octahedral cages. The activated Ni-MOF (Ni-MOF-a) shows a high C<sub>2</sub>H<sub>2</sub> uptake capacity of 157 cm<sup>3</sup>/g with a moderate C<sub>2</sub>H<sub>2</sub>/CO<sub>2</sub> IAST selectivity of 3.3 at 298 K and 1 bar. More importantly, Ni-MOF-a shows a low adsorption heat for C<sub>2</sub>H<sub>2</sub> ranging from 24.6 to 27.1 kJ/mol at 298 K with a high separation potential of 2.85 mol/kg. In the computational simulation section, six sets of point charge derived from different approaches (Qeq, Mulliken, PACMOF, mCBAC, Mepoml, PACMAN) and two different force-fields (UFF and Dreiding) were used to calculate the C<sub>2</sub>H<sub>2</sub> and CO<sub>2</sub> adsorption isotherms and then compared with the experimental values. Our results reveal that great care should be taken in the selection of point charges and force fields, and the unsuitable combinations might result in an inappropriate C<sub>2</sub>H<sub>2</sub>/CO<sub>2</sub> selectivity which is against the experimental results.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 142042"},"PeriodicalIF":4.0,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143611469","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The EGFR inhibition treatment option, discovered due to in-depth research into the existence of a wide variety of cancer diseases and their treatment, has opened a new path in drug design and development. This study designed and synthesized 10 new cyclic secondary amine derivatives containing dithiocarbamate as EGFR inhibitors for cancer treatment. Moreover, it is derivatized with benzoxazinone or benzothiazonone rings. The structures of the newly synthesized compounds were elucidated by 1H NMR, 13C NMR, and HRMS spectroscopic methods. MTT analyses were performed to determine the antiproliferative activity of all synthesized compounds (2a-j). All synthesized compounds and Doxorubicin used as a reference drug, were tested against A549 and NIH3T3 cell lines. Compounds 2f and 2g, which gave the best results against the cell lines, were compared with erlotinib, an EGFR inhibitor, for EGFR tyrosine kinase inhibition. The IC50 value of the compound 2f with the best result was found to be 0.079 ± 0.002 µM, while the IC50 value of the reference drug Erlotinib was found to be 0.003 ± 0.001 µM. As a result of molecular docking studies, it was observed that compounds 2f and 2g had the best poses on the active site of EGFR (PDB ID: 4HJO) and interacted with amino acids important for activity. After in vitro and in silico studies evaluations of the designed and synthesized compounds, it was revealed that compounds 2f and 2g were promising compounds in future advanced EGFR inhibition research studies. Among the benzothiazinone and benzoxazinone derivatives carrying the same groups, benzothiazinone derivatives were found to have higher EGFR inhibitory effects.
{"title":"Design, synthesis, and antiproliferative activity evaluation of novel cyclic secondary amine containing dithiocarbamate derivatives as potent EGFR inhibitors","authors":"Harun Uslu , Derya Osmaniye , Elif Öncü , Merve Güven , Yusuf Özkay , Zafer Asım Kaplancikli","doi":"10.1016/j.molstruc.2025.142036","DOIUrl":"10.1016/j.molstruc.2025.142036","url":null,"abstract":"<div><div>The EGFR inhibition treatment option, discovered due to in-depth research into the existence of a wide variety of cancer diseases and their treatment, has opened a new path in drug design and development. This study designed and synthesized 10 new cyclic secondary amine derivatives containing dithiocarbamate as EGFR inhibitors for cancer treatment. Moreover, it is derivatized with benzoxazinone or benzothiazonone rings. The structures of the newly synthesized compounds were elucidated by <sup>1</sup>H NMR, <sup>13</sup>C NMR, and HRMS spectroscopic methods. MTT analyses were performed to determine the antiproliferative activity of all synthesized compounds (<strong>2a</strong>-<strong>j</strong>). All synthesized compounds and Doxorubicin used as a reference drug, were tested against A549 and NIH3T3 cell lines. Compounds <strong>2f</strong> and <strong>2g</strong>, which gave the best results against the cell lines, were compared with erlotinib, an EGFR inhibitor, for EGFR tyrosine kinase inhibition. The IC<sub>50</sub> value of the compound <strong>2f</strong> with the best result was found to be 0.079 ± 0.002 µM, while the IC<sub>50</sub> value of the reference drug Erlotinib was found to be 0.003 ± 0.001 µM. As a result of molecular docking studies, it was observed that compounds <strong>2f</strong> and <strong>2g</strong> had the best poses on the active site of EGFR (PDB ID: 4HJO) and interacted with amino acids important for activity. After <em>in vitro</em> and <em>in silico</em> studies evaluations of the designed and synthesized compounds, it was revealed that compounds <strong>2f</strong> and <strong>2g</strong> were promising compounds in future advanced EGFR inhibition research studies. Among the benzothiazinone and benzoxazinone derivatives carrying the same groups, benzothiazinone derivatives were found to have higher EGFR inhibitory effects.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 142036"},"PeriodicalIF":4.0,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-11DOI: 10.1016/j.molstruc.2025.142039
