全文获取类型
收费全文 | 12704篇 |
免费 | 1666篇 |
国内免费 | 1067篇 |
专业分类
化学 | 8954篇 |
晶体学 | 142篇 |
力学 | 661篇 |
综合类 | 66篇 |
数学 | 1507篇 |
物理学 | 4107篇 |
出版年
2023年 | 205篇 |
2022年 | 231篇 |
2021年 | 351篇 |
2020年 | 497篇 |
2019年 | 436篇 |
2018年 | 381篇 |
2017年 | 378篇 |
2016年 | 565篇 |
2015年 | 562篇 |
2014年 | 623篇 |
2013年 | 929篇 |
2012年 | 1083篇 |
2011年 | 1121篇 |
2010年 | 788篇 |
2009年 | 747篇 |
2008年 | 857篇 |
2007年 | 702篇 |
2006年 | 676篇 |
2005年 | 601篇 |
2004年 | 515篇 |
2003年 | 441篇 |
2002年 | 386篇 |
2001年 | 280篇 |
2000年 | 240篇 |
1999年 | 192篇 |
1998年 | 129篇 |
1997年 | 132篇 |
1996年 | 142篇 |
1995年 | 125篇 |
1994年 | 91篇 |
1993年 | 103篇 |
1992年 | 74篇 |
1991年 | 60篇 |
1990年 | 60篇 |
1989年 | 58篇 |
1988年 | 50篇 |
1987年 | 44篇 |
1986年 | 54篇 |
1985年 | 67篇 |
1984年 | 61篇 |
1983年 | 46篇 |
1982年 | 43篇 |
1981年 | 34篇 |
1980年 | 32篇 |
1979年 | 36篇 |
1978年 | 27篇 |
1977年 | 24篇 |
1976年 | 29篇 |
1975年 | 29篇 |
1974年 | 18篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Guanlin Li Ling Zhao Yicong Luo Youbin Peng Kai Xu Dr. Xiaohong Huo Prof. Dr. Wanbin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(24):e202200273
Asymmetric desymmetrization has been demonstrated to be a powerful strategy for building stereocenters in asymmetric synthesis. Herein, a Pd/Cu catalyzed asymmetric desymmetrization reaction with a simple geminal dicarboxylate is reported. A wide scope of imino esters bearing an aryl or heteroaromatic group were compatible with this bimetallic catalytic system. The reactions proceeded smoothly, giving the desired products in good yields with high to excellent regio-, diastereo-, and enantioselectivity (up to 20 : 1 branched:linear, >20 : 1 dr, >99 % ee). Notably, the reaction favored branched selectivity, which is unusual for the Pd-catalyzed allylic alkylation reaction. In addition, the standard product could be easily transformed to other valuable molecules such as chiral allylic alcohols, carbamates, and organic boron compounds. Furthermore, DFT calculations were conducted to explain the origin of the branched selectivity. 相似文献
2.
Kai Cheng Xiao-Shuai Zhang Jie An Cheng Li Ruo-Yun Zhang Run Ye Prof. Dr. Bang-Jiao Ye Prof. Dr. Bo Liu Prof. Dr. Yuan-Di Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(31):7553-7560
Given their superior penetration depths, photosensitizers with longer absorption wavelengths present broader application prospects in photodynamic therapy (PDT). Herein, Ag2S quantum dots were discovered, for the first time, to be capable of killing tumor cells through the photodynamic route by near-infrared light irradiation, which means relatively less excitation of the probe compared with traditional photosensitizers absorbing short wavelengths. On modification with polydopamine (PDA), PDA-Ag2S was obtained, which showed outstanding capacity for inducing reactive oxygen species (increased by 1.69 times). With the addition of PDA, Ag2S had more opportunities to react with surrounding O2, which was demonstrated by typical triplet electron spin resonance (ESR) analysis. Furthermore, the PDT effects of Ag2S and PDA-Ag2S achieved at longer wavelengths were almost identical to the effects produced at 660 nm, which was proved by studies in vitro. PDA-Ag2S showed distinctly better therapeutic effects than Ag2S in experiments in vivo, which further validated the enhanced regulatory effect of PDA. Altogether, a new photosensitizer with longer absorption wavelength was developed by using the hitherto-unexplored photodynamic function of Ag2S quantum dots, which extended and enhanced the regulatory effect originating from PDA. 相似文献
3.
A variety of heterobiaryl compounds have been synthesized by the Suzuki‐Miyaura coupling reactions of heteroaryl halides with potassium aryltrifluoroborates. Pd (OAc)2 was found to be highly efficient for the Suzuki‐Miyaura coupling reactions of various heteroaryl halides with potassium aryltrifluoroborates in aqueous systems, delivering the corresponding heterobiaryl compounds in good to excellent yields. 相似文献
4.
For an integer , a graph is -hamiltonian if for any vertex subset with , is hamiltonian, and is -hamiltonian connected if for any vertex subset with , is hamiltonian connected. Thomassen in 1984 conjectured that every 4-connected line graph is hamiltonian (see Thomassen, 1986), and Ku?zel and Xiong in 2004 conjectured that every 4-connected line graph is hamiltonian connected (see Ryjá?ek and Vrána, 2011). In Broersma and Veldman (1987), Broersma and Veldman raised the characterization problem of -hamiltonian line graphs. In Lai and Shao (2013), it is conjectured that for , a line graph is -hamiltonian if and only if is -connected. In this paper we prove the following.(i) For an integer , the line graph of a claw-free graph is -hamiltonian if and only if is -connected.(ii) The line graph of a claw-free graph is 1-hamiltonian connected if and only if is 4-connected. 相似文献
5.
