全文获取类型
收费全文 | 15433篇 |
免费 | 2806篇 |
国内免费 | 1822篇 |
专业分类
化学 | 11049篇 |
晶体学 | 160篇 |
力学 | 1132篇 |
综合类 | 65篇 |
数学 | 1655篇 |
物理学 | 6000篇 |
出版年
2024年 | 15篇 |
2023年 | 339篇 |
2022年 | 351篇 |
2021年 | 502篇 |
2020年 | 630篇 |
2019年 | 585篇 |
2018年 | 530篇 |
2017年 | 483篇 |
2016年 | 836篇 |
2015年 | 728篇 |
2014年 | 919篇 |
2013年 | 1130篇 |
2012年 | 1459篇 |
2011年 | 1444篇 |
2010年 | 983篇 |
2009年 | 921篇 |
2008年 | 1071篇 |
2007年 | 945篇 |
2006年 | 855篇 |
2005年 | 761篇 |
2004年 | 531篇 |
2003年 | 434篇 |
2002年 | 423篇 |
2001年 | 348篇 |
2000年 | 305篇 |
1999年 | 306篇 |
1998年 | 262篇 |
1997年 | 232篇 |
1996年 | 266篇 |
1995年 | 266篇 |
1994年 | 186篇 |
1993年 | 147篇 |
1992年 | 151篇 |
1991年 | 145篇 |
1990年 | 125篇 |
1989年 | 101篇 |
1988年 | 85篇 |
1987年 | 67篇 |
1986年 | 50篇 |
1985年 | 41篇 |
1984年 | 30篇 |
1983年 | 25篇 |
1982年 | 14篇 |
1981年 | 16篇 |
1980年 | 9篇 |
1978年 | 2篇 |
1972年 | 1篇 |
1957年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Dr. Gao Li Wu-Yue Yang Wen-Hao Li Yun-Yi Luo Yeh-Jun Lim Prof. Dr. Yang Li Dr. Ashim Paul Prof. Dr. Daniel Segal Liu Hong Prof. Dr. Yan-Mei Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(16):3499-3503
It has been reported that many molecules could inhibit the aggregation of Aβ (amyloid-β) through suppressing either primary nucleation, secondary nucleation, or elongation processes. In order to suppress multiple pathways of Aβ aggregation, we screened 23 small molecules and found two types of inhibitors with different inhibiting mechanisms based on chemical kinetics analysis. Trp-glucose conjugates ( AS2 ) could bind with fibril ends while natural products ( D3 and D4 ) could associate with monomers. A cocktail of these two kinds of molecules achieved co-inhibition of various fibrillar species and avoid unwanted interference. 相似文献
72.
Prof. Dr. Qian Miao Dr. Farzaneh Rouhani Dr. Hamed Moghanni-Bavil-Olyaei Dr. Kuan-Guan Liu Xue-Mei Gao Jing-Zhe Li Xiu-De Hu Prof. Dr. Zhi-Min Jin Prof. Mao-Lin Hu Prof. Ali Morsali 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9518-9526
As redox-active based supercapacitors are known as highly desirable next-generation supercapacitor electrodes, the targeted design of two ferrocene-functionalized (Fc(COOH)2) clusters based on coinage metals, [(PPh3)2AgO2CFcCO2Ag(PPh3)2]2 ⋅ 7 CH3OH (SC1: super capacitor) and [(PPh3)3CuO2CFcCO2Cu(PPh3)3] ⋅ 3 CH3OH (SC2), is reported. Both structures are fully characterized by various techniques. The structures are utilized as energy storage electrode materials, giving 130 F g−1 and 210 F g−1 specific capacitance at 1.5 A g−1 in Na2SO4 electrolyte, respectively. The obtained results show that the presence of CuI instead of AgI improves the supercapacitive performance of the cluster. Further, to improve the conductivity, the PSC2 ([(PPh3)2CuO2CFcCO2]∞), a polymeric structure of SC2, was synthesized and used as an energy storage electrode. PSC2 displays high conductivity and gives 455 F g−1 capacitance at 3 A g−1. The PSC2 as a supercapacitor electrode presents a high power density (2416 W kg−1), high energy density (161 Wh kg−1), and long cycle life over 4000 cycles (93 %). These results could lead to the amplification of high-performance supercapacitors in new areas to develop real applications and stimulate the use of the targeted design of coordination polymers without hybridization or compositions with additive materials. 相似文献
73.