Zhichao Xu , Xin Huang , Liyan Zhang , Duojun Cao , Dongdong Liu , Guozan Yuan
Metal complexes, with their well-defined molecular structures and design flexibility, offer an ideal platform for developing CO2 reduction photocatalysts. While ligand modification is an effective strategy to enhance catalytic performance, it also presents several challenges. In this work, two 8-hydroxyquinoline-based organic ligands bearing different substituents were initially synthesized. Two ligands were subsequently employed in reactions with Fe(III) ion, respectively, generating two distinct molecular complexes, designated 1-Fe and 2-Fe. The binuclear structures of two complexes were unambiguously elucidated by single-crystal X-ray diffraction (SCXRD), and ESI-MS spectra. Under visible-light irradiation, both complexes demonstrated photocatalytic activity for CO2 reduction to CO in aqueous solution. Notably, complex 1-Fe exhibited a marked improvement in both activity (TONCO = 3106) and selectivity (SelCO = 81 %) compared to the 2-Fe catalyst (TONCO = 1641, SelCO = 61 %). Furthermore, the superior CO2 photoreduction performance of 1-Fe was comprehensively investigated by electrochemical tests, and photoinduced electron transfer dynamics, as well as in-situ attenuated total reflection infrared fourier transform spectroscopy (ATR-IFTS).
{"title":"Enhancing photocatalytic CO2-to-CO conversion by iron complexes through 8-hydroxyquinoline ligand regulation","authors":"Zhichao Xu , Xin Huang , Liyan Zhang , Duojun Cao , Dongdong Liu , Guozan Yuan","doi":"10.1016/j.molstruc.2025.142039","DOIUrl":"10.1016/j.molstruc.2025.142039","url":null,"abstract":"<div><div>Metal complexes, with their well-defined molecular structures and design flexibility, offer an ideal platform for developing CO<sub>2</sub> reduction photocatalysts. While ligand modification is an effective strategy to enhance catalytic performance, it also presents several challenges. In this work, two 8-hydroxyquinoline-based organic ligands bearing different substituents were initially synthesized. Two ligands were subsequently employed in reactions with Fe(III) ion, respectively, generating two distinct molecular complexes, designated <strong>1-Fe</strong> and <strong>2-Fe</strong>. The binuclear structures of two complexes were unambiguously elucidated by single-crystal X-ray diffraction (SCXRD), and ESI-MS spectra. Under visible-light irradiation, both complexes demonstrated photocatalytic activity for CO<sub>2</sub> reduction to CO in aqueous solution. Notably, complex <strong>1-Fe</strong> exhibited a marked improvement in both activity (TON<sub>CO</sub> = 3106) and selectivity (Sel<sub>CO</sub> = 81 %) compared to the <strong>2-Fe</strong> catalyst (TON<sub>CO</sub> = 1641, Sel<sub>CO</sub> = 61 %). Furthermore, the superior CO<sub>2</sub> photoreduction performance of <strong>1-Fe</strong> was comprehensively investigated by electrochemical tests, and photoinduced electron transfer dynamics, as well as <em>in-situ</em> attenuated total reflection infrared fourier transform spectroscopy (ATR-IFTS).</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 142039"},"PeriodicalIF":4.0,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619341","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-10DOI: 10.1016/j.molstruc.2025.141989
Minghao Lin , Gangan Wang , Junqi Li , Chaoyi Chen , Yuanpei Lan
Calcined kaolinite (CK)/TiO2 composites were synthesized through hydrolysis precipitation of titanyl sulfate (TiOSO4) and calcination. Under optimized hydrolysis conditions (pH 2.5, duration 2.0 h, temperature 90 °C, and mass ratio (TiO2/CK) = 1.0), a precipitation efficiency of 81.4 % was achieved. The phase composition remained consistent under varying hydrolysis conditions after significant TiO2 formation. Furthermore, the oil absorption (mass ratio = 2.0) and hiding power (mass ratio = 1.4) of the composites were determined to be 38.8 g/100 g and 88.4 %, respectively. The composites exhibited high good chemical stability as a pigment, maintaining resistance to strong acid erosion, with only 4.0 % dissolution observed after a 15-day immersion in a pH 2.0 solution. H2TiO3 underwent the dehydration and desulfurization more rapidly in an oxygen-rich environment, and anatase formation was well-developed at a calcination temperature of 750 °C for 1 h. Further analysis revealed that phase transition process of TiO2 was influenced by TiO2 content, disordered structure of CK and calcination conditions. TiO2 particles formed single- or multi-layered chemical coatings on the active CK surface, although the presence of exposed mullite impeded coating formation. This study successfully developed cost-effective CK/TiO2 composites with favorable pigment properties, providing a certain reference for CK selection. The composites have potential applications in coatings, pigments and related fields.
