ChemRxiv最新文献_第4页

A Near-Infrared-Absorbing Osmium(II) Complex as a Photosensitizer for Photodynamic Therapy inducing Immunogenic Cell Death 作为光敏剂的近红外吸收锇（II）复合物可用于诱导免疫性细胞死亡的光动力疗法

ChemRxiv Pub Date : 2024-09-19 DOI: 10.26434/chemrxiv-2024-6dnl2

Gilles, Gasser, Yiyi, Zhang, Pierre, Mesdom, Eduardo, Izquierdo-García, João, António, Bruno, Saubamea, Johanne, Seguin, Morgane , Moinard, Philippe, Arnoux, Céline, Frochot, Kevin, Cariou, Bich-Thuy, Doan

{"title":"A Near-Infrared-Absorbing Osmium(II) Complex as a Photosensitizer for Photodynamic Therapy inducing Immunogenic Cell Death","authors":"Gilles, Gasser, Yiyi, Zhang, Pierre, Mesdom, Eduardo, Izquierdo-García, João, António, Bruno, Saubamea, Johanne, Seguin, Morgane , Moinard, Philippe, Arnoux, Céline, Frochot, Kevin, Cariou, Bich-Thuy, Doan","doi":"10.26434/chemrxiv-2024-6dnl2","DOIUrl":"https://doi.org/10.26434/chemrxiv-2024-6dnl2","url":null,"abstract":"Immunogenic cell death (ICD), which converts tumor cells into their own vaccine, plays a pivotal role in the development of novel anti-cancer therapies. Here, a small series of osmium(II) polypyridyl complexes were synthesized and their biological activity in the dark and upon light irradiation against various cancer cell lines was studied. The compound Os2 (bearing two 4,7-diphenyl-1,10-phenanthrolines and one substituted bipyridine ligand) was discovered to be the most effective photosensitizer (PS) for photodynamic therapy (PDT) of this series through the photogeneration of 1O2 and •OH. In addition, Os2 was found to exhibit promising toxicity upon near-infrared (NIR) irradiation under both normoxia and hypoxia. These observations indicate that this PS is working through a mixture of Type-I and Type-II mechanisms. More interestingly, upon 740 nm irradiation, Os2 can stimulate a strong ICD response both in vitro and in vivo. A comprehensive immune analysis showed that mice vaccinated with Os2-treated CT26-luc cells boosted the systemic specific adaptive immune responses, including the activation of CD8+ T cells and reprograming of macrophages, leading to effective inhibition of tumor growth. Os2 is, to the best of our knowledge, the first photoactive osmium-based complex inducing ICD.","PeriodicalId":9813,"journal":{"name":"ChemRxiv","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267252","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Patterning of photochromic diarylethene crystals by sublimation for morphological controls 通过升华对光致变色二元乙烯晶体进行图案化以实现形态控制

ChemRxiv Pub Date : 2024-09-19 DOI: 10.26434/chemrxiv-2024-j0sdf

Mami, Isobe, Daichi, Kitagawa, Seiya, Kobatake

引用次数: 0

Implications of weaving pattern on the material properties of two-dimensional molecularly woven fabrics 编织模式对二维分子编织物材料特性的影响

ChemRxiv Pub Date : 2024-09-19 DOI: 10.26434/chemrxiv-2024-x07sq

Zhi-Hui, Zhang, Shiwei, Chen, Yuntao, Li, Yijing, Chen, Jinrong, Yang, Xiao, He, Liang, Zhang

{"title":"Implications of weaving pattern on the material properties of two-dimensional molecularly woven fabrics","authors":"Zhi-Hui, Zhang, Shiwei, Chen, Yuntao, Li, Yijing, Chen, Jinrong, Yang, Xiao, He, Liang, Zhang","doi":"10.26434/chemrxiv-2024-x07sq","DOIUrl":"https://doi.org/10.26434/chemrxiv-2024-x07sq","url":null,"abstract":"Similar to macroscopic woven fabrics, molecularly woven polymers constructed from identical molecular strands but different weaving architectures are anticipated to display diverse physical and mechanical characteristics. Nonetheless, identifying these distinctions and comprehending the underlying mechanisms poses a significant challenge. Herein, we evaluate the impacts of different weaving patterns—plain, mix, and basket—on the characteristics of two-dimensional (2D) organic woven polymers through systematic all-atom simulation. Three weaves, consisting of the same molecular strands, are produced by adjusting the connections of the enantiomers of an inherently chiral 2×2 interwoven grid. Among the tested patterns, the plain weave exhibits superior stability, minimal structural deformation, and the most consistent pore size compared to others. The maintenance of the weaves in kinetically stable high-energy states is attributed to both aromatic stacking and hydrogen bonding interactions between warp and weft strands, while the alteration of weaving patterns leads to variations in the type and strength of these weak interactions. Despite the differences on the weaving pattern, the mechanical stress tends to localize at the contact field. Further analysis on impact resistance and in-plane stretchability highlights how weaving architectures influence the energy dissipation pathways and reinforce the mechanical properties of individual molecular chains. Simulation outcomes indicate that the disparities resulting from various weave patterns primarily stem from the total number and density of entanglements, as well as the interstrand non-covalent interactions. This research highlights the critical influence of weaving architecture on molecularly interlacing material properties, providing valuable insights for future invention and engineering of molecular-level weaving.","PeriodicalId":9813,"journal":{"name":"ChemRxiv","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