Honghua Zhang Huihong Wang Yi Jiang Fei Cao Weiwei Gao Longqing Zhu Yuhang Yang Xiaodong Wang Yongqiang Wang Jinhong Chen Yiyue Feng Xuemei Deng Yingmei Lu Xiaoling Hu Xiangxiang Li Juan Zhang Tao Shi Prof. Zhen Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17289-17317
Sulfur-containing scaffold, as a ubiquitous structural motif, has been frequently used in natural products, bioactive chemicals and pharmaceuticals, particularly C−S/N−S bonds are indispensable in many biological important compounds and pharmaceuticals. Development of mild and general methods for C−S/N−S bonds formation has great significance in modern research. Iodine and its derivatives have been recognized as inexpensive, environmentally benign and easy-handled catalysts or reagents to promote the construction of C−S/N−S bonds under mild reaction conditions, with good regioselectivities and broad substrate scope. Especially based on this, several new strategies, such as oxidation relay strategy, have been greatly developed and accelerated the advancement of this field. This review focuses on recent advances in iodine and its derivatives promoted hybridized C−S/N−S bonds formation. The features and mechanisms of corresponding reactions are summarized and the results of some cases are compared with those of previous reports. In addition, the future of this domain is discussed. 相似文献
74.
Dr. Yanwei Cao Wenjing Li Tian Gao Pi Ding Prof. Dr. Renjun Pei 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(39):8631-8638
Numerous studies have shown compelling evidence that incorporation of an inversion of polarity site (IPS) in G-rich sequences can affect the topological and structural characteristics of G-quadruplexes (G4s). Herein, the influence of IPS on the formation of a previously studied intramolecular parallel G4 of d(G3TG3TG3TG3) (TTT) and its stacked higher-order structures is explored. Insertion of 3′–3′ or 5′–5′ IPS did not change the parallel folding pattern of TTT. However, both the species and position of the IPS in TTT have a significant impact on the G4 stability and end-stacking through the alteration of G4–G4 interfaces properties. The data demonstrate that one base flip in each terminal G-tetrad can stabilize parallel G4s and facilitate intermolecular packing of monomeric G4s. Such modifications can also enhance the fluorescence and enzymatic performances by promoting interactions between parallel G4s with N-methyl mesoporphyrin IX (NMM) and hemin, respectively. 相似文献
75.
Dr. Jindong Ren Dr. Henning Klaasen Melanie C. Witteler Lena Viergutz Prof. Dr. Johannes Neugebauer Dr. Hong-Ying Gao Prof. Dr. Armido Studer Prof. Dr. Harald Fuchs 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(70):16727-16732
The reactivity of aryl triflates in on-surface C−C coupling is reported. It is shown that the triflate group in aryl triflates enables regioselective homo coupling with preceding or concomitant hydrodetriflation on Cu(111). Three different symmetrical π-systems with two and three triflate functionalities were used as monomers leading to oligomeric conjugated π-systems. The cascade, comprising different intermediates at different reaction temperatures as observed for one of the molecules, proceeds via initial removal of the trifluoromethyl sulfonyl group to give an aryloxy radical which in turn is deoxygenated to the corresponding aryl radical. Thermodynamically driven regioselective 1,2-hydrogen atom transfer leads to a translocated aryl radical which in turn undergoes coupling. For a sterically more hindered bistriflate, where one ortho position was blocked, dehydrogenative coupling occurred at remote position with good regioselectivity. Starting materials, intermediates as well as products were analyzed by scanning tunneling microscopy. Structures and suggested mechanism were further supported by DFT calculations. 相似文献
76.
77.
