全文获取类型
收费全文 | 48458篇 |
免费 | 7648篇 |
国内免费 | 5489篇 |
专业分类
化学 | 25858篇 |
晶体学 | 519篇 |
力学 | 2460篇 |
综合类 | 286篇 |
数学 | 4462篇 |
物理学 | 14699篇 |
无线电 | 13311篇 |
出版年
2024年 | 144篇 |
2023年 | 1162篇 |
2022年 | 1261篇 |
2021年 | 1718篇 |
2020年 | 1843篇 |
2019年 | 1680篇 |
2018年 | 1483篇 |
2017年 | 1446篇 |
2016年 | 2036篇 |
2015年 | 2190篇 |
2014年 | 2605篇 |
2013年 | 3200篇 |
2012年 | 3964篇 |
2011年 | 4097篇 |
2010年 | 2915篇 |
2009年 | 3036篇 |
2008年 | 3204篇 |
2007年 | 2895篇 |
2006年 | 2816篇 |
2005年 | 2218篇 |
2004年 | 1699篇 |
2003年 | 1500篇 |
2002年 | 1402篇 |
2001年 | 1183篇 |
2000年 | 1168篇 |
1999年 | 1129篇 |
1998年 | 1021篇 |
1997年 | 908篇 |
1996年 | 926篇 |
1995年 | 813篇 |
1994年 | 693篇 |
1993年 | 539篇 |
1992年 | 559篇 |
1991年 | 419篇 |
1990年 | 350篇 |
1989年 | 279篇 |
1988年 | 238篇 |
1987年 | 188篇 |
1986年 | 177篇 |
1985年 | 163篇 |
1984年 | 112篇 |
1983年 | 74篇 |
1982年 | 69篇 |
1981年 | 39篇 |
1980年 | 17篇 |
1979年 | 10篇 |
1977年 | 2篇 |
1971年 | 1篇 |
1959年 | 1篇 |
1957年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 468 毫秒
891.
CuO-BaO/SiO2催化剂的结构表征 总被引:9,自引:0,他引:9
以XRD、XPS和EXAFS手段对CuO-BaO/Sic2催化剂及其还原态的结构进行了研究.结果表明,在CuO-BaO/SiO2体系中铜和钡都是以氧化态的形式存在,超细SiO2载体对所负载的CuO的结构有影响.随着样品负载量的逐渐降低,Cu-O和Cu-Cu睡的健长和配位数逐渐征小,而且低载量样品的健长和配位数减小的幅度最大.在总负载量>13.39%的样品中,CuO以晶相的形式存在;总负载量<13.39%的样品中,CUO呈现单层分布的高分出状态.还原态样品中钢以本价铜的形式存在,随负载量的降低,还原态Cu-Cu健的镇长和配位数也分别呈现出逐渐减小的趋势.还原态中心铜原子在催化剂表面的分布状态基本上保持了氧化态催化剂中CuO物相的分市状态. 相似文献
892.
单晶X射线衍射分析表明, α-单取代环十二酮与氨衍生物羟胺和氨基硫脲发生缩合反应得到两种母体构象均为[3333], 而取代基为边外向或角反向的α-单取代环十二酮肟或缩氨基硫脲. 利用底物的“角位羰基参与反应”原理, “记忆效应”及进攻试剂与底物是否形成氢键解释了这一实验结果. 通常情况下, 试剂从空间障碍小的一面进攻羰基而生成α-角反取代环十二酮肟或缩氨基硫脲. 当试剂与底物的取代基之间能够形成分子间氢键时, 则生成α-边外取代环十二酮肟或缩氨基硫脲. 相似文献
893.