[1,n]-Metal migrations for directional translational motion at the molecular level 分子水平上定向平移运动的[1,n]-金属迁移

ChemRxiv Pub Date : 2024-09-18 DOI: 10.26434/chemrxiv-2024-nkrd8-v2

Beatrice, Collins, Emma, Hollis, Michael, Chronias, Carlijn, van Beek, Paul, Gates

{"title":"[1,n]-Metal migrations for directional translational motion at the molecular level","authors":"Beatrice, Collins, Emma, Hollis, Michael, Chronias, Carlijn, van Beek, Paul, Gates","doi":"10.26434/chemrxiv-2024-nkrd8-v2","DOIUrl":"https://doi.org/10.26434/chemrxiv-2024-nkrd8-v2","url":null,"abstract":"The controlled translational motion displayed by nature’s motor proteins underpins a wealth of processes integral to life, from organelle transport to muscle contraction. The motor proteins move along one dimensional cytoskeletal tracks, with their motion characterised by high association of the enzyme to the biopolymer combined with highly dynamic motion along the track. Efforts to mimic this dynamic association and control translational motion in fully synthetic systems have been dominated by rotaxane-based systems, where the properties of the mechanical bond ensure complete association between the moving component (the macrocycle) and the track it encircles, while allowing high rates of translation through shuttling of the moving component under Brownian motion. In addition to the dynamic association displayed by many rotaxane systems, by careful design of the track and macrocyclic component, elegant strategies have been employed to further control the motion in these mechanically interlocked systems, with both energy and information ratchet mechanisms allowing directional translational motion to be achieved. Other than mechanical bonds, alternative platforms for achieving controlled translational motion in fully synthetic systems have had more limited success, with bipedal walker systems that exhibit dynamic association lacking mechanisms to achieve inherent directionality, and bipedal systems that do display high levels of directionality requiring stepwise intervention of an experimentalist (i.e., they lack the dynamic autonomous behaviour that underpins nature’s walkers). Here we introduce carbon-to-carbon metal migration as a new platform for dynamic association and show how such migrations, in combination with the incorporation of a simple hydrocarbon fuel, can be harnessed to achieve autonomous directional translational motion of a metal centre along the length of a polyaromatic thread.","PeriodicalId":9813,"journal":{"name":"ChemRxiv","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267140","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Effect of minor differences in sequences of huntingtin peptides on their interactions with sucrose and trehalose: in silico investigation 狩猎蛋白肽序列的微小差异对其与蔗糖和树胶糖相互作用的影响：硅学研究

ChemRxiv Pub Date : 2024-09-18 DOI: 10.26434/chemrxiv-2024-5dk2f

Inna, Ermilova, Linnea, Ögren, Olivia, Borg, Maria, Weber, Elinor, Einarsson, Erik, Podda Grahn, Jan, Swenson

{"title":"Effect of minor differences in sequences of huntingtin peptides on their interactions with sucrose and trehalose: in silico investigation","authors":"Inna, Ermilova, Linnea, Ögren, Olivia, Borg, Maria, Weber, Elinor, Einarsson, Erik, Podda Grahn, Jan, Swenson","doi":"10.26434/chemrxiv-2024-5dk2f","DOIUrl":"https://doi.org/10.26434/chemrxiv-2024-5dk2f","url":null,"abstract":"In this work the behavior of two Huntingtin (Htt) peptides in mixtures with water and either sucrose or trehalose were investigated by classical molecular dynamics (MD) simulations. Structures of those peptides are listed in the Protein Databank as 2LD2 (Biophys. J., 2013, 105, 699-710) and 6N8C (Proc. Natl. Acad. Sci., 2019, 116, 9, 3562-3571). The principal difference between those peptides is in their C- and N-terminals. Since Huntington’s disease is related to the aggregation of proteins containing consecutive polyglutamine in their amino acid chains, the aim was to investigate if smaller amounts of disaccharides could reduce aggregation of two peptides from the Htt protein. Computational results revealed that both sugars alter the secondary structures of peptides and decrease the total number of contacts (the sum of hydrophobic contacts and hydrogen bonds) between these biomolecules. However, regarding only the number of hydrogen bonds, the disaccharides reduced this value for peptide-peptide interactions for 6N8C, while for 2LD2 sucrose and trehalose instead promoted an increase of this number. Such a difference in behaviors of peptides could be related to dissimilarities in their sequences, pointing out the importance to consider amino-acid residues in C- and N-terminal when developing drugs. Furthermore, both disaccharides demonstrated abilities to slow down the dynamics of simulated mixtures, which was concluded from rotational correlation and self-intermediate scattering functions. Amino-acid residues MET(1), GLU(5), LYS(6), LYS(9), GLU(12), LYS(15), PHE(17) and GLN(18) are identified as the main candidate amino acids involved in interpeptide binding and binding to disaccharides, where the glutamic acid residues (GLU(5) and GLU(12)) had the highest number of hydrogen bonds with sucrose and trehalose.","PeriodicalId":9813,"journal":{"name":"ChemRxiv","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267383","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Weighted distribution of relaxation time analysis of battery impedance spectra using Gaussian process regression for noise estimation 利用高斯过程回归对电池阻抗谱进行加权弛豫时间分布分析以估计噪声