ABSTRACTA striking feature of lyotropic chromonic liquid crystals confined in cylinder model exhibit double-twist director configurations. Evidence suggests that saddle-splay deformation is among the most important factors for the distortions of director. Previous researches limit the director to distort at a fixed plane (r-? plane) by using specific boundary conditions such as degenerate planar anchoring condition. In this work, we consider lyotropic chromonic liquid crystals confined between two coaxial cylinders with free-surface boundary conditions and Rapini-Papoular-type anchoring conditions. By using finite-difference iterative method to solve the numerical solution of Euler equation, we find that saddle-splay deformation leads to double-twist director configurations under free-surface boundary conditions, which consist of the result under degenerate planar anchoring conditions. Furthermore, at Rapini-Papoular-type anchoring conditions, saddle-splay deformation has a great influence on the director in the radial direction (r direction) and the director distorts in three-dimensional space. Remarkably, our method provides a more accurate theory basis for the measured values of saddle-splay elastic constant K24。 相似文献
78.
Yan Gao Saimeng Zhang Xiaoguang Li Shuyao Jiang Yajing Yang Xiaohong Chang 《应用有机金属化学》2020,34(2):e5330
Salicylaldimine-bridged dinuclear cyclopalladated complexes were synthesized by the reactions of cyclopalladated chloro dimers [Pd{(4-R)C6H3CH=N-C6H3–2,6-i-Pr2}(μ-Cl)]2 (R = H; OMe) with salen-based bridging ligands. The complexes were characterized by FTIR, NMR spectroscopy, elemental analysis and X-ray crystallography. The binding interaction of cyclopalladated complexes to bovine serum albumin (BSA) was investigated by UV–vis, fluorescence and synchronous fluorescence spectroscopy. The experimental results showed that these Pd (II) complexes could bind to BSA with high affinity and quench its intrinsic fluorescence by a static or combined process. Also the interaction of Pd complexes with BSA affected the conformation of the tryptophan and tyrosine residues. 相似文献
79.
New pyridinium-functionalized metalloporphyrins MEtPpBr4 (M = Zn2+, Co2+, Ni2+, Cu2+; EtPp = 5, 10, 15, 20-tetra(4-(3-(N-ethyl-4-pyridyl)pyrazolyl)phenyl)porphyrin) were synthesized as bifunctional catalysts for the cycloaddition reactions of epoxides and CO2. The effects of catalyst loading, CO2 pressure, reaction temperature and time on catalytic activity were investigated. ZnEtPpBr4 ( 1 ) and CoEtPpBr4 ( 2 ) exhibited efficient activities in the cycloaddition reactions of various epoxides with CO2 as at 120 °C under 2 MPa of CO2 pressure without solvent. Most of corresponding cyclic carbonates could be obtained in almost quantitative yields and > 99.9% selectivity with molar ratio of epoxide/catalyst 2222 after 8 hr of reaction. 相似文献
80.
Three novel complexes, namely [Nd·L1·HCOO·(H2O)4] ( 1 ), [Pr·L1·HCOO·(H2O)4] ( 2 ) and [In·L2·Cl·(H2O)2] ( 3 ) (L1 = 1,1-bis(5-(pyrazin-2-yl)-1,2,4-triazol-3-yl)methane, L2 = 1,1-bis(5-(pyrazin-2-yl)-1,2,4-triazol-3-yl)ketone), were synthesized and characterized. The molecular structures of 1 – 3 were confirmed using single-crystal X-ray diffraction. All three obtained complexes are zero-dimensional and connected to each other by hydrogen bonds. In 1 and 2 the metal is surrounded by nine donors and 3 has seven coordination sites. The interaction of 1 – 3 with calf thymus DNA (CT-DNA) was explored using UV absorption spectra and fluorescence spectra. The intrinsic binding constants of 1 – 3 with CT-DNA are about 1.9 × 104, 1.4 × 104 and 1.1 × 104, respectively. Stern–Volmer quenching plots of 1 – 3 have slopes of 0.1508, 0.134 and 0.1205, respectively. The ability of these complexes to cleave pBR322 plasmid DNA was demonstrated using gel electrophoresis assay. Apoptosis studies of the three novel complexes showed a significant inhibitory effect on HeLa cells. Furthermore, MTT assays were used to evaluate the anticancer activity of the three complexes. The cytotoxicity study indicated that complex 1 possesses a higher inhibitory rate of HeLa cells than the other complexes. Especially, the efficacy of 1 was shown to be the highest for cisplatin at 24 h. A further molecular docking technique was introduced to understand the binding of the complexes toward the target DNA. 相似文献