Guo-xiang Xu Lu Qi Bi-tao Yu Lei Wen Department of Applied Chemistry College of Chemistry Molecular Engineering Peking University Beijing China Department of Inorganic Nonmetal Materials School of Materials Science Engineering University of Science Technology Beijing Beijing China 《高分子科学》2006,(3):307-313
PVC disulfide (2SPVC) was synthesized by solution crosslink and its molecular structure was confirmed by infrared spectrum. 2SPVC's specific area is 36.1 m2·g-1 tested by stand BET method, and granularity experiment gives out the particle size of d0.5= 11.3μm. With SEM (Scanning Electron Microscope) experiment the surface morphology and particle shape of 2SPVC were observed. Cyclic voltammetry (scan rate: 0.5 mV·s-1) shows that 2SPVC experience an obvious S-S redox reaction in charge-discharge process. When 2SPVC was used as cathode material for secondary lithium battery in a 1 mol·L-1 solution of lithium bis(trifluoromethylsulfonyl) imide (Li(CF3SO2)2N) in a 5:45:50 volume ratio mixture of o-xylene (oxy), diglyme (DG) and dimethoxymethane (DME) at 30℃, the first discharge capacity of 2SPVC is about 400.3 mAh·g-1 which is very close to its theoretical value (410.5 mAh·g-1) at a constant discharge current of 15 mA·g-1. It can retain at about 346.1 mAh·g-1 of discharge capacity after 30 charge-discharge cycles. So 2SPVC is a very promising cathode candidate for rechargeable lithium batteries. 相似文献
894.
Mass spectrometry (MS) is attractive as a multiplexed immunoassay readout benefiting from its high sensitivity, speed and mass resolution. Here, a simple paper-based hexaplex immunoassay with an on-line MS readout was proposed, using functionalized paper as the immune substrates, along with rhodamine-based mass tags assembled on gold nanoparticles prepared as the mass probes (MPs). Simultaneous immune capture and labeling were conducted in one step on paper substrates in 96-well plates with a high throughput within 30 minutes, and the on-line efficient dissociation of the mass tags highly facilitated the hexaplex readout of the immune signals by a newly established on-line paper substrate-based electrospray ionization-MS setup. Six MPs were synthesized for the simultaneous quantification of six important cancer protein markers (cancer antigen 15-3, cancer antigen 19-9, carcinoma embryonic antigen, cancer antigen 125, human epididymis protein 4, and alpha fetoprotein) using only 10 μL serum, presenting satisfactory sensitivity, accuracy and specificity. This platform was further tested in screening for the six biomarkers in serum samples of patients with breast, liver and gastric cancers, showing its high potential for sensitive and specific early cancer diagnosis.On-line paper substrate based electrospray ionization mass spectrometry for hexaplex immunoassays. 相似文献
895.
Bivas Mondal Rakesh Maiti Xing Yang Jun Xu Weiyi Tian Jia-Lei Yan Xiangyang Li Yonggui Robin Chi 《Chemical science》2021,12(25):8778
4,5-Dihydropyridazinones bearing an aryl substituent at the C6-position are important motifs in drug molecules. Herein, we developed an efficient protocol to access aryl-dihydropyridazinone molecules via carbene-catalyzed asymmetric annulation between dinucleophilic arylidene hydrazones and bromoenals. Key steps in this reaction include polarity-inversion of aryl aldehyde-derived hydrazones followed by chemo-selective reaction with enal-derived α,β-unsaturated acyl azolium intermediates. The aryl-dihydropyridazinone products accessed by our protocol can be readily transformed into drugs and bioactive molecules.Polarity inversion of arylidene hydrazones to react with bromoenals via carbene organic catalysis is disclosed. The reaction enantioselectively affords 6-aryl-4,5-dihydropyridazinones and related drugs with proven commercial applications. 相似文献
896.
Mei Y Wu T Xu C Langenbach KJ Elliott JT Vogt BD Beers KL Amis EJ Washburn NR 《Langmuir : the ACS journal of surfaces and colloids》2005,21(26):12309-12314
A simple yet versatile method was developed to prepare a low-density polymerization initiator gradient, which was combined with surface-initiated atom transfer radical polymerization (ATRP) to produce a well-defined poly(2-hydroxyethyl methacrylate) (HEMA) gradient substrate. A smooth variation in film thickness was measured across the gradient, ranging from 20 A to over 80 A, but we observed a nonmonotonic variation in water contact angle. Fits of X-ray reflectivity profiles suggested that at the low graft density end, the polymer chain structure was in a "mushroom" regime, while the polymer chains at high graft density were in a "brush" regime. It was found that the "mushroom" region of the gradient could be made adhesive to cells by adsorbing adhesion proteins, and cell adhesion could be tuned by controlling the density of the polymer grafts. Fibroblasts were seeded on gradients precoated with fibronectin to test cellular responses to this novel substrate, but it was found that cell adhesion did not follow the expected trend; instead, saturated cell adhesion and spreading was found at the low grafting density region. 相似文献
897.
