化学最新文献

{"title":"Sum-frequency order parameter ratio determination for molecules with high-symmetry vibrational modes.","authors":"Aruna Kumarasiri, Amin Yousefi, Dennis Hore","doi":"10.1063/5.0350318","DOIUrl":"https://doi.org/10.1063/5.0350318","url":null,"abstract":"<p><p>The structure of molecules at surfaces and buried interfaces can be probed by second-order nonlinear optical techniques that derive their response from environments with broken centrosymmetry, thereby simultaneously enhancing the signal from the molecules of interest and suppressing the responses of the adjacent bulk phases. However, even though these methods are surface-sensitive, extracting orientation information has often relied on significant assumptions about the shape of the orientation distribution and the underlying molecular electronic structure. Here, we illustrate that the measurement of the relative magnitude and the phase of tensor elements that govern the vibrational sum frequency response can be used to construct a ratio of order parameters ⟨P3⟩/⟨P1⟩. This structural parameter does not require knowledge of the hyperpolarizability or even the hyperpolarizability ratio, thereby dramatically increasing the accuracy of its determination. We then show how this parameter can be used to comment on the most probable distribution of tilt angles. This is demonstrated for para-cyanophenol at three different interfaces.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 15","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149220244","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}

{"title":"Supramolecular Synthon-Driven Design, Synthesis, and Single-Crystal Structures of a Series of Diacylhydrazines as Potential Supramolecular GelatorsExploring the Gel Matrix for Drug Delivery","authors":"Asish Pharas,&nbsp;Subhajit Ghosh,&nbsp;Parthasarathi Dastidar","doi":"10.1021/acs.cgd.6c00993","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00993","url":null,"abstract":"<p>Supramolecular assembly of small molecules occasionally leads to viscoelastic materials like supramolecular gels that are important for various applications in material science including drug delivery. However, the a priori design of such soft materials remains an elusive goal. Understanding of the supramolecular synthon and its importance in the context of crystal engineering proved to be handy in occasional prediction of gelation. Herein, we report the supramolecular synthon-driven design, synthesis, and single-crystal structures of a series of diacylhydrazines as potential supramolecular gelators. Conjugation of various arylcarboxylic acids including a few non-steroidal-<em>anti</em>-inflammatory drugs (NSAIDs), namely, naproxen (<strong>NAP</strong>), ibuprofen (<strong>IBU</strong>), and flurbiprofen (<strong>FLB</strong>), with hydrazine afforded seven diacylhydrazine molecules, all of which were found to be gelators of various solvents. The gels were routinely characterized by dynamic rheology and electron microscopy. While hydrogen-bonded self-assembly involving the N−N fused amide moieties in these molecules as revealed by single-crystal structures appeared to have played a pivotal role in gelation, one such gelator <strong>NAP_Hydz</strong> showed the capability of loading drugs like sulfasalazine or <strong>SUL</strong> (NSAID) and doxorubicin or <strong>DOX</strong> (anti-cancer) onto the corresponding supramolecular gel matrix. In vitro studies revealed that the drug-loaded xerogels, i.e., <strong>NAP_Hydz@SUL</strong> (xerogel) and <strong>NAP_Hydz@DOX</strong> (xerogel), were effective in reducing inflammation in inflamed normal cells RAW 264.7 and killing melanoma cells (B16−F10), respectively. The rheoreversibility, injectability, and shape sustainability of the supramolecular gels of <strong>NAP_Hydz</strong> suggested a plausible drug delivery application via the topical route.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8415–8428"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221955","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}

