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1.
以一种新型的醌类光敏剂—菌生素 (HMB)为模型化合物 ,利用量子化学从头算HF/ 6 31G和含时密度泛函TD B3LYP/ 6 31G方法计算研究了卤代作用对醌类光敏剂分子性质和光敏活性的影响 .结果发现 ,卤代作用降低了HMB母体的HOMO和LUMO能级 (EHOMO和ELUMO)及其差值△E ,随卤族元素从上到下 ,EHOMO和ELUMO呈增大趋势 ,而△E呈减小趋势 ,使得分子激发光谱有不同程度的红移 ,在增加PQP三重态量子产率的同时降低了分子最低三重激发态的能量 ,两种作用相互抵消 ,使得卤代物的 1O2 量子产率与母体相似 ;增加了分子的绝热电子亲合势 ,使分子产生O2 -的能力下降 ;卤原子的引入 ,降低了HMB母体分子内氢键的强度 ,同时使顺式构型的分子内质子传递势垒增大 ,而使反式构型势垒减小 . 相似文献
2.
新型光敏剂叶绿酸f对人膀胱癌T24细胞的光动力杀伤作用 总被引:1,自引:0,他引:1
将自主研发的新型光敏剂叶绿酸f与T24细胞共同孵育后,以650nm激光照射,通过MTT法检测光动力处理后T24细胞的生长抑制率,流式细胞术检测凋亡情况,同时利用激光共聚焦显微镜488nm和405nm双波长激发,应用线粒体探针,进行叶绿酸f的亚细胞定位。结果显示叶绿酸f为浓度2.5,5,10μg/mL对T24细胞生长抑制率在光能量密度4J/cm2下为17.68%,49.35%和84.42%,在1J/cm2时为4.34%,37.42%和78.38%;流式细胞术显示T24细胞光动力处理后,凋亡率为(45.23±1.2)%,显著高于对照组;激光共聚焦显微镜显示504nm激发叶绿酸f发出的红光与488nm激发线粒体探针产生的绿光分布基本一致。实验证明叶绿酸f对T24细胞杀伤效果明显,主要是通过作用于线粒体,诱导细胞凋亡来完成的。 相似文献
3.
4.
Derek C. Church Jonathan K. Pokorski 《Angewandte Chemie (International ed. in English)》2020,59(28):11379-11383
Cell‐based therapies are gaining prominence in treating a wide variety of diseases and using synthetic polymers to manipulate these cells provides an opportunity to impart function that could not be achieved using solely genetic means. Herein, we describe the utility of functional block copolymers synthesized by ring‐opening metathesis polymerization (ROMP) that can insert directly into the cell membrane via the incorporation of long alkyl chains into a short polymer block leading to non‐covalent, hydrophobic interactions with the lipid bilayer. Furthermore, we demonstrate that these polymers can be imbued with advanced functionalities. A photosensitizer was incorporated into these polymers to enable spatially controlled cell death by the localized generation of 1O2 at the cell surface in response to red‐light irradiation. In a broader context, we believe our polymer insertion strategy could be used as a general methodology to impart functionality onto cell‐surfaces. 相似文献
5.
通过Knoevenagel缩合反应制备了一个具有溶酶体靶向的近红外光敏剂IMBDP-Lys, 用于双光子荧光成像和光动力治疗. IMBDP-Lys由2个吲哚吗啉功能团连接到氟硼二吡咯(BODIPY)母核的3?位和8?位构筑而成, 是一种重原子诱导的光敏剂. 采用高斯09W理论计算光敏剂S1态和T2态能量值相差0.12 eV, 可以有效地发生系间窜越. 在二氯甲烷溶液中, 光敏剂IMBDP-Lys的最大吸收波长为631 nm, 最大发射波长为684 nm. 在 660 nm的光照下, 以亚甲基蓝为参比, 单线态氧量子产率经计算为48.3%. 此外, 含有2个吗啉基团的光敏剂IMBDP-Lys具有良好的生物相容性和精准的靶向能力, 可以快速地进入斑马鱼体内进行双光子荧光成像, 并且与溶酶体绿色染料Lyso-Tracker Green共定位系数为0.95. 溴化噻唑蓝四氮唑(MTT)实验结果表明, 光敏剂具有低的暗毒性(≥85%)和高的光毒性(IC50=0.52 μmol/L). 在660 nm的光照下, 利用活性氧荧光探针2’,7’-二氯二氢荧光素二乙酸酯(DCFH-DA)证明光敏剂可以产生活性氧, 同时吖啶橙/溴化乙锭(AO/EB)染色实验和细胞迁移实验表明产生的活性氧不仅能诱导A549细胞凋亡, 还能有效地抑制肿瘤细胞迁移. 因此, 近红外光敏剂IMBDP-Lys在双光子荧光成像和溶酶体靶向的光动力治疗中具有重要的应用价值. 相似文献
6.