ChemRxiv Pub Date : 2024-09-18 DOI: 10.26434/chemrxiv-2024-1gxgq

Franz Philipp, Bereck, Christian Hippolyt, Bartsch, Limei, Jin, Andreas, Mertens, Rüdiger-Albert, Eichel, Christoph, Scheurer, Josef, Granwehr

{"title":"Weighted distribution of relaxation time analysis of battery impedance spectra using Gaussian process regression for noise estimation","authors":"Franz Philipp, Bereck, Christian Hippolyt, Bartsch, Limei, Jin, Andreas, Mertens, Rüdiger-Albert, Eichel, Christoph, Scheurer, Josef, Granwehr","doi":"10.26434/chemrxiv-2024-1gxgq","DOIUrl":"https://doi.org/10.26434/chemrxiv-2024-1gxgq","url":null,"abstract":"Electrochemical impedance spectroscopy (EIS) is one of the most widely deployed methods to characterise electrochemical systems such as batteries, fuel cells or electrolyzers. The distribution of relaxation times (DRT) represents a technique to simplify EIS data by deconvolution with a suitable kernel, while with equivalent circuit modelling (ECM) a user-selected function is fitted to characterize the investigated system. Ideally, the residuals of a DRT fit should represent random white noise without systematic residuals, hence no useful data is lost by this analysis step. Thereby DRT can provide the number of distinguishable features based solely on the EIS data, without a priori knowledge of the response of the investigated system. It is demonstrated that such a 'lossless' DRT inversion is possible if the local noise amplitude is considered, which requires a weighted DRT procedure and a method to estimate the frequency dependent noise amplitude. A noise estimate to determine the necessary weights was obtained using multiple EIS acquisitions of the same battery at identical state-of-charge. Alternatively, it is shown that Gaussian process regression (GPR) is capable of estimating an equivalent weighting matrix from a single data set as a prerequisite for automatized weighted DRT inversion without user intervention. The obtained DRT spectrum is then used for the selection of an equivalent circuit model, its initial parametrization, and setting of constraints. The robustness and reliability of this technique is tested numerically using a simple digital twin model. Eventually, by means of the investigated battery it is discussed that using a combination of DRT and ECM, a more physically relevant description of processes in an electrochemical system can be achieved.","PeriodicalId":9813,"journal":{"name":"ChemRxiv","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267139","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

High-efficiency and long-lifetime deep-blue phosphorescent OLEDs using deuterated exciplex-forming host 使用氘化赋形剂宿主的高效、长寿命深蓝色磷光 OLED

ChemRxiv Pub Date : 2024-09-18 DOI: 10.26434/chemrxiv-2024-8bn7g

Wenbo, Yuan, Tianyu, Huang, Jianping, Zhou, Man-Chung, Tang, Dongdong, Zhang, Lian, Duan

引用次数: 0

Low-Temperature Borylation of C(sp3)–O Bonds of Alkyl Ethers by Gold-Metal Oxide Cooperative Catalysis 金-金属氧化物协同催化烷基醚 C（sp3）-O 键的低温硼酸化作用

