全文获取类型
收费全文 | 27060篇 |
免费 | 3531篇 |
国内免费 | 2867篇 |
专业分类
化学 | 12794篇 |
晶体学 | 203篇 |
力学 | 1286篇 |
综合类 | 159篇 |
数学 | 1824篇 |
物理学 | 7176篇 |
综合类 | 10016篇 |
出版年
2024年 | 116篇 |
2023年 | 472篇 |
2022年 | 781篇 |
2021年 | 866篇 |
2020年 | 866篇 |
2019年 | 700篇 |
2018年 | 652篇 |
2017年 | 621篇 |
2016年 | 927篇 |
2015年 | 1027篇 |
2014年 | 1306篇 |
2013年 | 1522篇 |
2012年 | 1923篇 |
2011年 | 1969篇 |
2010年 | 1411篇 |
2009年 | 1342篇 |
2008年 | 1567篇 |
2007年 | 1398篇 |
2006年 | 1466篇 |
2005年 | 1255篇 |
2004年 | 1005篇 |
2003年 | 900篇 |
2002年 | 926篇 |
2001年 | 849篇 |
2000年 | 728篇 |
1999年 | 918篇 |
1998年 | 740篇 |
1997年 | 746篇 |
1996年 | 699篇 |
1995年 | 579篇 |
1994年 | 555篇 |
1993年 | 472篇 |
1992年 | 453篇 |
1991年 | 347篇 |
1990年 | 333篇 |
1989年 | 283篇 |
1988年 | 263篇 |
1987年 | 169篇 |
1986年 | 114篇 |
1985年 | 66篇 |
1984年 | 38篇 |
1983年 | 35篇 |
1982年 | 15篇 |
1981年 | 21篇 |
1980年 | 7篇 |
1979年 | 2篇 |
1966年 | 1篇 |
1957年 | 5篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
891.
In this study, a more sensitive and reliable quantitative method based on ultra‐high performance liquid chromatography coupled with Q‐Exactive‐Orbitrap‐MS in full‐mass scan was developed and validated for the determination of PF‐04620110 in dog plasma. After protein precipitation with acetonitrile, the sample separations were carried out on an Acquity BEH C18 column with 1 mm ammonium acetate in water and acetonitrile containing 0.1% acetic acid as mobile phase, at a flow rate of 0.4 mL/min. The assay showed excellent linearity over the concentration range of 1–2000 ng/mL with correlation coefficient >0.9980 (r > 0.9980). The LLOQ was 1 ng/mL. The inter‐ and intra‐day precision (RSD, %) was within 9.69% while the accuracy (RE, %) was in the range of ?8.59–11.24%. The extraction recovery was >85.37% and the assay was free of matrix effects. PF‐04620110 was demonstrated to be stable under various processing and handing conditions. The validated method was successfully applied to the pharmacokinetic study of PF‐04620110 in dogs and the results revealed that PF‐04620110 was slowly eliminated from plasma with a clearance of 60.81 ± 7.11 mL/h/kg for intravenous administration and 81.44 ± 25.79 mL/h/kg for oral administration. The oral bioavailability was determined to be 77.89% in dogs. 相似文献
892.
Fanfan Du Ying Zheng Wenhua Yuan Guorong Shan Yongzhong Bao Suyun Jie Pengju Pan 《Journal of polymer science. Part A, Polymer chemistry》2019,57(2):90-100
Development of effective organocatalysts for the living ring‐opening polymerization (ROP) of lactones is highly desired for the preparation of biocompatible and biodegradable polyesters with controlled microstructures and physical properties. Herein, a new class of hydrogen‐bond donating bisurea catalysts is reported for the ROP of lactones under solvent‐free conditions. ROP of lactones mediated by the bisurea/7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD) catalyst exhibits a living/controlled manner, affording the polymers and copolymers with the well‐defined structure, predictable molecular weight, narrow molecular weight distribution, and high selectivity for monomer at low catalyst loadings at ambient temperature. The possible mechanism of bisurea/MTBD‐catalyzed ROP of lactones is proposed, in which the bisurea activates the carbonyl group of lactones while MTBD facilitates the nucleophilic attack of the initiating/propagating alcohol by hydrogen bonding. Moreover, the poly(ε‐caprolactone‐co‐δ‐valerolactone) [P(CL‐co‐VL)] random copolymers with various compositions were synthesized using the bisurea/MTBD catalyst. The measurements of thermal properties and crystalline structure demonstrate that the CL and VL units are cocrystallized in the crystalline phase of P(CL‐co‐VL) copolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 90–100 相似文献
893.