{"title":"MAlB3O6F2 (M = Ca and Pb): Two New Fluoroaluminoborates Featuring π-Conjugated [BO3] and [AlO4F2] Units with Large Birefringence","authors":"Yaozu Li,&nbsp;Chao Wei,&nbsp;Wenjing Zhang,&nbsp;Huiyi Zhang,&nbsp;Bo Zhao,&nbsp;Bingbing Zhang,&nbsp;Ying Wang","doi":"10.1021/acs.cgd.6c00931","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00931","url":null,"abstract":"<p>Current birefringent crystals (e.g., MgF₂, α-BBO, and YVO₄) are limited by either small birefringence or insufficient deep-UV transparency. Achieving both properties simultaneously remains a key challenge. To address this issue, recent research based on the “confined π-conjugated” strategy has turned its attention to fluoroaluminoborates. In this structural design, non-π-conjugated [Al−O/F] units connect and isolate planar π-conjugated groups, effectively broadening the bandgap while maintaining optical anisotropy. Building on this concept and incorporating different cations, this study reports two new fluoroaluminoborate compounds: CaAlB₃O₆F₂ (CABOF) and its isostructural analogue, PbAlB₃O₆F₂ (PABOF). In PABOF, the introduction of Pb²⁺ induces local structural distortion, thereby enhancing the optical anisotropy. Both CABOF and PABOF exhibit birefringence values exceeding 0.1 at 546 nm, with PABOF demonstrating the largest birefringence among the known fluoroaluminoborates. In addition, both compounds exhibit excellent thermal stability. This work identifies two potential UV-birefringent materials, further enriching the fluoroaluminoborate family.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8356–8364"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221982","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}

{"title":"Investigation of Lamotrigine Crystal Polymorphs Using Crystal Structure Prediction and Terahertz Spectroscopy","authors":"Salvatore Zarrella,&nbsp;Mizuki Mohara,&nbsp;Kei Shimura,&nbsp;Timothy M. Korter","doi":"10.1021/acs.cgd.6c00916","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00916","url":null,"abstract":"<p>Crystal structure prediction (CSP) plays a significant role in exploring the crystal polymorphism of pharmaceutical solids. Determination of the atomic-level structures of crystalline materials is a fundamental step in understanding their bulk physical and chemical properties and behavior in drug products. CSP can be performed using numerous computational approaches, but all ultimately require comparison with experimental measurements to confirm the CSP findings. In this work, terahertz (THz) vibrational spectroscopy is combined with powder X-ray diffraction (PXRD) to demonstrate a new metrics framework for the validation of CSP investigations. Terahertz spectroscopy probes the low-frequency (≤150 cm⁻¹) lattice vibrations of molecular crystals and provides a polymorph specific spectral profile that complements diffraction methods. This methodology is applied to the anti-epileptic drug lamotrigine, the subject of multiple crystal engineering studies to improve its formulated performance. A CSP search was performed on lamotrigine starting with a fast molecular mechanics survey for initial crystal structure candidates (∼800,000 structures), followed by high-accuracy solid-state density functional theory to refine the most promising candidates. The accuracy of the CSP output was evaluated by numerical comparison of simulated and experimental PXRD and THz datasets, with both benchmarks unambiguously indicating the lowest energy CSP candidate to be a structural match to the published lamotrigine polymorph (Form I, C 2/<em>c</em> space group). The success of the overall approach highlights THz spectroscopy as an effective orthogonal experimental benchmark for CSP and the combined experimental validation process represents a compelling procedure for advancing predictive solid-state modeling of pharmaceutical materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8332–8344"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222042","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}

{"title":"Liquid−Liquid Phase Separation-Controlled Polymorphism and Stoichiomorphism in the Pterostilbene-(E)-1,2-bis(pyridin-4-yl)ethene Cocrystal","authors":"Mythili Aruchamy,&nbsp;Srivaishnavi Devi Beetukooru,&nbsp;Sunil Kumar Nechipadappu,&nbsp;Sridhar Balasubramanian","doi":"10.1021/acs.cgd.6c00366","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00366","url":null,"abstract":"<p>Liquid−liquid phase separation (LLPS) can severely hinder controlled nucleation and crystal growth during cocrystallization, restricting access to phase-pure polymorphs and stoichiomorphs. During the cocrystallization of the Pterostilbene-(E)-1,2-bis(pyridin-4-yl)ethene (PTB-BPE) system, LLPS emerged as a major experimental barrier to crystal development. In situ microscopic observations revealed that strong PTB-solvent interactions under specific solvent environments promoted LLPS, thereby suppressing nucleation and crystal growth. This limitation was overcome through mechanochemical crystallization approaches combined with the ability of BPE to form stabilizing O−H···N hydrogen bond interactions with PTB. Systematic solvent modulation afforded four crystalline phases of PTB-BPE: Form I (plate, PTB/BPE = 1:0.5), Form II (needle, PTB/BPE = 1:0.5), and Form III (block, PTB/BPE = 2:1) as polymorphic forms, while Form IV (rod, PTB/BPE = 1:1.5) represents a distinct stoichiomorph. Mechanical pretreatment followed by slow evaporation enabled the formation of multiple solid forms; other mechanochemical routes predominantly yielded Form III, and slurry conversion selectively produced bulk Form IV. Single-crystal X-ray diffraction confirmed differences in packing, symmetry, and asymmetric unit composition among the forms. Lattice energy calculations and void analysis indicate comparable thermodynamic stability among the polymorphs, with Form III exhibiting strong intermolecular interactions and efficient packing within the PTB-BPE solid-form landscape.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8068–8085"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149222080","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}

