全文获取类型
收费全文 | 5010篇 |
免费 | 123篇 |
国内免费 | 27篇 |
专业分类
化学 | 3484篇 |
晶体学 | 62篇 |
力学 | 147篇 |
数学 | 608篇 |
物理学 | 859篇 |
出版年
2022年 | 26篇 |
2021年 | 46篇 |
2020年 | 59篇 |
2019年 | 60篇 |
2018年 | 39篇 |
2017年 | 46篇 |
2016年 | 112篇 |
2015年 | 77篇 |
2014年 | 106篇 |
2013年 | 216篇 |
2012年 | 276篇 |
2011年 | 328篇 |
2010年 | 183篇 |
2009年 | 140篇 |
2008年 | 266篇 |
2007年 | 301篇 |
2006年 | 309篇 |
2005年 | 274篇 |
2004年 | 229篇 |
2003年 | 225篇 |
2002年 | 207篇 |
2001年 | 63篇 |
2000年 | 64篇 |
1999年 | 34篇 |
1998年 | 49篇 |
1997年 | 52篇 |
1996年 | 86篇 |
1995年 | 47篇 |
1994年 | 52篇 |
1993年 | 45篇 |
1992年 | 27篇 |
1991年 | 47篇 |
1990年 | 49篇 |
1989年 | 39篇 |
1988年 | 47篇 |
1987年 | 29篇 |
1986年 | 32篇 |
1985年 | 70篇 |
1984年 | 67篇 |
1983年 | 39篇 |
1982年 | 67篇 |
1981年 | 64篇 |
1980年 | 61篇 |
1979年 | 48篇 |
1978年 | 55篇 |
1977年 | 53篇 |
1976年 | 41篇 |
1975年 | 44篇 |
1974年 | 40篇 |
1973年 | 39篇 |
排序方式: 共有5160条查询结果,搜索用时 15 毫秒
151.
On-line preconcentration strategies for trace analysis of metabolites by capillary electrophoresis 总被引:1,自引:0,他引:1
Analysis of low concentrations of metabolites is required for new fields of biological research, such as metabolomics. In this review, recent work in our laboratory aimed at developing improved strategies for on-line sample preconcentration of metabolites by capillary electrophoresis (CE) is presented. Dynamic pH junction, sweeping and dynamic pH junction-sweeping represent three complementary methods for electrokinetic focusing of large volumes of sample directly on-capillary. Focusing selectivity and focusing efficiency are two factors that can be used to assess the suitability of each method for different classes of metabolites. Buffer properties can be selected to enhance the focusing of specific types of metabolites based on knowledge of the analyte physicochemical properties. The application of on-line preconcentration CE for trace analysis of metabolites in real samples of interest, such as biological fluids and cellular extracts, is also demonstrated. Under optimum conditions, up to three orders of magnitude increase in concentration sensitivity can be realized for several classes of metabolites, including catecholamines, purines, nucleosides, nucleotides, amino acids, steroids and coenzymes. Recent work on hyphenating on-line preconcentration with multiplexed CE is highlighted as a promising platform for sensitive and high-throughput analyses of metabolites. 相似文献
152.
A series of optically active main chain polyesters were synthesized by high temperature polycondensation from biphenolic azo chromophores with azobenzene-4,4'-dicarbonylchloride and 1,4:3,6-dianhydro-D-sorbitol ([!]D25=+42.5°). The second harmonic generation of the polyesters is studied in thin films. The polar order in films is determined from the UV-visible absorption spectra. The variation in SHG intensity with chiral monomer concentration is explained as a function of polar order. The polymers with chiral units showed good second harmonic efficiency. The intensity of second harmonic light (532 nm) increased with angle of incidence and indicated the polar order in the plane of the film. The SH signal also showed good temporal stability. 相似文献
153.
Selective chemical treatment of cellular microdomains using multiple laminar streams 总被引:1,自引:0,他引:1
Takayama S Ostuni E LeDuc P Naruse K Ingber DE Whitesides GM 《Chemistry & biology》2003,10(2):123-130
There are many experiments in which it would be useful to treat a part of the surface or interior of a cell with a biochemical reagent. It is difficult, however, to achieve subcellular specificity, because small molecules diffuse distances equal to the extent of the cell in seconds. This paper demonstrates experimentally, and analyzes theoretically, the use of multiple laminar fluid streams in microfluidic channels to deliver reagents to, and remove them from, cells with subcellular spatial selectivity. The technique made it possible to label different subpopulations of mitochondria fluorescently, to disrupt selected regions of the cytoskeleton chemically, to dislodge limited areas of cell-substrate adhesions enzymatically, and to observe microcompartmental endocytosis within individual cells. This technique does not require microinjection or immobilization of reagents onto nondiffusive objects; it opens a new window into cell biology. 相似文献
154.