Ling-Ying Xia Dr. Ying-Ning Zheng Prof. Wen-Bin Liang Dr. Meng-Jie Li Tao Hu Prof. Ruo Yuan Prof. Ya-Qin Chai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(16):4087-4092
A new cosensitization photoelectrochemical (PEC) strategy was established by using a donor–acceptor-type photoactive material, poly{4,8-bis[5-(2-ethylhexyl)thiophen-2-yl]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl-alt-3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophene-4,6-diyl} (PTB7-Th), as a signal indicator, which was cosensitized with bis(4,4′dicarboxyl-2,2′-bipyridyl)(4,5,9,14-tetraazabenzo[b]triphenylene)ruthenium(II) ([Ru(dcbpy)2dppz]2+) embedded in the grooves of the DNA duplex and fullerene (nano-C60) immobilized on the surface of DNA nanoflowers for microRNA assay. [Ru(dcbpy)2dppz]2+ and nano-C60 could effectively enhance the photoelectric conversion efficiency (PCE) of PTB7-Th as a result of well-matched energy levels among nano-C60, [Ru(dcbpy)2dppz]2+ and PTB7-Th, leading to a clearly enhanced photocurrent signal. Meanwhile, a target recycling magnification technique based on duplex-specific nuclease was applied in this work to obtain higher detection sensitivity. The proposed biosensor demonstrated excellent analytical properties within a linear detection range of 2.5 fm to 2.5 nm and a limit of detection down to 0.83 fm . Impressively, this cosensitization PEC strategy offers an effective and convenient avenue to significantly improve the PCE of a photoactive material, resulting in a remarkably improved photocurrent signal for ultrasensitive and highly accurate detection of various targets. 相似文献
894.
Dr. Lu Peng Dr. Ruirui Wei Yifei Guo Xiaokun Zheng Yue Zheng Yiwen Ding Prof. Yu Xiang Prof. Aijun Tong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(34):8043-8052
Tuning fluorescence colour of solid-state materials has become a topic of increasing interest for both fundamental mechanism study and practical applications such as sensors, optical recording and security printing. In this work, a fluorescent colour tuneable molecule BA-C16 is rationally designed and facilely synthesized by attaching flexible long alkyl chains to 2-hydroxybenzophenone azine ( BA ), which shows both aggregation-induced emission (AIE) and excited-state intramolecular proton transfer (ESIPT) characteristics. Compared to BA , the simple introduction of long alkyl chains in BA-C16 leads to an emission wavelength redshift from 542 to 558 nm. This strategy of extending emission wavelength is rarely reported, and is ascribed to the enlarged through-space π-conjugation between interplanar molecules in the aggregate of BA-C16 . Three crystals of BA-C16 are obtained with green, yellowish green and yellow emission. According to characterization by X-ray crystallography, X-ray powder diffraction and differential scanning calorimetry, alkyl chains play an important role in inducing different stacking modes of the three crystals, which further leads to polymorph-dependent fluorescence colour. BA-C16 exhibits tuneable solid-state fluorescence upon vapor fumigation, or annealing based on a transition between a “near-monomer” crystalline state and a “dimer” crystalline state. BA-C16 is further applied for rewritable fluorescence printing tuned by vapor- and thermal-treatment. 相似文献
895.
Anxun Zheng Chang Shen Prof. Qian Tang Dr. Cheng-Bin Gong Dr. Cheuk-Fai Chow 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(41):9643-9649
Herein, a catalytic chemosensing assay (CCA), based on a bimetallic complex, [RuII(bpy)2(CN)2]2(CuII)2 (bpy=2,2′-bipyridine), is described. This complex integrates a task-specific catalyst (CuI-catalyst) and a signaling unit ([RuII(bpy)2(CN)2]) to specifically hydrolyze methyl parathion, a highly toxic organophosphate (OP) pesticide. The bimetallic complex catalyzed the hydrolysis of the phosphate ester to generate o,o-dimethyl thiophosphate (DTP) anion and 4-nitrophenolate. Intrinsically, 4-nitrophenolate absorbed UV/Vis light at λmax=400 nm, creating the first level of the chemosensing signal. DTP interacted with the original complex to displace the chromophore, [RuII(bpy)2(CN)2], which was monitored by spectrofluorometry; this was classified as the second level of chemosensing signal. By integrating both spectroscopic and spectrofluorometric signals with a simple AND logic gate, only methyl parathion was able to provide a positive response. Other aromatic and aliphatic OP pesticides (diazinon, fenthion, meviphos, terbufos, and phosalone) and 4-nitrophenyl acetate provided negative responses. Furthermore, owing to the metal-catalyzed hydrolysis of methyl parathion, the CCA system led to the detoxification of the pesticide. The CCA system also demonstrated its catalytic chemosensing properties in the detection of methyl parathion in real samples, including tap water, river water, and underground water. 相似文献
896.