{"title":"The development of a high-accuracy, low-cost, numerical tensor method for the P states of three-particle systems.","authors":"Brice Kammegne Tcheugam, Henryk A Witek, Hazel Cox","doi":"10.1063/5.0356420","DOIUrl":"https://doi.org/10.1063/5.0356420","url":null,"abstract":"<p><p>In this paper, we solve the non-relativistic many-body Schrödinger equation (SE) for the excited P states (L = 1) of three-particle systems with natural and unnatural parity. The exact separation of the rotational degrees of freedom from the internal degrees of freedom presented by Sadhukhan et al. [arXiv:2506.23962 (2025)] is exploited. The angular matrix elements involve the product of two bipolar harmonics and are calculated using an explicit analytical expression containing the Wigner 3j- and 6j-symbols. Using a symmetry and parity adapted wavefunction for P states in perimetric coordinates, the variational form of the SE in canonical tensor format is derived. This consists of a sum of triple tensor products of factor matrices and is an exact representation. From this canonical format, the SE can be solved in full tensor format or used to derive an exact representation as a second-order tensor train. Two formulations are presented. In the first, scaled perimetric coordinates are used; it is assumed that the like-charged particles have the same asymptotic behavior so that the orthonormality of the Laguerre functions can be exploited and the matrices are sparse. In the second, the like-charged particles are not constrained to have the same asymptotic behavior and an analytical integral is used which results in dense matrices. It is shown that by optimizing either one or two non-linear variational parameters, it is possible to obtain excited P state energies that are accurate to the picohartree, for atomic and molecular systems in less than 25 min on a standard desktop computer.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"165 15","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149220281","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}

{"title":"Engineering Fe Species on USY Zeolite Support for the Oxidative Cleavage of Lignin to Bio-Based Diethyl Maleate","authors":"Rujia Chen,Kejia Wu,Xiudan Zhao,Yun Tian,Zhenping Cai,Jinrong Liang,Weilu Ding,Wentao Mu,Xuehui Li","doi":"10.1021/acssuschemeng.6c08496","DOIUrl":"https://doi.org/10.1021/acssuschemeng.6c08496","url":null,"abstract":"The development of sustainable routes for polymer monomers is crucial for the chemical industry. Herein, we report a highly efficient and selective oxidative depolymerization strategy for converting lignin into diethyl maleate (DEM), a valuable precursor for polyaspartic polyurea resins. A series of iron oxide catalysts supported on commercial USY zeolites via a simple impregnation-calcination method were developed. Notably, the catalyst prepared using iron sulfate (Fe2(SO4)3) as the precursor exhibited superior performance, achieving a maximum DEM yield of 53.0 wt % and a selectivity of 72.4% from organosolv bagasse lignin, outperforming the iron nitrate- and chloride-derived catalysts by 29.2 and 31.9 wt % in yield, respectively. Comprehensive characterizations revealed that the unique highly dispersed Fe(SO4)x phases significantly increased the proportion of Fe3+ species and facilitated electron transfer across the support-iron interface. The synergistic interplay between sulfur-induced Brønsted acid sites and isolated octahedral iron sites was identified as the key factor driving the efficient cleavage of lignin linkages and subsequent oxidative ring-opening. By combining commercially available supports and earth-abundant metals, this work offers an environmentally viable pathway for lignin depolymerization into polymer monomers, demonstrating significant potential for industrial scalability.","PeriodicalId":25,"journal":{"name":"ACS Sustainable Chemistry & Engineering","volume":"73 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Precise Fabrication of Supported Zero-valent Nano-noble Metals via Reductant-Preset Cascade In-Situ Reduction: Nitroaromatics Reduction as Probe Reaction","authors":"Tianrui Deng,Xingye Zhao,Xue Zhao,Cuiyu Li,Yanjuan Zhao,Zhuo Zhao,Yicheng Zhang,Guangzhi Hu","doi":"10.1039/d6cc05471d","DOIUrl":"https://doi.org/10.1039/d6cc05471d","url":null,"abstract":"Precise synthesis of noble metal nanoparticles is the key to cost reduction and efficiency enhancement, and this study has developed a ‘reductant preset cascade in-situ reduction’ strategy that achieves precise synthesis of supported noble metal nanoparticles through directed manipulation at the molecular level.","PeriodicalId":67,"journal":{"name":"Chemical Communications","volume":"7 1","pages":""},"PeriodicalIF":4.9,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221812","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}