{"title":"Preparation of Calcined kaolinite/TiO2 composites by titanyl sulfate (TiOSO4) hydrolysis precipitation","authors":"Minghao Lin , Gangan Wang , Junqi Li , Chaoyi Chen , Yuanpei Lan","doi":"10.1016/j.molstruc.2025.141989","DOIUrl":"10.1016/j.molstruc.2025.141989","url":null,"abstract":"<div><div>Calcined kaolinite (CK)/TiO<sub>2</sub> composites were synthesized through hydrolysis precipitation of titanyl sulfate (TiOSO<sub>4</sub>) and calcination. Under optimized hydrolysis conditions (pH 2.5, duration 2.0 h, temperature 90 °C, and mass ratio (TiO<sub>2</sub>/CK) = 1.0), a precipitation efficiency of 81.4 % was achieved. The phase composition remained consistent under varying hydrolysis conditions after significant TiO<sub>2</sub> formation. Furthermore, the oil absorption (mass ratio = 2.0) and hiding power (mass ratio = 1.4) of the composites were determined to be 38.8 g/100 g and 88.4 %, respectively. The composites exhibited high good chemical stability as a pigment, maintaining resistance to strong acid erosion, with only 4.0 % dissolution observed after a 15-day immersion in a pH 2.0 solution. H<sub>2</sub>TiO<sub>3</sub> underwent the dehydration and desulfurization more rapidly in an oxygen-rich environment, and anatase formation was well-developed at a calcination temperature of 750 °C for 1 h. Further analysis revealed that phase transition process of TiO<sub>2</sub> was influenced by TiO<sub>2</sub> content, disordered structure of CK and calcination conditions. TiO<sub>2</sub> particles formed single- or multi-layered chemical coatings on the active CK surface, although the presence of exposed mullite impeded coating formation. This study successfully developed cost-effective CK/TiO<sub>2</sub> composites with favorable pigment properties, providing a certain reference for CK selection. The composites have potential applications in coatings, pigments and related fields.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 141989"},"PeriodicalIF":4.0,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143593761","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A Schiff base, L (6,6′-((1E)-((disulfanediylbis(2,1-phenylene))bis(azanylylidene))bis(methanylylidene))bis(2-methoxyphenol)), was synthesised via a heatless condensation of 2,2 diaminodiphenyl disulfide and o-vanillin. Its structure was confirmed by single crystal X-ray diffraction. Hirshfeld surface analysis highlighted significant intermolecular interactions among ligand molecules. Three Cu(II) complexes, [CuL(OAc)].OAc, [Cu2L(SO4)].H2O, and [Cu2L(NO3)], were synthesised using ultrasonic irradiation. Characterization of L and the metal complexes included elemental analysis, molar conductance, magnetic moments, FTIR, UV–Vis, EPR, mass spectrometry, and Job's Analysis. The molar conductance values of the complexes [CuL(OAc)].OAc, [Cu2L(SO4)], [Cu2L(NO3)].NO3 were respectively 25, 14 and 78 Ω−1 cm−1 mol−1, suggesting that [CuL(OAc)].OAc and [Cu2L(NO3)].NO3 are electrolytic in nature. The complexes exhibited paramagnetic behavior with a d⁹ electronic configuration, as indicated by their magnetic moment values ranging from 1.74 to 1.77 BM. Computational methods supported structural and stability assessments. Stability order was [CuL(OAc)].OAc < [Cu2L(NO3)].NO3 < [Cu2L(SO4)].H2O < L. DNA binding studies using UV–vis spectroscopy, fluorescence assays, and viscosity measurements confirmed intercalative binding, with intrinsic binding constants (Kb) and quenching constants (Ksv) values of 105 M−1. [Cu2L(NO3)].NO3 showed the highest antibacterial activity against gram-positive bacteria with a zone of inhibition up to 13 mm and the lowest MIC values. The antioxidant and anti-inflammatory properties of the complex were assessed through DPPH and egg albumin denaturation assays. The complex [Cu2L(NO3)].NO3 exhibited promising activity, with IC₅₀ values of 11.79 µg/mL for the antioxidant assay and 96.13 µg/mL for the anti-inflammatory study. Molecular docking studies on CT-DNA revealed strong binding affinities, with [Cu2L(NO3)].NO3 exhibiting the lowest binding energy of -8.36 kcal/mol. The synthesised compounds demonstrate significant potential for applications in medicinal chemistry and biological studies.
