全文获取类型
收费全文 | 145569篇 |
免费 | 29024篇 |
国内免费 | 13517篇 |
专业分类
化学 | 113435篇 |
晶体学 | 1502篇 |
力学 | 7814篇 |
综合类 | 737篇 |
数学 | 15662篇 |
物理学 | 48960篇 |
出版年
2024年 | 428篇 |
2023年 | 2486篇 |
2022年 | 4118篇 |
2021年 | 4437篇 |
2020年 | 5688篇 |
2019年 | 6490篇 |
2018年 | 4842篇 |
2017年 | 4307篇 |
2016年 | 8574篇 |
2015年 | 8567篇 |
2014年 | 9649篇 |
2013年 | 12154篇 |
2012年 | 12970篇 |
2011年 | 12592篇 |
2010年 | 9720篇 |
2009年 | 9429篇 |
2008年 | 9438篇 |
2007年 | 8104篇 |
2006年 | 7300篇 |
2005年 | 6357篇 |
2004年 | 5119篇 |
2003年 | 4231篇 |
2002年 | 4806篇 |
2001年 | 3745篇 |
2000年 | 3447篇 |
1999年 | 2727篇 |
1998年 | 2084篇 |
1997年 | 1992篇 |
1996年 | 2000篇 |
1995年 | 1703篇 |
1994年 | 1483篇 |
1993年 | 1242篇 |
1992年 | 1095篇 |
1991年 | 1005篇 |
1990年 | 819篇 |
1989年 | 654篇 |
1988年 | 450篇 |
1987年 | 390篇 |
1986年 | 410篇 |
1985年 | 337篇 |
1984年 | 209篇 |
1983年 | 154篇 |
1982年 | 119篇 |
1981年 | 74篇 |
1980年 | 52篇 |
1979年 | 27篇 |
1977年 | 6篇 |
1976年 | 9篇 |
1975年 | 8篇 |
1957年 | 35篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine 下载免费PDF全文
Diego García‐Gómez Encarnación Rodríguez‐Gonzalo Rita Carabias‐Martínez 《Biomedical chromatography : BMC》2015,29(8):1190-1196
In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
52.
53.
DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex 下载免费PDF全文
Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献
54.
Rong Yin Jihui Zhang Xudong Shang 《Mathematical Methods in the Applied Sciences》2020,43(15):8736-8752
This paper is dedicated to studying the following Schrödinger–Poisson system Under some different assumptions on functions V(x), K(x), a(x) and f(u), by using the variational approach, we establish the existence of positive ground state solutions. 相似文献
55.
56.
Naphthalimide‐phthalimide derivative based photoinitiating systems for polymerization reactions under blue lights 下载免费PDF全文
Pu Xiao Frédéric Dumur Jing Zhang Bernadette Graff Didier Gigmes Jean Pierre Fouassier Jacques Lalevée 《Journal of polymer science. Part A, Polymer chemistry》2015,53(5):665-674
Naphthalimide‐phthalimide derivatives (NDPDs) have been synthesized and combined with an iodonium salt, N‐vinylcarbazole, amine or 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine to produce reactive species (i.e., radicals and cations). These generated reactive species are capable of initiating the cationic polymerization of epoxides and/or the radical polymerization of acrylates upon exposure to very soft polychromatic visible lights or blue lights. Compared with the well‐known camphorquinone based systems used as references, the novel NDPD based combinations employed here demonstrate clearly higher efficiencies for the cationic polymerization of epoxides under air as well as the radical polymerization of acrylates. Remarkably, one of the NDPDs (i.e., NDPD2) based systems is characterized by an outstanding reactivity. The structure/reactivity/efficiency relationships of the investigated NDPDs were studied by fluorescence, cyclic voltammetry, laser flash photolysis, electron spin resonance spin trapping, and steady state photolysis techniques. The key parameters for their reactivity are provided. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 665–674 相似文献
57.
Nonclassical light states are important for both conceptual and practical reasons: they are basic ingredients in testing and exploring quantum foundations, and are crucial resources in quantum technologies. Various useful criteria have been developed to detect nonclassicality in the literature, and several meaningful measures of nonclassicality have been introduced and measured experimentally. In this work, by use of a non-Hermitian generalization of the Wigner-Yanase-Dyson skew information and playing with operator ordering in evaluating average photon number, we develop a novel family of criteria for detecting nonclassicality of light based on Lieb's concavity, which is a deep and powerful result concerning interaction between quantum states and observables. We elucidate the information-theoretic as well as the physical meaning of the criteria, and illustrate their effectiveness in capturing and quantifying nonclassicality of various important light states. 相似文献
58.
Kai He Tsegaye TadesseTsega Xi Liu Jiantao Zai Xin‐Hao Li Xuejiao Liu Wenhao Li Nazakat Ali Xuefeng Qian 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(34):12029-12035
The modulation of electron density is an effective option for efficient alternative electrocatalysts. Here, p‐n junctions are constructed in 3D free‐standing FeNi‐LDH/CoP/carbon cloth (CC) electrode (LDH=layered double hydroxide). The positively charged FeNi‐LDH in the space‐charge region can significantly boost oxygen evolution reaction. Therefore, the j at 1.485 V (vs. RHE) of FeNi‐LDH/CoP/CC achieves ca. 10‐fold and ca. 100‐fold increases compared to those of FeNi‐LDH/CC and CoP/CC, respectively. Density functional theory calculation reveals OH? has a stronger trend to adsorb on the surface of FeNi‐LDH side in the p‐n junction compared to individual FeNi‐LDH further verifying the synergistic effect in the p‐n junction. Additionally, it represents excellent activity toward water splitting. The utilization of heterojunctions would open up an entirely new possibility to purposefully regulate the electronic structure of active sites and promote their catalytic activities. 相似文献
59.
Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons 下载免费PDF全文
Dr. François Riobé Rózsa Szűcs Dr. Pierre‐Antoine Bouit Dr. Denis Tondelier Bernard Geffroy Fátima Aparicio Julia Buendía Prof. Luis Sánchez Prof. Régis Réau Prof. László Nyulászi Prof. Muriel Hissler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6547-6556
We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs). 相似文献
60.