全文获取类型
收费全文 | 11522篇 |
免费 | 2223篇 |
国内免费 | 2090篇 |
专业分类
化学 | 8481篇 |
晶体学 | 280篇 |
力学 | 746篇 |
综合类 | 180篇 |
数学 | 1167篇 |
物理学 | 4981篇 |
出版年
2024年 | 27篇 |
2023年 | 197篇 |
2022年 | 403篇 |
2021年 | 422篇 |
2020年 | 464篇 |
2019年 | 449篇 |
2018年 | 421篇 |
2017年 | 456篇 |
2016年 | 590篇 |
2015年 | 629篇 |
2014年 | 754篇 |
2013年 | 954篇 |
2012年 | 1164篇 |
2011年 | 1206篇 |
2010年 | 886篇 |
2009年 | 869篇 |
2008年 | 890篇 |
2007年 | 807篇 |
2006年 | 771篇 |
2005年 | 677篇 |
2004年 | 480篇 |
2003年 | 331篇 |
2002年 | 349篇 |
2001年 | 316篇 |
2000年 | 245篇 |
1999年 | 197篇 |
1998年 | 168篇 |
1997年 | 133篇 |
1996年 | 98篇 |
1995年 | 88篇 |
1994年 | 74篇 |
1993年 | 64篇 |
1992年 | 60篇 |
1991年 | 51篇 |
1990年 | 35篇 |
1989年 | 21篇 |
1988年 | 16篇 |
1987年 | 8篇 |
1986年 | 12篇 |
1985年 | 12篇 |
1984年 | 13篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 1篇 |
1971年 | 2篇 |
1959年 | 2篇 |
1957年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Tetra-Schiff base macrocyclic compound containing benzo-12-crown-4 was synthesized via condensation of 2,6-diformyl-4-methyl-phenol with 4′,5′-diaminobenzo-12-C-4 promoted by proton. The compound was characterized by MS,IR ^1HNMR spectroscopy and elemental analysis. 相似文献
72.
以1,4-萘醌为原料,合成了含硫的醌构稠杂环化合物苯并[b]萘并[2',3':5,6][1,4]二噻英并[2,3-i]噻蒽-5,7,9,14,16,18-六酮(4),其结构经1H NMR和IR确证.采用波长为800 nm,脉宽为80 fs的Ti:Sapphire飞秒激光,运用双光束简并四波混频法测定了4的三阶非线性光学性能,结果表明,4的三阶非线性光学极化率χ(3),非线性折射率n2,分子二阶超极化率γ和响应时间分别为2.89×10-13 esu, 5.31×10-12 esu, 3.14×10-31 esu和101 fs.并分析了4的分子结构对其三阶非线性光学性能的影响. 相似文献
73.
电热蒸发进样—等离子体原子发射光谱中钒和钛的蒸发机理研究 总被引:1,自引:0,他引:1
自1974年Nixon报道钽丝电热蒸发作为ICP-AES进样技术以来,这一技术已引起了人们的极大兴趣,受到越来越广泛的重视。电热蒸发(ETV)-ICP-AES是一种将蒸发和激发分步进行的联用技术。石墨是目前普遍使用的蒸发器材料。然而,在高温下某些元素和石墨材料可以发生碳化反应,形成热稳定的碳化物,使分析物蒸发不完全或根本不蒸发,从而影响分析结果的灵敏度和准确性。为了解决这一问题,我们曾提出了以聚四氟乙烯(PTFE)悬浮体为氟化剂,氟化辅助ETV-ICP-AES直接测定粉煤标样中钒和钛的新方法,其检出限 相似文献
74.
Xiao Jie He Qun Qiu Shengchao Li Haoquan Wang Binghua Zhang Bin Bu Weifeng 《中国科学:化学(英文版)》2020,63(6):792-801
It is well-known that amphiphilic star-shaped copolymers can self-assemble in selective solvents to form complicated micellar constructs as a synergistic result of both the topological constraints and relative volume fractions of the arms. Although the association phenomena of amphiphilic stars have been observed in nonselective solvents, both the structural detail and formation mechanism of these associates are not clear yet. Moreover, these experimental observations are controversial with respect to molecularly dispersed starlike copolymers in nonselective solvents as is popularly believed. To clarify these issues, we have synthesized a series of polyoxometalate-based polystyrene-poly(ethylene glycol)(PS-PEG) miktoarm star supramolecular copolymers(SEW-1–5) by coupling a Keggin-type polyoxometalate of K_4[α-SiW_(12)O_(40)] with 1,2,3-triazolium bridged block copolymers of-PS_n-b~+-PEG_mI~-(n=17, 26, 39, 57, 81; m=45) through ionic exchange reactions, respectively. TEM imaging,contact angle and ~1H NMR studies reveal that SEW-2–5 self-assemble in chloroform, THF, and toluene to create micellelike aggregates ranging from cylinder to sphere with a PS corona and a PEG core, while for SEW-1, reverse bilayers are captured with a PEG corona and a PS core. Among these aggregates, the Keggin clusters of [α-SiW_(12)O_(40)]~(4-) localize at the core-corona interfaces between PS and PEG. In terms of solvent quality, chloroform, THF, and toluene are only slightly poorer for PEG than that for PS with a relative order of chloroformTHFtoluene. These unexpected aggregates originate from the topological constraints of the chemically different arms of PS and PEG in the miktoarm stars, where the weak incompatibility between the PS and PEG arms is intensified appropriately. The presence of the reverse bilayered structures of SEW-1 is due to the magnified steric hindrance of the PEG45 arm with decreasing the molecular weight of the PS17 arm. However, to the best of our knowledge,these are the first examples clearly indicating that miktoarm star copolymers can self-assemble in common good solvents or slightly selective solvents to generate micellelike aggregates. This scenario is not only in sharp contrast to the intuitively considered behavior of unimolecular miktoarm stars in nonselective solvents, but also rather different from the conventional selfassembly behavior of amphiphilic star copolymers in selective solvents. 相似文献
75.
Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was used to determine the structures of anhydroicaritin glycosides by the MS/MS experiments of anhydroicaritin glycosides and their methylated derivatives,With high accuracy FT-ICR-MS provides much information about the structures of compounds ,FT-ICR-MS shows the great potential application in the structural characterization of unknown compounds. 相似文献
76.
银微电极微分电位溶出分析法研究 总被引:3,自引:1,他引:3
本文首次报道了银微电极微分电位溶出分析法。用化学刻蚀法方便地制作了银微电极,用于DPSA具有背景值低,分辨率好、精密度及灵敏度高,在不搅拌,仅需一定酸度而酸度而无其它介质的条件下就能测试等优点,对人工试样及自来水样分析,结果令人满意。 相似文献
77.
实验研究结果表明双核金属酞菁类化合物MPc-PcM(M=V、Cr、Mn、Fe、Co、Ni、Cu)是催化H_2S液相氧化反应的良好催化剂,且其催化活性顺序为Co>Ni>V>Fe>Cu>Cr>Mn.采用量子化学理论计算方法(INDO/S)分析了其前线分子轨道的构成特征,结果表明这几种MPc-PcM的LUMO轨道皆为有金属离子参与形成的π轨道,但HOMO轨道间的差异却很大.M=Co、Ni、Cu、Cr时,其HOMO为π轨道;而M=Fe、Mn时,其HOMO却为σ轨道.正是在前线分子轨道的轨道类型、共轭程度及金属轨道贡献三方面因素的协同作用下,才导致MPc-PcM的催化活性顺序并非按中心金属离子价电子层d电子数的递变而呈现出规律性的变化. 相似文献
78.
钇对2618合金组织及性能的影响 总被引:7,自引:1,他引:7
采用X射线,光学显微镜及扫描电镜等手段研究了2618合金中的组织与相结构,并研究了元素钆在2618合金中的存在形式及其对合金力学性能的影响。结果表明,微量钆元素在铝合金中是以化合物形式存在的;钆对合金中的铸态组织及Al9FeNi仃形态没有影响。由于微量钆的加入,降低了铜与镁在2618合金中的固溶量,减少了时效析出相A2CuMg数量,从而降低2618合金的室温强度帮在250℃的高温瞬时强度;但由于微量钆减少了铜与镁在2618合金中的扩散速度,延缓了时效机的粗化,并由于第二相数量的增多,因此提高了2618合金在250℃经100h高温热暴露后的高温瞬时强度。 相似文献
79.
[structure: see text] Total synthesis of a cyclic depsipeptide with proposed structure of palau'amide is achieved, which features a stereoselective elaboration of its 5,7-dihydroxy-2,6-dimethyldodec-2-en-11-ynoic acid unit. The synthetic compound has potent cytotoxicity against three tumor cell lines but different rotation and NMR data compared to those reported for palau'amide, which implies that its conformation is close to that of palau'amide but that some stereochemistry in palau'amide was misassigned. 相似文献
80.
Proper epidemiological, risk assessment and exposure analysis of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD, dioxin) and related halogenated aromatic hydrocarbons (HAHs) requires accurate measurements of these chemicals both in the species of interest and in various exposure matrices (i.e. biological, environmental, food and feed). High-resolution instrumental analysis techniques are established for these chemicals, however, these procedures are very costly and time-consuming and as such, they are impractical for large scale sampling studies (i.e. for epidemiological studies and assessment of areas with widespread contamination). Accordingly, numerous bioanalytical methods have been developed for the detection of these chemicals in extracts from a variety of matrices, the majority of which take advantage of the ability of these chemicals to activate the aromatic hydrocarbon receptor (AhR) and the AhR signal transduction pathway. Here we review the currently available in vitro AhR-based cell bioassay systems with a focus on recent recombinant reporter gene cell lines that have been developed for detection and relative quantitation of TCDD and related HAHs. Comparison of the relative sensitivities of the various cell bioassays and examples of their use in screening and analysis of environmental, biological, and food and feed samples are presented. Currently available experimental results and validation studies demonstrate the utility of these cell bioassay systems to provide a relatively rapid, accurate, and cost effective screening approach for the detection of TCDD and related HAHs in a variety of environmental, biological, food and feed samples. The availability of these cell bioassay systems will not only facilitate the large scale sampling studies needed for accurate assessment of contamination and exposure to these environmental chemicals, but they provide avenues for the identification of novel classes of TCDD-like chemicals. 相似文献