{"title":"Investigation of disulfide-based Schiff base and its mono and binuclear Cu(II) complexes: Green synthesis, crystal structure analysis, Hirshfeld surface analysis, in-vitro biological assessment, DNA binding studies, and computational studies","authors":"Thangjam Sanjurani, Sneha Paul, Diganta Kumar Bharali, Pranjit Barman","doi":"10.1016/j.molstruc.2025.141997","DOIUrl":"10.1016/j.molstruc.2025.141997","url":null,"abstract":"<div><div>A Schiff base, <strong>L</strong> (6,6′-((1E)-((disulfanediylbis(2,1-phenylene))bis(azanylylidene))bis(methanylylidene))bis(2-methoxyphenol)), was synthesised via a heatless condensation of 2,2 diaminodiphenyl disulfide and o-vanillin. Its structure was confirmed by single crystal X-ray diffraction. Hirshfeld surface analysis highlighted significant intermolecular interactions among ligand molecules. Three Cu(II) complexes, <strong>[CuL(OAc)].OAc, [Cu<sub>2</sub>L(SO<sub>4</sub>)].H<sub>2</sub>O</strong>, and <strong>[Cu<sub>2</sub>L(NO<sub>3</sub>)]</strong>, were synthesised using ultrasonic irradiation. Characterization of <strong>L</strong> and the metal complexes included elemental analysis, molar conductance, magnetic moments, FTIR, UV–Vis, EPR, mass spectrometry, and Job's Analysis. The molar conductance values of the complexes <strong>[CuL(OAc)].OAc, [Cu<sub>2</sub>L(SO<sub>4</sub>)], [Cu<sub>2</sub>L(NO<sub>3</sub>)].NO<sub>3</sub></strong> were respectively 25, 14 and 78 Ω<sup>−1</sup> cm<sup>−1</sup> mol<sup>−1</sup>, suggesting that <strong>[CuL(OAc)].OAc</strong> and <strong>[Cu<sub>2</sub>L(NO<sub>3</sub>)].NO<sub>3</sub></strong> are electrolytic in nature. The complexes exhibited paramagnetic behavior with a d⁹ electronic configuration, as indicated by their magnetic moment values ranging from 1.74 to 1.77 BM. Computational methods supported structural and stability assessments. Stability order was <strong>[CuL(OAc)].OAc</strong> < <strong>[Cu<sub>2</sub>L(NO<sub>3</sub>)].NO<sub>3</sub></strong> < <strong>[Cu<sub>2</sub>L(SO<sub>4</sub>)].H<sub>2</sub>O</strong> < <strong>L</strong>. DNA binding studies using UV–vis spectroscopy, fluorescence assays, and viscosity measurements confirmed intercalative binding, with intrinsic binding constants (K<sub>b</sub>) and quenching constants (K<sub>sv</sub>) values of 10<sup>5</sup> M<sup>−1</sup>. <strong>[Cu<sub>2</sub>L(NO<sub>3</sub>)].NO<sub>3</sub></strong> showed the highest antibacterial activity against gram-positive bacteria with a zone of inhibition up to 13 mm and the lowest MIC values. The antioxidant and anti-inflammatory properties of the complex were assessed through DPPH and egg albumin denaturation assays. The complex <strong>[Cu<sub>2</sub>L(NO<sub>3</sub>)].NO<sub>3</sub></strong> exhibited promising activity, with IC₅₀ values of <strong>11.79 µg/mL</strong> for the antioxidant assay and <strong>96.13 µg/mL</strong> for the anti-inflammatory study. Molecular docking studies on CT-DNA revealed strong binding affinities, with <strong>[Cu<sub>2</sub>L(NO<sub>3</sub>)].NO<sub>3</sub></strong> exhibiting the lowest binding energy of -8.36 kcal/mol. The synthesised compounds demonstrate significant potential for applications in medicinal chemistry and biological studies.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 141997"},"PeriodicalIF":4.0,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-10DOI: 10.1016/j.molstruc.2025.142031
Yali Cui , Ziqin Song , Xiaomeng Guo , Yunbo Chu , Lingxin Yi , Yuanqiang Hao
