全文获取类型
收费全文 | 24167篇 |
免费 | 4441篇 |
国内免费 | 7584篇 |
专业分类
化学 | 17762篇 |
晶体学 | 1013篇 |
力学 | 1753篇 |
综合类 | 671篇 |
数学 | 3079篇 |
物理学 | 11914篇 |
出版年
2024年 | 59篇 |
2023年 | 234篇 |
2022年 | 832篇 |
2021年 | 892篇 |
2020年 | 937篇 |
2019年 | 873篇 |
2018年 | 825篇 |
2017年 | 1116篇 |
2016年 | 999篇 |
2015年 | 1338篇 |
2014年 | 1654篇 |
2013年 | 2017篇 |
2012年 | 1948篇 |
2011年 | 2255篇 |
2010年 | 2156篇 |
2009年 | 2170篇 |
2008年 | 2378篇 |
2007年 | 2099篇 |
2006年 | 2069篇 |
2005年 | 1713篇 |
2004年 | 1276篇 |
2003年 | 951篇 |
2002年 | 874篇 |
2001年 | 933篇 |
2000年 | 903篇 |
1999年 | 502篇 |
1998年 | 295篇 |
1997年 | 246篇 |
1996年 | 232篇 |
1995年 | 182篇 |
1994年 | 168篇 |
1993年 | 168篇 |
1992年 | 185篇 |
1991年 | 80篇 |
1990年 | 103篇 |
1989年 | 76篇 |
1988年 | 90篇 |
1987年 | 67篇 |
1986年 | 53篇 |
1985年 | 46篇 |
1984年 | 41篇 |
1983年 | 45篇 |
1982年 | 19篇 |
1981年 | 20篇 |
1980年 | 8篇 |
1979年 | 31篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1971年 | 5篇 |
1959年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
狄尔斯-阿尔德(Diels-Alder)可以构建结构丰富的有机化合物,被认为是现代有机化学中的基石反应之一。自1928年被发现以来,Diels-Alder (D-A)反应得到了深入发展,这主要是由于该反应能够产生六元环结构,可以一步反应得到具有四个立体中心的产物,从而大大增加分子的复杂性。这种特殊的转化已广泛应用于复杂天然产物的合成、药物化学以及材料科学等领域。近十年,大量天然生物酶(如SpnF、MaDA等)被发现可用于体外单独催化D-A反应,同时,大量的非酶催化剂(如路易斯酸、过渡金属与配体复合物等)也被应用于催化D-A反应。本文主要从D-A反应催化剂的类型分类,对近年来天然酶、酸、过渡金属、电催化等参与的D-A反应进行简要概述,同时对催化剂所存在的问题和局限性进行总结,并对今后发展做了展望。 相似文献
992.
993.
Thiacalixarene-supported Co32nanoclusters encapsulated in polyacrylonitrile nanofibers(Co32@PAN-NFs) by electrospinning have been utilized as precursors to fabricate N-doped CoO@Co9S8 carbon nanofibers(CoO@Co9S8@CNFs) for superior Li-ion storage. The S-rich Co32 clusters capped by organic sheets afforded the well dispersed cobalt oxide/sulfide nanoparticles embedded in carbon nanofiber composites by direct calcination. The N-doped CoO@Co9S8@CNFs nanocomposites have been utilized as anode materials for lithium ion battery with the reversible capabilities being of 1051.8, 967.6, 894.7, 782.7, 669.5 and 525.4 mA·h/g at 0.1, 0.2, 0.5, 1, 2 and 3 A/g, respectively. The CoO@Co9S8@CNFs also showed a relatively high stable capacity of 551.7 mA·h/g at the current density of 1 A/g after 200 cycles of rate experiments. The as-obtained N-doped CoO@Co9S8@CNFs nanocomposites exhibited superior reversible capacity, rate performance, Coulomb efficiency(74.5% vs. 63.9%) and cyclic stability comparing with the CoO@Co9S8@C derived from simple annealing of Co32 templates. 相似文献
994.