Yosselin Huentupil Patricio Chung Néstor Novoa A. Hugo Klahn Manuela E. Medina Jonathan Cisterna Iván Brito Andrés Rivera Rodrigo López-Muñoz Rodrigo Arancibia 《应用有机金属化学》2020,34(9):e5788
In the research of new compounds with multifunctional applications, heterobinuclear palladium (II) complexes based on organometallic dithiocarbazates (DTCZs) have been isolated. The organometallic DTCZ ligands of the general formula [{(η5-C5H4)-CH=NNHC(S)SCH3}]MLn [MLn = Re (CO)3 ( 2a ); Mn (CO)3 ( 2b ); FeCp ( 2c )] were prepared by the reaction between formyl organometallic precursors ( 1a−c ) with S-methyldithiocarbazate. Subsequently, a two-step reaction of 2a−c with: (i) K2[PdCl4] and (ii) PPh3 yielded heterobinuclear complexes [Pd{MLn(η5-C5H4)-CH=NNHC(S)SCH3}–(Cl)(PPh3)] [MLn = Re (CO)3 ( 3a ); Mn (CO)3 ( 3b ); FeCp ( 3c )]. All compounds were characterized by conventional spectroscopic techniques (infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectrometry and elemental analysis). In addition, the molecular structures of 2a , 2c and 3c were determined by single-crystal X-ray diffraction. The new palladium (II) complexes ( 3a−c ) were evaluated as antiproliferative agents against non-small cell lung cancer cells (H1299 cells). Complexes 3a and 3b containing cyrhetrenyl- and cymantrenyl-DTCZ ligands, respectively, were more active than their ferrocenyl analogue 3c . The activity was associated with the electron-withdrawing properties of the (η5-C5H4)M (CO)3 moieties and their better lipophilicity than that of the ferrocenyl analogue. In addition, we studied the capacity of metalloligands ( 2a−c ) and palladium (II) complexes ( 3a−c ) to remove methylene blue in water under UV–visible light irradiation. The results established that the complexes showed moderate efficiency and were less active than their corresponding free ligands. 相似文献
6.
Sing Lai Cong Roy Anitha Hui Lok Yong Mun Chan Sook Rajak Harish Karunakaran Rohini Ravichandran Veerasamy 《Structural chemistry》2022,33(3):649-669
Structural Chemistry - Quinoline- and acridine-based drugs are widely used as anti-breast cancer agents. These drugs act through various mechanisms of action; for example, neratinib acts on... 相似文献
7.
Nonlinear Dynamics - A multilayer membrane element of absolute nodal coordinate formulation is proposed for dynamic modeling of multilayer dielectric elastomer actuators (DEAs). The coupled... 相似文献
8.
提出了一种基于特征正交分解(POD)和有限元法的瞬态非线性热传导问题的模型降阶快速分析方法, 建立了导热系数随温度变化的一类瞬态非线性热传导问题有限元格式的POD降阶模型. 在隐式时间推进方法的基础上有效结合单元预转换方法和多级线性化方法发展了一种加速求解瞬态非线性热传导降阶模型的新型计算方法,并通过二维和三维算例验证了该方法的准确性和高效性. 研究结果表明: (1)降阶模型解的均方根误差在经过初始时段轻微的脉动后稳定于0.01%以下, 而其计算效率比有限元全阶模型提高2$\sim $3个数量级, 并且自由度数量(DOFs)愈大提高的幅度也愈加显著; (2)新型算法解决了常规算法在计算非线性降阶模型时加速性能差的问题, 即使是在DOFs比较小的时候也能够明显提高计算效率; (3)常数边界条件下得到的POD模态可以用来建立相同求解域在各种复杂时变边界条件下的瞬态非线性热传导降阶模型, 并对其传热过程和温度场进行快速准确的分析与预测, 具有很好的工程应用价值. 相似文献
9.
10.
Extraordinary transport behavior of gases in isothermally annealed poly(4‐methyl‐1‐pentene) membranes 下载免费PDF全文
Ywu‐Jang Fu Cheng‐Lee Lai Chien‐Chieh Hu Yi‐Ming Sun Shuan‐Ying Wu Jung‐Tsai Chen Shu‐Hsien Huang Wei‐Song Hung Kueir‐Rarn Lee 《Journal of Polymer Science.Polymer Physics》2016,54(22):2368-2376
Poly(4‐methyl‐1‐pentene) (PMP) membranes were modified through isothermal annealing to investigate the change of their crystalline structure and rigid and mobile amorphous fractions (RAF and MAF), assuming a three‐phase model, affected the gas transport behavior. The crystalline structure was characterized by wide‐angle X‐ray diffraction (WAXD) and small‐angle X‐ray scattering (SAXS) techniques, and the free volume properties were analyzed by positron annihilation lifetime spectroscopy. Compared with the pristine membrane, the annealed membranes show higher crystallinity; the crystals undergo partial structural change from form III to form I. The lamellar crystal thickness, rigid amorphous fraction thickness, and long period in the lamellar stacks increase with crystallinity. The annealed PMP membranes exhibit higher permeability due to the increase in larger size free volumes in MAF and higher selectivity due to the increase in smaller size free volumes in RAF, respectively. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2368–2376 相似文献