Several pseudohalide containing ionic liquids with quarternary ammonium counter cations of the general formula [R3MeN]X [R = ethyl ( 1X ), n‐butyl ( 2X ) with X– = CN–, N3–, OCN–, and SCN–] were synthesized by decomposition of the corresponding trialkylammonium methylcarbonate in the reaction with Me3Si–X. We also treated 2CN with OP(OMe)3, yielding [nBu3MeN][O2P(OMe)2] and acetonitrile (Me‐CN). The double salt [nBu3MeN]2{[B(OMe)3(CN)](CN)} was obtained from the reaction of 2CN with B(OMe)3, featuring the formation of the monocyanotrimethoxyborate anion, [B(OMe)3(CN)]–, co‐crystallized with [nBu3MeN]CN. [nBu3MeN]2{[B(OMe)3(CN)](CN)} was fully characterized including structure elucidation. 相似文献
155.
Dr. Samantha A. Orr Dr. Emily C. Border Prof. Philip C. Andrews Dr. Victoria L. Blair 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(51):11876-11882
By exploring lithium–bromide exchange reactivity of aromatic Schiff's bases with tert-butyllithium (tBuLi), we have revealed unprecedented competitive intermolecular and intramolecular cascade annulation pathways, leading to valuable compounds, such as iso-indolinones and N-substituted anthracene derivatives. A series of reaction parameters were probed, including solvent, stoichiometry, sterics and organolithium reagent choice, in order to understand the influences that limit such ring-closing pathways. With two viable reactivity options for the organolithium on the imine; namely, nucleophilic addition or lithium–bromide exchange, a surprising competitive nature was observed, where nucleophilic addition dominated, even under cryogenic conditions. Considering the most commonly used solvents for lithium–bromide exchange, tetrahydrofuran (THF) and diethyl ether (Et2O), contrasting reactivity outcomes were revealed with nucleophilic addition promoted in THF, while Et2O yielded almost double the conversion of cyclic products than in THF. 相似文献
156.
Digital microfluidics for cell-based assays 总被引:1,自引:0,他引:1
We introduce a new method for implementing cell-based assays. The method is based on digital microfluidics (DMF) which is used to actuate nanolitre droplets of reagents and cells on a planar array of electrodes. We demonstrate that this method is advantageous for cell-based assays because of automated manipulation of multiple reagents in addition to reduced reagent use and analysis time. No adverse effects of actuation by DMF were observed in assays for cell viability, proliferation, and biochemistry. A cytotoxicity assay using Jurkat T-cells was performed using the new method, which had approximately 20 times higher sensitivity than a conventional well plate assay. These results suggest that DMF has great potential as a simple yet versatile analytical tool for implementing cell-based assays on the microscale. 相似文献
157.
The total synthesis of 6,7-dideoxysqualestatin H5 (3) has been completed by a concise approach that features the stereoselective intramolecular vinylogous aldol reaction of the furoic ester 25a to give 30 or its trimethylsilyl ether derivative 34, which possess the requisite absolute stereochemistry at C(3)-C(5) of 3. Compound 34 was reduced to the saturated bislactone 39, and the C(1) side chain subunit 47 was introduced leading to a mixture of the hemiacetals 48 and the corresponding ketone 49. When this mixture was stirred with methanolic acid, transketalization occurred to give a mixture of 50 and the spirocyclic methyl acetals 51a,b. Oxidation of the primary alcohol group in 50 followed by saponification of the two remaining ester groups gave 3. The longest linear sequence in the synthesis commences with commercially available erythronolactone (26) and requires 17 chemical steps with only 10 isolated intermediates. 相似文献
158.
The syntheses of 1-methyl-1-germaadamantane and 1-chloro-1-germaadamantane are described. Attempts to prepare the 1-methyl-1-stannaadamantane and the novel cage systems, 1-silatris-nor- and 1-silatris-homo-adamantanes are also described as well as the syntheses of a variety of Group IV 1,3,5-trisubstituted cyclohexanes. 相似文献
159.
160.
Eric E. Boros Istvan Kaldor Philip S. Turnbull 《Journal of heterocyclic chemistry》2011,48(3):733-736
2‐Methyl‐4‐(trifluoromethyl)‐1H‐indole‐5‐carbonitrile is a key intermediate in the synthesis of selective androgen receptor modulators discovered in these laboratories. A practical and convergent synthesis of the title compound starting from 4‐nitro‐3‐(trifluoromethyl)phenol and tert‐butyl acetoacetate was developed, including a telescoped procedure for synthesis (without isolation) and Nenitzescu reaction of 2‐trifluoromethyl‐1,4‐benzoquinone. Conversion of the known Nenitzescu indole product to a novel triflate intermediate followed by palladium‐catalyzed cyanation afforded a penultimate carbonitrile. Removal of the C‐3 tert‐butyl ester group on the indole through a decarboxylative pathway completed the synthesis of the title compound in six steps (27% overall yield) from 4‐nitro‐3‐(trifluoromethyl)phenol (five steps, 37% overall yield from tert‐butyl acetoacetate). J. Heterocyclic Chem., (2011). 相似文献