A novel coumarin-based ratiometric fluorescent probe, NPCN, was developed for the highly selective and sensitive detection of cysteine (Cys). The dual reaction site design of the probe enables effective differentiation of Cys from other biothiols, such as homocysteine (Hcy) and glutathione (GSH). Upon reacting with Cys, the probe exhibited a significant blue shift in its emission spectrum, allowing for ratiometric detection at 472 nm and 590 nm with a good linear relationship (0–100 μM) and a low detection limit (0.18 μM). Further investigations demonstrated excellent selectivity and biocompatibility of NPCN for Cys detection. In cell imaging experiments, NPCN effectively visualized both endogenous and exogenous Cys, showing outstanding cellular permeability and low cytotoxicity. Moreover, using a zebrafish model, NPCN successfully achieved in vivo imaging of Cys, exhibiting a concentration-dependent fluorescence response. Overall, NPCN represents a promising tool for real-time imaging and analysis of Cys in biological samples, providing critical technological support for disease diagnosis and therapeutic research.
{"title":"A highly selective ratiometric fluorescent probe for cysteine detection","authors":"Yali Cui , Ziqin Song , Xiaomeng Guo , Yunbo Chu , Lingxin Yi , Yuanqiang Hao","doi":"10.1016/j.molstruc.2025.142031","DOIUrl":"10.1016/j.molstruc.2025.142031","url":null,"abstract":"<div><div>A novel coumarin-based ratiometric fluorescent probe, <strong>NPCN</strong>, was developed for the highly selective and sensitive detection of cysteine (Cys). The dual reaction site design of the probe enables effective differentiation of Cys from other biothiols, such as homocysteine (Hcy) and glutathione (GSH). Upon reacting with Cys, the probe exhibited a significant blue shift in its emission spectrum, allowing for ratiometric detection at 472 nm and 590 nm with a good linear relationship (0–100 μM) and a low detection limit (0.18 μM). Further investigations demonstrated excellent selectivity and biocompatibility of <strong>NPCN</strong> for Cys detection. In cell imaging experiments, <strong>NPCN</strong> effectively visualized both endogenous and exogenous Cys, showing outstanding cellular permeability and low cytotoxicity. Moreover, using a zebrafish model, <strong>NPCN</strong> successfully achieved in vivo imaging of Cys, exhibiting a concentration-dependent fluorescence response. Overall, <strong>NPCN</strong> represents a promising tool for real-time imaging and analysis of Cys in biological samples, providing critical technological support for disease diagnosis and therapeutic research.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 142031"},"PeriodicalIF":4.0,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143601053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-10DOI: 10.1016/j.molstruc.2025.142003
Eugen Dukhopelnikov , Ekaterina Bereznyak , Volodymyr Ivanov , Natalia Gladkovskaya , Iuliia Blyzniuk , Anna Khrebtova
The possible existence and interactions of two tautomeric forms of proflavine dihydrochloride with polyethylene glycol (PEG) have been investigated using a combination of quantum chemistry calculations at the DFT B3LYP/6–31+G(d,p) level and experimental (IR spectroscopy) approach. The calculations have shown the energetic preference for the proflavine protonation at the nitrogen atom in the central ring (N+H). However, experimental investigations have not provided evidence supporting the existence of such a form in the condensed phase. At the same time, a less energetically favorable form of proflavine protonated at the peripheral amino group N+H3 is clearly detected in the IR spectra. Calculations have demonstrated that the binding with polyethylene glycol is energetically favorable for both tautomeric forms of proflavine. The highest total energetic advantage occurred when the protonated amino group of proflavine (N+H3) formed two hydrogen bonds with PEG. Experimental findings indicate that at a high relative content of polyethylene glycol in the mixture with proflavine, not only N+H3 groups but also NH2 groups of drug bind to the polymer. These complexes can form either within a single PEG molecule or between different polymer molecules.