{"title":"Correction to “Boundary Mismatch Free Energy Links Activity Coefficients and Cooperativity in Molecular Solids”","authors":"Alejandro G. Marangoni,&nbsp;Erica Pensini","doi":"10.1021/acs.cgd.6c01315","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c01315","url":null,"abstract":"","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8636–8636"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221954","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}

{"title":"Ligand-Induced Polyoxometalate Supramolecular Hybrids for Efficient Tetracycline Photodegradation","authors":"Ning Li,&nbsp;Xue-Yi Wang,&nbsp;Yu-Heng Liu,&nbsp;Dong-Dong Yang,&nbsp;Jin Zhang,&nbsp;Tai-Ran Wang,&nbsp;Yong-Xin Gu,&nbsp;Qiu-Yu Bao,&nbsp;Su-Fang Zhang","doi":"10.1021/acs.cgd.6c00719","DOIUrl":"https://doi.org/10.1021/acs.cgd.6c00719","url":null,"abstract":"<p>The construction of efficient and durable photocatalysts for antibiotic elimination remains a formidable challenge. Herein, two novel polyoxometalate-based metal−organic complexes, [Zn₄(Hppb)₆(ppb)₂(H₂O)₂][PW₁₂O₄₀]₂·H₂O (<strong>1</strong>) and [Ni(Hppb)₂(H₂O)₂]₂[PW₁₂O₄₀]·COOH·4H₂O (<strong>2</strong>), were successfully synthesized via a hydrothermal method by incorporating Keggin-type [PW₁₂O₄₀]^3- polyanions and transition metal ions (Zn²⁺/Ni²⁺) with a rigid π-conjugated Hppb ligand (where Hppb = 2-(3-(pyridin-2-yl)-1<em>H</em>-pyrazol-1-yl)benzoate). Both compounds feature stable three-dimensional supramolecular architectures constructed through coordination bonds, C−H···O hydrogen bonds, and π−π interactions, which bridge the metal−organic units and polyoxoanions. The π-conjugated Hppb ligand facilitates light harvesting and charge transfer, while the synergistic cooperation between the metal−organic matrix and POM units endows the hybrids with excellent photocatalytic activity for tetracycline degradation under both visible and UV light. Under optimized visible light, <strong>1</strong> and <strong>2</strong> achieved high degradation efficiencies of 92.7% and 90.6% within 110 and 140 min, respectively; under UV light, the degradation proceeded more rapidly, with <strong>1</strong> and <strong>2</strong> attaining 93.8% and 89.7% degradation within just 80 and 100 min, respectively. Structure−activity and photoelectrochemical analyses reveal that <strong>1</strong> outperforms <strong>2</strong> due to its more favorable structural features and charge separation efficiency. EPR results, together with radical trapping experiments, identified ^•O₂⁻ as the dominant reactive species. Both catalysts exhibited good recyclability. This work provides a viable strategy for designing robust POM-based photocatalysts for antibiotic-contaminated water remediation.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"26 20","pages":"8161–8172"},"PeriodicalIF":3.6,"publicationDate":"2026-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221994","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}