Zi-Han Li Yuan-Qi Zhai Dr. Wei-Peng Chen Dr. You-Song Ding Prof. Dr. Yan-Zhen Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(71):16219-16224
Eight-coordinated DyIII centres with D6h symmetry are expected to act as high-performance single-molecule magnets (SMMs) due to the simultaneous fulfilment of magnetic axiality and a high coordination number (a requisite for air stability). But the experimental realization is challenging due to the requirement of six coordinating atoms in the equatorial plane of the hexagonal bipyramid; this is usually too crowded for the central DyIII ion. Here a hexaaza macrocyclic Schiff base ligand and finetuned axial alkoxide/phenol-type ligands are used to show that a family of hexagonal bipyramidal DyIII complexes can be isolated. Among them, three complexes possess nearly perfect D6h local symmetry. The highest effective magnetic reversal barrier is found at 1338(3) K and an open hysteresis temperature of 6 K at the field sweeping rate of 1.2 mT s−1; this represents a new record for D6h SMMs. 相似文献
897.
金属调控蛋白是微生物体内通过转录抑制或激活机制严格控制金属离子摄入、外排和储存的特异性金属离子结合蛋白,对维持体内适宜的金属离子浓度和平衡起着举足轻重的作用。本文综述了目前主要的七大家族金属调控蛋白的调控机制和拓扑结构,详细介绍了金属离子结合区域的结构特征和金属-配体的配位构型。基于金属-配体的配位构型,重点讨论了每类金属调控蛋白对目标金属离子特异性选择的机理。此外,本文还介绍了金属调控蛋白在重金属离子检测和吸附方面的应用,拓展了金属调控蛋白的研究和应用领域,同时为生物无机化学的研究方向开辟了新的思路。 相似文献
898.
Wang Yao Cui Jiewu Wang Yan Yu Dongbo Cheng Sheng Zheng Hongmei Shu Xia Zhang Yong Wu Yucheng 《Journal of Solid State Electrochemistry》2019,23(1):135-142
Journal of Solid State Electrochemistry - Substrate materials play a significant role in the improvement of electrochemical biosensors. In the present work, NiO nanoflake arrays were fully and... 相似文献
899.
Chang Mingning Wang He Zheng Yonglei Li Ningning Chen Siheng Wan Yong Yuan Feng Shao Weiquan Xu Sheng 《Journal of Solid State Electrochemistry》2019,23(2):607-613
Journal of Solid State Electrochemistry - Li1.2Ni1/3Co1/3Mn1/3O2 was synthesized as a cathode material for lithium-ion batteries and coated with various amounts of CoAl2O4 (0–5 wt%)... 相似文献
900.
Li-Dan Lin Prof. Dr. Dan Zhao Prof. Dr. Xin-Xiong Li Prof. Dr. Shou-Tian Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):442-453
During the past decade, research on the design and synthesis of zeolite-like metal–organic frameworks (ZMOFs) has developed greatly. As an important subclass of ZMOFs, zeolite-like cluster organic frameworks (ZCOFs) built from 4-connected metal-cluster secondary building units (SBUs) and appropriate linear organic ligand bridges have attracted sustained interest, because such materials not only integrate the merits of inorganic zeolites, ZMOFs, and metal clusters, including interesting topologies, high surface areas, extra-large cavities and channels, structural tunability, and unique physicochemical properties from various metal clusters, but also open up a new avenue to design and fabricate hybrid zeolite-like materials that have many potential applications in material sciences. In this review, recent developments in ZCOFs are summarized by classifying the ZCOFs into four categories according to the composition of the SBUs: 1) ZCOFs based on metal–halide cluster SBUs, 2) ZCOFs based on metal–oxygen cluster SBUs, 3) ZCOFs based on metal–chalcogen cluster SBUs, and 4) ZCOFs based on mixed types of metal-cluster SBUs. Besides, challenges associated with the design and synthesis of ZCOFs and the vast potential of this area are also discussed. 相似文献