{"title":"IR spectra of proflavine in complex with polyethylene glycol. Quantum chemistry investigation vs experimental data","authors":"Eugen Dukhopelnikov , Ekaterina Bereznyak , Volodymyr Ivanov , Natalia Gladkovskaya , Iuliia Blyzniuk , Anna Khrebtova","doi":"10.1016/j.molstruc.2025.142003","DOIUrl":"10.1016/j.molstruc.2025.142003","url":null,"abstract":"<div><div>The possible existence and interactions of two tautomeric forms of proflavine dihydrochloride with polyethylene glycol (PEG) have been investigated using a combination of quantum chemistry calculations at the DFT B3LYP/6–31+G(d,p) level and experimental (IR spectroscopy) approach. The calculations have shown the energetic preference for the proflavine protonation at the nitrogen atom in the central ring (N<sup>+</sup><em>H</em>). However, experimental investigations have not provided evidence supporting the existence of such a form in the condensed phase. At the same time, a less energetically favorable form of proflavine protonated at the peripheral amino group N<sup>+</sup>H<sub>3</sub> is clearly detected in the IR spectra. Calculations have demonstrated that the binding with polyethylene glycol is energetically favorable for both tautomeric forms of proflavine. The highest total energetic advantage occurred when the protonated amino group of proflavine (N<sup>+</sup>H<sub>3</sub>) formed two hydrogen bonds with PEG. Experimental findings indicate that at a high relative content of polyethylene glycol in the mixture with proflavine, not only N<sup>+</sup>H<sub>3</sub> groups but also NH<sub>2</sub> groups of drug bind to the polymer. These complexes can form either within a single PEG molecule or between different polymer molecules.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 142003"},"PeriodicalIF":4.0,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-10DOI: 10.1016/j.molstruc.2025.142014
K.P. Safna Hussan , G. Govindaraj , Natália T. Correia , Naoki Shinyashiki , M. Shahin Thayyil , Thekkekara D Babu
Background
Cancer remains a leading cause of mortality worldwide despite advancements in oncology. Chemotherapy is essential for treating aggressive cancers, but its efficacy is limited by systemic toxicity, off-target effects, and drug resistance. Poor aqueous solubility and low oral bioavailability of many anticancer drugs necessitate high doses or intravenous administration, increasing adverse effects. Erlotinib-HCl (ERL), a tyrosine kinase inhibitor, has poor aqueous solubility and low oral bioavailability, limiting its clinical use. Strategies like salt formation, prodrugs, nano-formulations, and cyclodextrin complexation improve solubility. Among them, amorphous solid dispersion (ASD) is a highly effective approach.
Aim
The study aimed to characterise the ASD formulations of ERL using polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), and their combinations.
Experimental section
Physical characterization of ASD was analyzed by optical microscopy, powder X-ray diffraction (PXRD), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), molecular dynamics (MD) simulations, broadband dielectric spectroscopy (BDS), and temperature-modulated differential scanning calorimetry (TMDSC).
Results and discussion
Microscopic images and PXRD pattern revealed the amorphization of ERL. DSC and TMDSC indicated no residual crystallinity, with glass transitions at 252 K, 373 K, and 272 K for ERL+PEG, ERL+PVP, and ERL+PEG+PVP, respectively. MD simulations showed PEG and PVP influenced the spatial distribution and dynamics of ERL, enhancing miscibility. ASDs modify intermolecular forces and cohesive energy density. ERL+PEG exhibits α (portions within the semi-crystalline phase of PEG, 331 K) and β (glassy state) relaxations, while ERL+PVP shows a single α relaxation linked to segmental motions in the entire amorphous phase of PVP (373 K). ERL+PEG+PVP displays two α relaxations (PVP and PEG) and one β relaxation. Fragility indices are 148 (ERL+PEG), 62.1 (ERL+PVP), and 45.5 (ERL+PEG+PVP), indicating improved stability.
Conclusion
The study characterized amorphous solid dispersions of ERL with enhanced amorphization, miscibility and molecular interactions. The reduced fragility index in ERL+PEG+PVP suggests improved stability, making it a promising formulation for enhanced drug solubility.