Membrane technology is of particular significance for the sustainable development of society owing to its potential capacity to tackle the energy shortage and environmental pollution. Membrane materials are the core part of membrane technology. Researchers have always been pursuing predictable structures of advanced membrane materials, which provides a possibility to fully unlock the potential of membranes. Covalent organic frameworks(COFs), with the advantage of controllable pore microenvironment, are considered to be promising candidates to achieve this design concept. The customizable function of COF membranes through pore engineering does well in the enhancement of selective permeability performance, which offers COF membranes with great application potentials in separation and transportation fields. In this context, COF-based membranes have been developed rapidly in recent years. Herein, we present a brief overview on the strategies developed for pore engineering of COF membranes in recent years, including skeleton engineering, pore surface engineering, host-guest chemistry and membrane fabrication. Moreover, the features of transmission or separation of molecules/ions based on COF membranes and corresponding applications are also introduced. In the last part, the challenges and prospects of the development of COF membranes are discussed. 相似文献
995.
Mixed Quantum Classical Reaction Rates based on the Phase Space Formulation of the Hierarchical Equations of Motion 下载免费PDF全文
In a previous work [J. Chem. Phys. 140 , 174105 (2014)], we have shown that a mixed quantum classical (MQC) rate theory can be derived to investigate the quantum tunneling effects in the proton transfer reactions. However, the method is based on the high temperature approximation of the hierarchical equation of motion (HEOM) with the Debye-Drude spectral density, and results in a multi-state Zusman type of equation. We now extend this theory to include quantum effects of the bath degrees of freedom. By writing the full HEOM into a multidimensional partial differential equation in phase space, we can define a new reaction coordinate, and the previous method can be generalized to the full quantum regime. The validity of the new method is demonstrated by using numerical examples, including the spin-Boson model, and the double well model for proton transfer reaction. The new method is found to resolve some key problems of the previous theory based on high temperature approximation, including possible numerical instability in long time simulation and wrong rate constant at low temperatures. 相似文献
996.
本研究探讨了超声内镜联合CT门静脉成像技术对肝硬化食管胃静脉曲张(GOV)程度及治疗效果的评价价值。选取72例肝硬化GOV患者为研究对象,根据食管静脉曲张套扎术(EVL)治疗效果分为良好组与不良组。结果发现,不良组总横断面表面积、胃左静脉、门静脉、脾静脉、肠系膜上静脉直径及门静脉长度均大于良好组,曲张静脉壁厚度小于良好组(P<0.05);总横断面表面积、胃左静脉、门静脉、脾静脉、肠系膜上静脉直径及门静脉长度与肝功能Child-Pugh分级、静脉曲张程度呈正相关,曲张静脉壁厚度与肝功能Child-Pugh分级、静脉曲张程度呈负相关(P<0.05);总横断面表面积、曲张静脉壁厚度/胃左静脉、门静脉、脾静脉、肠系膜上静脉直径及门静脉长度均为肝硬化GOV患者治疗效果的影响因素(P<0.05);超声内镜、CT门静脉成像参数联合预测肝硬化GOV患者治疗效果的AUC为0.857。可见,超声内镜、CT门静脉成像参数与肝硬化GOV程度、肝功能分级及EVL治疗效果密切相关,可为临床预测EVL治疗效果提供一定参考。 相似文献
997.
Comparative Analysis of Hydration Layer Reorientation Dynamics of Antifreeze Protein and Protein Cytochrome P450 下载免费PDF全文
Antifreeze proteins (AFPs) inhibit ice recrystallization by a mechanism remaining largely elusive. Dynamics of AFPs' hydration water and its involvement in the antifreeze activity have not been identified conclusively. We herein, by simulation and theory, examined the water reorientation dynamics in the first hydration layer of an AFP from the spruce budworm, Choristoneura fumiferana, compared with a protein cytochrome P450 (CYP). The increase of potential acceptor water molecules around donor water molecules leads to the acceleration of hydrogen bond exchange between water molecules. Therefore, the jump reorientation of water molecules around the AFP active region is accelerated. Due to the mutual coupling and excitation of hydrogen bond exchange, with the acceleration of hydrogen bond exchange, the rearrangement of the hydrogen bond network and the frame reorientation of water are accelerated. Therefore, the water reorientation dynamics of AFP is faster than that of CYP. The results of this study provide a new physical image of antifreeze protein and a new understanding of the antifreeze mechanism of antifreeze proteins. 相似文献
998.