Jannik Brückmann Dr. Carolin Müller Tamar Maisuradze Dr. Alexander K. Mengele Dr. Djawed Nauroozi Sven Fauth Andreas Gruber Prof. Dr. Stefanie Gräfe Prof. Dr. Kerstin Leopold Dr. Stephan Kupfer Prof. Dr. Benjamin Dietzek-Ivanšić Prof. Dr. Sven Rau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(51):e202200766
The synthesis and detailed characterization of a new Ru polypyridine complex containing a heteroditopic bridging ligand with previously unexplored metal-metal distances is presented. Due to the twisted geometry of the novel ligand, the resultant division of the ligand in two distinct subunits leads to steady state as well as excited state properties of the corresponding mononuclear Ru(II) polypyridine complex resembling those of prototype [Ru(bpy)3]2+ (bpy=2,2'-bipyridine). The localization of the initially optically excited and the nature of the long-lived excited states on the Ru-facing ligand spheres is evaluated by resonance Raman and fs-TA spectroscopy, respectively, and supported by DFT and TDDFT calculations. Coordination of a second metal (Zn or Rh) to the available bis-pyrimidyl-like coordination sphere strongly influences the frontier orbitals, apparent by, for example, luminescence quenching. Thus, the new bridging ligand motif offers electronic properties, which can be adjusted by the nature of the second metal center. Using the heterodinuclear Ru−Rh complex, visible light-driven reduction of NAD+ to NADH was achieved, highlighting the potential of this system for photocatalytic applications. 相似文献
7.
Yu Zhang Dr. Novruz G. Akhmedov Prof. Jeffrey L. Petersen Prof. Carsten Milsmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):3042-3052
Luminescent seven-coordinated zirconium and hafnium complexes bearing three mono-anionic 2,2′-pyridylpyrrolide ligands and one chloride were synthesized. Solid-state structures and the dynamic behaviors in solution were probed by X-ray crystallography and variable temperature 1H NMR experiments, respectively. Absorption spectroscopy and time-dependent density functional theory (TD-DFT) calculations supported a hybrid of ligand-to-metal charge transfer (LMCT)/ligand-to-ligand charge transfer (LLCT) for the visible light absorption band. The complexes (MePMPMe)3MCl (M=Zr, Hf, MePMPMe=3,5-dimethyl-2-(2-pyridyl)pyrrolide) are emissive in solution at room temperature upon irradiation with visible light due to a combination of phosphorescence and fluorescence characterized by excited state lifetimes in the μs and low to sub-ns timescale, respectively. Electrochemical experiments revealed that the zirconium complex possesses a reversible redox event under highly reducing condition (−2.29 V vs. Fc+/0). 相似文献
8.
ShiGuoSUN XiaoJunPENG MingWenFAN YongQianXU LeiSHI LiChengSU 《中国化学快报》2004,15(8):965-968
Two novel rhenium(I) 2, 2′-bipyridyl complexes, [(4,4′-di-COOEt-bipy) Re(CO)3 (NCCH3)PF6] and [(4,4′-di-COOEt-bipy) Re (CO)3 (NCS)], a model complex [(4,4′-di-COOEt-bipy) Re (CO)3 (pyridine)PF6], were synthesized. Their ground state electronic spectra and emission spectra were measured in acetonitrile. The MLCT absorption maximum of the complex exhibited a considerable red shift as the ligand changed from pyridine to CNCH3, or SCN. 相似文献
9.
以功能化氮配体为导向,以4,7-二苯基-1,10-菲咯啉为原料,经季铵化、氧化、卤化和醚化合成了一类新型的2,9-二烷氧基-4,7-二苯基-1,10-菲咯啉配体5a~5e。再以Xantphos为膦配体,通过原位配位方法合成一系列氮磷杂配铜光敏剂(CuPS A~H),在均相光解水制氢体系中研究其光敏活性。制氢结果表明,以2,9-二乙氧基为较佳取代基,CuPS D的催化产氢总转换数(TON)可达270。在光电物理性能分析中,发现这类杂配铜配合物都有一个相似的氧化还原电位(Eoxd=-0.8 V,Ered=-1.2 V)。具有乙氧取代基的铜配合物CuPS D相对于其他取代基的铜基配合物,荧光最弱,表明乙氧基有助于提高荧光淬灭效率,增强铜光敏剂的光化学转换能力。 相似文献
10.
Synthesis of Cationic Dumbbell-shaped Fullerene Nanostructures as Potential Photodynamic Sensitizers
A design of novel hydrophilic tetracationic dumbbell-shaped [60]fullerene nanostructures was made by balancing the hydrophilicity and hydrophobicity characteristics of the fullerene adduct for their potential application as photodynamic sensitizers in the PDT treatment. A sequential protection-deprotection reaction pathway was applied for the functional differentiation between primary and secondary amine moieties of pentaethylene hexamine. Synthesis of the target molecule involves two key steps of unsymmetrical esterification and amidation of malonic acid and subsequent fullerenation. The synthetic strategy was accomplished using mild reaction conditions in the intermediate molecule preparation and led a moderate overall product yield. 相似文献