{"title":"Molecular dynamics and interactions in amorphous solid dispersion of Erlotinib HCl for improved cancer therapy","authors":"K.P. Safna Hussan , G. Govindaraj , Natália T. Correia , Naoki Shinyashiki , M. Shahin Thayyil , Thekkekara D Babu","doi":"10.1016/j.molstruc.2025.142014","DOIUrl":"10.1016/j.molstruc.2025.142014","url":null,"abstract":"<div><h3>Background</h3><div>Cancer remains a leading cause of mortality worldwide despite advancements in oncology. Chemotherapy is essential for treating aggressive cancers, but its efficacy is limited by systemic toxicity, off-target effects, and drug resistance. Poor aqueous solubility and low oral bioavailability of many anticancer drugs necessitate high doses or intravenous administration, increasing adverse effects. Erlotinib-HCl (ERL), a tyrosine kinase inhibitor, has poor aqueous solubility and low oral bioavailability, limiting its clinical use. Strategies like salt formation, prodrugs, nano-formulations, and cyclodextrin complexation improve solubility. Among them, amorphous solid dispersion (ASD) is a highly effective approach.</div></div><div><h3>Aim</h3><div>The study aimed to characterise the ASD formulations of ERL using polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), and their combinations.</div></div><div><h3>Experimental section</h3><div>Physical characterization of ASD was analyzed by optical microscopy, powder X-ray diffraction (PXRD), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), molecular dynamics (MD) simulations, broadband dielectric spectroscopy (BDS), and temperature-modulated differential scanning calorimetry (TMDSC).</div></div><div><h3>Results and discussion</h3><div>Microscopic images and PXRD pattern revealed the amorphization of ERL. DSC and TMDSC indicated no residual crystallinity, with glass transitions at 252 K, 373 K, and 272 K for ERL+PEG, ERL+PVP, and ERL+PEG+PVP, respectively. MD simulations showed PEG and PVP influenced the spatial distribution and dynamics of ERL, enhancing miscibility. ASDs modify intermolecular forces and cohesive energy density. ERL+PEG exhibits α (portions within the semi-crystalline phase of PEG, 331 K) and <em>β</em> (glassy state) relaxations, while ERL+PVP shows a single α relaxation linked to segmental motions in the entire amorphous phase of PVP (373 K). ERL+PEG+PVP displays two α relaxations (PVP and PEG) and one <em>β</em> relaxation. Fragility indices are 148 (ERL+PEG), 62.1 (ERL+PVP), and 45.5 (ERL+PEG+PVP), indicating improved stability.</div></div><div><h3>Conclusion</h3><div>The study characterized amorphous solid dispersions of ERL with enhanced amorphization, miscibility and molecular interactions. The reduced fragility index in ERL+PEG+PVP suggests improved stability, making it a promising formulation for enhanced drug solubility.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1336 ","pages":"Article 142014"},"PeriodicalIF":4.0,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143631766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-10DOI: 10.1016/j.molstruc.2025.142022
Melda Bolat , Dursun Ali Köse
In recent years, with the increasing popularity of complementary and alternative therapies worldwide, interest in dietary supplements has also begun to rise. It is known that boron is effective in energy, mineral, hormone, bone, and skeletal metabolism. It is accepted that it has a regulatory function in maintaining various other biological processes. The chemical state of boron is very important in nutrition. In plants, boron is found in the form of sugar esters. Boron sugar esters are the best chemical form for assimilation by cells. It is necessary to emphasize and enhance the positive effects of boron on cells by obtaining complex structures with -OBO- ester bonds. It has been observed that the boron compounds in these foods are "boron ester derivatives". There are specific biochemical, preclinical, and clinical studies investigating the dietary intake of boron ester derivatives. However, studies on the synthesis and structural characterization of boron esters are more limited. Within the scope of this study, the synthesis, structural characterization, and various application studies of borate compounds examined by our group and different researchers have been compiled. By researching the synthesis and structural characterization of borate esters, we believe we will contribute to the literature on these compounds, which are known to be promising for a healthy life.