为了准确测定板栗中矿物元素和稀土元素的含量水平,采用冷冻干燥方式预处理样品,选用硝酸和过氧化氢体系微波消解样品,结合电感耦合等离子体质谱技术,建立了板栗中钠(Na)、钾(K)、镁(Mg)、锰(Mn)、铁(Fe)、钒(V)、钴(Co)等19种矿物元素及镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钇(Y)等15种稀土元素的同时分析测定方法。方法检出限为0.0027~0.78μg/L,相对标准偏差为1.4%~6.3%。通过国家标准物质GBW10019苹果的准确度实验验证,测定结果均在标准证书值范围内。实验结果表明,方法适用于板栗中矿物元素及稀土元素的同时测定。 相似文献
999.
Peng Sun Zihan Xia Zhongfang Li Ziwei Fan Fengqi He Qiang Liu Xiaoyan Yin 《Materials Today Chemistry》2022
A high-temperature proton exchange membrane with high proton conductivity over a wide humidity range still remains a challenge. PBI dendrimer containing triazine rings (TPBI) was synthesized to approach this aim considering its high content of hygroscopic terminal groups and of larger free volume. A novel proton conductor previously synthesized (zirconium 3-sulfopropyl phosphonate, ZrSP) was doped due to its good proton conductivity over a wide humidity range. TPBI was post-crosslinked with a tetrafunctional epoxy resin (N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenylmethane, TGDDM) to enhance the mechanical stability at low cross-linking degrees, which allowed high doping levels of ZrSP, and thus, high conductivity. The prepared membranes (TPBI-TGDDM/ZrSP) showed good thermal stability, high proton conductivity over wide humidity range, and good dimensional stability. At suitable degrees of branching, TPBI-TGDDM/ZrSP exhibited superior mechanical property, oxidative stability, methanol barrier property, and membrane selectivity than its linear analog (mPBI-TGDDM/ZrSP). As ZrSP instead of PA was applied as the proton conductor, TPBI-TGDDM/ZrSP showed good durability of proton conductivity, especially in comparison with TPBI-TGDDM/PA, which highly retarded decline in conductivity caused by PA leaking. The proton conductivity at 180 °C of TPBI(20)-TGDDM(10)/ZrSP(50) achieved 142, 84.2 and 23.6 mS cm?1 at 100%, 50%, and 0 RH, respectively. 相似文献
1000.
Anling Li Qianrui Kang Shuaiyang Ren Yong Zhang Fengwei Zhang Qiang He 《Arabian Journal of Chemistry》2021,14(8):103247
To study the influence of different concentrations of zinc oxide (ZnO)/silicon dioxide (SiO2) composite coating on hydrophobic property and mechanical stability of paper mulch film, three kinds of ZnO/SiO2 composite coating paper mulch films (2%, 4%, 6%) with different coating substance contents were prepared by brush coating method. Through particle size analysis, contact angle, rolling angle and mechanical stability test, combined with scanning electron microscope, three-dimensional morphology and roughness measuring instrument, the optimal concentration of ZnO/SiO2 composite coated paper mulch film was screened out. Through acid-base salt corrosion test, silver mirror reaction and surface self-cleaning, the optimal concentration of composite coated paper mulch film was compared with the original paper mulch film to prove its excellent chemical stability and hydrophobicity. The results show that the paper mulch film with 4% coating material has excellent hydrophobicity and mechanical stability, can effectively reduce the surface roughness of paper mulch film, and has remarkable effects in resisting acid, alkali and salt and self-cleaning. 相似文献