ChemRxiv Pub Date : 2024-09-18 DOI: 10.26434/chemrxiv-2024-h6mw9

Hiroki, Miura, Hidenori, Nishio, Tetsuya, Shishido

{"title":"Low-Temperature Borylation of C(sp3)–O Bonds of Alkyl Ethers by Gold-Metal Oxide Cooperative Catalysis","authors":"Hiroki, Miura, Hidenori, Nishio, Tetsuya, Shishido","doi":"10.26434/chemrxiv-2024-h6mw9","DOIUrl":"https://doi.org/10.26434/chemrxiv-2024-h6mw9","url":null,"abstract":"Since ether moieties are often found not only in petrochemical products but also in natural organic molecules, the development of methods for manipulating C–O bonds of ethers is important for expanding the range of compound libraries synthesized from biomass resources, which should contribute to the goal of carbon neutrality. We report herein that gold nanoparticles supported on Lewis acidic metal oxides, namely α-Fe2O3, showed excellent catalytic activity for the reaction of dialkyl ethers and diborons, which enables the conversion of unactivated C(sp3)–O bonds to C(sp3)–B bonds at around room temperature. Various acyclic and cyclic ethers as well as a series of diborons participated in the heterogeneous gold-catalyzed borylation of unactivated C(sp3)–O bonds, to give a series of alkylboronates in high yields. Mechanistic studies corroborated that the present borylation of C(sp3)–O bonds of dialkyl ethers proceeded at the interface between gold nanoparticles and Lewis acidic metal oxides. Furthermore, adsorption IR measurements supported the notion that strong Lewis acid sites were generated at the boron atom of diborons adsorbed at the interface between Lewis acidic metal oxides and gold nanoparticles, which enabled us to ensure that the cooperation of gold nanoparticles and Lewis acidic metal oxides was responsible for the efficient transformation of unactivated C(sp3)–O bonds in ethers under mild conditions. This novel reaction technology which is specific to heterogeneous catalysts enables the activation of stable C(sp3)–O bonds of oxygenated chemical feedstock, which is beneficial for the sustainable synthesis of value-added organoboron compounds.","PeriodicalId":9813,"journal":{"name":"ChemRxiv","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142269840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Improved LC-MS detection of opioids, amphetamines, and psychedelics using TrEnDi 利用 TrEnDi 改进对阿片类药物、苯丙胺和迷幻剂的 LC-MS 检测

ChemRxiv Pub Date : 2024-09-18 DOI: 10.26434/chemrxiv-2024-7gb0p

Jeffrey, Smith, Christian, Rosales, Noah, Lepinsky, Wondewossen, Gebeyehu, Karl, Wasslen, Benjamin, Warnes, Jasmine, Chihabi, Jeffrey, Manthorpe

{"title":"Improved LC-MS detection of opioids, amphetamines, and psychedelics using TrEnDi","authors":"Jeffrey, Smith, Christian, Rosales, Noah, Lepinsky, Wondewossen, Gebeyehu, Karl, Wasslen, Benjamin, Warnes, Jasmine, Chihabi, Jeffrey, Manthorpe","doi":"10.26434/chemrxiv-2024-7gb0p","DOIUrl":"https://doi.org/10.26434/chemrxiv-2024-7gb0p","url":null,"abstract":"Substances of misuse are becoming increasingly difficult to analyze as unique methods of smuggling are adopted and due to the rapid emergence of new psychoactive substances, increasing the pool of compounds to characterize and identify. Technologies such as gas chromatography and liquid chromatography coupled to mass spectrometry (MS) represent the gold standard for accurate and robust analysis, with on-site ambient- and portable-MS systems providing rapid methods of drug screening and testing. For many samples containing residual analyte quantities, methods to improve sensitivity through chemical derivatization are critical for accurate determination. Herein, we demonstrate for the first time the use of trimethylation enhancement using diazomethane (TrEnDi) to improve the MS-based sensitivity of 13 different drugs of misuse. All analytes were successfully permethylated, with 11 demonstrating improved analytical characteristics from TrEnDi with MS sensitivity enhancements of 1.2–24.2-fold and increases in reversed-phase chromatographic retention. Derivatization using 13C-isotopically labelled TrEnDi reagents were used to successfully resolve isobaric interference issues between three pairs of controlled substances. The sensitivity of a TrEnDi-modified analyte was increased several orders of magnitude using an unconventional aprotic solvent system for electrospray ionization. Finally, TrEnDi was employed to boost the sensitivity of morphine in a real urine matrix. Our results demonstrate a percent recovery of 103.1% and a sensitivity enhancement of 2.4-fold, demonstrating versatility and applicability of TrEnDi to pre-existing analytical workflows for trace analysis.","PeriodicalId":9813,"journal":{"name":"ChemRxiv","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142267142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Gasification for SNG-power cogeneration using coal as material integrated with calcium looping for enhancing CO2 absorption 以煤为原料的气化 SNG 热电联产与钙循环相结合，提高二氧化碳吸收率

ChemRxiv Pub Date : 2024-09-18 DOI: 10.26434/chemrxiv-2024-grhpq

Yuan, Chen, Can, Deng, Jingyuan, Zhu, Bingyang, Du, Rui, Zhang, Ziyu, Li, Huimin, Liu

引用次数: 0