{"title":"Boron Ester compounds as daily food supplements","authors":"Melda Bolat , Dursun Ali Köse","doi":"10.1016/j.molstruc.2025.142022","DOIUrl":"10.1016/j.molstruc.2025.142022","url":null,"abstract":"<div><div>In recent years, with the increasing popularity of complementary and alternative therapies worldwide, interest in dietary supplements has also begun to rise. It is known that boron is effective in energy, mineral, hormone, bone, and skeletal metabolism. It is accepted that it has a regulatory function in maintaining various other biological processes. The chemical state of boron is very important in nutrition. In plants, boron is found in the form of sugar esters. Boron sugar esters are the best chemical form for assimilation by cells. It is necessary to emphasize and enhance the positive effects of boron on cells by obtaining complex structures with -O<img>B<img>O- ester bonds. It has been observed that the boron compounds in these foods are \"boron ester derivatives\". There are specific biochemical, preclinical, and clinical studies investigating the dietary intake of boron ester derivatives. However, studies on the synthesis and structural characterization of boron esters are more limited. Within the scope of this study, the synthesis, structural characterization, and various application studies of borate compounds examined by our group and different researchers have been compiled. By researching the synthesis and structural characterization of borate esters, we believe we will contribute to the literature on these compounds, which are known to be promising for a healthy life.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1335 ","pages":"Article 142022"},"PeriodicalIF":4.0,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143601052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-10DOI: 10.1016/j.molstruc.2025.142026
Vipin Kumar, Prabhakar Chetti
Graphene nanocomposites have surfaced as a promising material for charge transfer-based dye-sensitized solar cell (DSSC) enhancement. Graphene nanocomposites coated with different metal oxides find extensive use in energy devices, including batteries, fuel cells, solar cells, sensors, electro-catalysis, and photo-catalysis. Nevertheless, little research has been done on these composite's potential use in DSSC applications. In this work, we investigated a multi-junction system consisting of D-A’-π-A sensitized (TiO2)16 nanocomposite at graphene oxide (dye@TiO2@GO) and the influence of numerous π-bridges on the push-pull dye system's optical and photovoltaic properties in light-harvesting device. The highest absorption wavelength is observed for TH1 (623 nm) which further increases in adsorbed systems. By changing the spacer unit, it is shown that light sensitivity can be tuned from visible to near-infrared region. Numerous photovoltaic metrics have been used to assess the D-A'-π-A system's performance like HOMO-LUMO gap (∆Eg), oxidation potential of excited-state (Edye*), open-circuit voltage (VOC), free energy of electron injection (Ginj) and reorganization energy (Z) by using DFT/TD-DFT approach. The lowest ∆Eg (1.88 eV) is observed for TH1 and ∆Eg further decreases after adsorption on TiO2 and GO. The lower Zh is observed than Ze for all the designed dyes and is lowest for dye TH5 (162 meV). The BZ5 dye demonstrates the highest power conversion efficiency of 12.66 % with JSC value of 15 mA cm−2. This study sheds light on the existing and potential future trends in graphene nanocomposite based DSSCs for improved solar device performance and enhanced solar light harvesting.
{"title":"Graphene-decorated Indigo based Photosensitizers for DSSC applications: A DFT approach","authors":"Vipin Kumar, Prabhakar Chetti","doi":"10.1016/j.molstruc.2025.142026","DOIUrl":"10.1016/j.molstruc.2025.142026","url":null,"abstract":"<div><div>Graphene nanocomposites have surfaced as a promising material for charge transfer-based dye-sensitized solar cell (DSSC) enhancement. Graphene nanocomposites coated with different metal oxides find extensive use in energy devices, including batteries, fuel cells, solar cells, sensors, electro-catalysis, and photo-catalysis. Nevertheless, little research has been done on these composite's potential use in DSSC applications. In this work, we investigated a multi-junction system consisting of <span>D</span>-A’-π-A sensitized (TiO<sub>2</sub>)<sub>16</sub> nanocomposite at graphene oxide (dye@TiO<sub>2</sub>@GO) and the influence of numerous π-bridges on the push-pull dye system's optical and photovoltaic properties in light-harvesting device. The highest absorption wavelength is observed for <strong>TH1</strong> (623 nm) which further increases in adsorbed systems. By changing the spacer unit, it is shown that light sensitivity can be tuned from visible to near-infrared region. Numerous photovoltaic metrics have been used to assess the <span>D</span>-A'-π-A system's performance like HOMO-LUMO gap (<em>∆E<sub>g</sub></em>), oxidation potential of excited-state (<em>E</em><sup>dye*</sup>), open-circuit voltage (<em>V</em><sub>OC</sub>), free energy of electron injection (<em>G</em><sub>inj</sub>) and reorganization energy (<em>Z</em>) by using DFT/TD-DFT approach. The lowest <em>∆E<sub>g</sub></em> (1.88 eV) is observed for <strong>TH1</strong> and <em>∆E<sub>g</sub></em> further decreases after adsorption on TiO<sub>2</sub> and GO. The lower Z<sub>h</sub> is observed than Z<sub>e</sub> for all the designed dyes and is lowest for dye <strong>TH5</strong> (162 meV). The <strong>BZ5</strong> dye demonstrates the highest power conversion efficiency of 12.66 % with J<sub>SC</sub> value of 15 mA cm<sup>−2</sup>. This study sheds light on the existing and potential future trends in graphene nanocomposite based DSSCs for improved solar device performance and enhanced solar light harvesting.</div></div>","PeriodicalId":16414,"journal":{"name":"Journal of Molecular Structure","volume":"1336 ","pages":"Article 142026"},"PeriodicalIF":4.0,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143631767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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