Changlun Chen Di Xu Xiaoli Tan Xiangke Wang 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(1):227-233
The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions.
The extent of sorption of divalent metal cations is controlled by a number of factors including cosorbing or complexing. In
this work, the effects of pH, humic acid HA/Co(II) addition orders, ionic strength, concentration of HA, and foreign cations
on the Co(II) sorption on γ-Al2O3 in the presence of HA were investigated. The sorption isotherms of Co(II) on γ-Al2O3 in the absence and presence HA were also studied and described by using S-type sorption model. The experimental results showed
that the Co(II) sorption is strongly dependent on the pH values, concentration of HA, but independent of HA/Co(II) addition
orders, ionic strength, and foreign cations in the presence of HA under our experimental conditions. The results also indicated
that HA enhanced the Co(II) sorption at low pH, but reduced the Co(II) sorption at high pH. It was hypothesized that the significantly
positive influence of HA at low pH on the Co(II) sorption on γ-Al2O3 was attributed to strong surface binding of HA on γ-Al2O3 and subsequently the formation of ternary surface complexes such as ≡S-OOC-R-(COO−)
x
Co2−x
. Chemi-complexation may be the main mechanism of the Co(II) sorption on γ-Al2O3 in the presence of HA. 相似文献
898.
Here, we report a new method based on the combination of membrane separation technology and nanomaterial to rapid detection of peptides and protein with MALDI-TOF MS. This method shows advantages as it can inhibit the heterogeneous of sample spot and enhance the target molecular signal intensity. 相似文献
899.
聚1-氨基蒽醌在二次锂电池正极材料中的应用 总被引:4,自引:0,他引:4
采用化学方法合成聚1-氨基蒽醌并用于二次锂电池正极材料,通过红外光谱、扫描电镜、粒度测试、循环伏安以及充放电测试等方法对材料的官能团结构、微观形貌、颗粒大小以及电化学性能等进行了研究与分析.实验表明,与金属锂组成二次锂电池后,聚1-氨基蒽醌达到了218.3 mAh•g-1的首次放电容量,经过25次循环后仍可保持较高的充放电效率.由于材料具有较高的能量密度且不含对环境有污染的元素S,因此是二次锂电池非常有希望的正极材料. 相似文献
900.
Hemocompatibility is an essential aspect of blood contacting polymers. Knowledge of the relationship between polymer structure and hemocompatibility is important in designing such polymers. In this work, the effect of swelling behavior and states of water on the hemocompatibility of poly(acrylonitrile-co-N-vinyl-2-pyrrolidone) (PANCNVP) films was studied. Platelet adhesion and plasma recalcification time tests were used to evaluate the hemocompatibility of the films. Considering the importance of surface properties on the hemocompatibility of polymers, static water contact angles were measured by both sessile drop and captive bubble methods. It was found that, on the film surface of PANCNVP with a higher NVP content, adhered platelets were remarkably suppressed and the recalcification time was longer. The total water content adsorbed on the PANCNVP film was determined through swelling experiments performed at temperatures of interest. Differential scanning calorimetry and thermogravimetric analysis were used to probe the states of water in the films. Based on the results from these experiments, it was hypothesized that the better hemocompatibility of PANCNVP films with higher NVP contents was due to their higher free water content, because water molecule exchange at the polymer/liquid interface, facilitated by a high free water content, is unfavorable for the formation of surface bound water, which causes poor hemocompatibility. [diagram in text]. 相似文献