全文获取类型
收费全文 | 7567篇 |
免费 | 1144篇 |
国内免费 | 973篇 |
专业分类
化学 | 5502篇 |
晶体学 | 46篇 |
力学 | 480篇 |
综合类 | 61篇 |
数学 | 827篇 |
物理学 | 2768篇 |
出版年
2024年 | 18篇 |
2023年 | 136篇 |
2022年 | 243篇 |
2021年 | 286篇 |
2020年 | 304篇 |
2019年 | 290篇 |
2018年 | 209篇 |
2017年 | 199篇 |
2016年 | 315篇 |
2015年 | 358篇 |
2014年 | 366篇 |
2013年 | 497篇 |
2012年 | 584篇 |
2011年 | 685篇 |
2010年 | 434篇 |
2009年 | 428篇 |
2008年 | 492篇 |
2007年 | 428篇 |
2006年 | 422篇 |
2005年 | 409篇 |
2004年 | 289篇 |
2003年 | 253篇 |
2002年 | 253篇 |
2001年 | 219篇 |
2000年 | 167篇 |
1999年 | 158篇 |
1998年 | 151篇 |
1997年 | 131篇 |
1996年 | 140篇 |
1995年 | 150篇 |
1994年 | 115篇 |
1993年 | 104篇 |
1992年 | 73篇 |
1991年 | 97篇 |
1990年 | 59篇 |
1989年 | 59篇 |
1988年 | 48篇 |
1987年 | 31篇 |
1986年 | 22篇 |
1985年 | 18篇 |
1984年 | 11篇 |
1983年 | 11篇 |
1982年 | 11篇 |
1981年 | 5篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1966年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有9684条查询结果,搜索用时 15 毫秒
101.
The ω-iodo-α,β-alkynoates and their ketone, sulfone or phosphonate analogues react with δ-chloropropylamines in MeCN assisted with K2CO3 to undergo a sequential SN2/Michael addition/SN2/SN2 reaction process, giving polysubstituted indolizidines or quinolizidines in good to excellent yields. This sequential reaction process is also compatible with three other substituted α,β-alkynoates, affording quinolizidine analogues in moderate to good yields. 相似文献
102.
一种新的滤纸基质固体表面低温荧光(燐光)测定装置 总被引:1,自引:0,他引:1
对自行研制的铜制滤纸基质低温荧光(燐光)测定的样品支架,进行了滤纸基质固体表面低温荧光测定的可行性研究。与同类冷冻装置和室温装置比较,本装置用于滤纸基质固体表面低温荧光(燐光)测定具有以下优点;样品的分析周期大大地缩短,由45min缩短为5-6min;装置简单、便宜耐用;操作简便,简化了室温测定时的滤纸干燥程序,应用范围广,方法的重现性好,检样分析结果的相对标准偏差RSD%小于10%,荧光(燐光)分析灵敏度高,检出限低,线性范围宽。 相似文献
103.
An electrochemical DNA hybridization detection assay based on a silver nanoparticle label 总被引:3,自引:0,他引:3
A novel, sensitive electrochemical DNA hybridization detection assay, using silver nanoparticles as the oligonucleotide labeling tag, is described. The assay relies on the hybridization of the target DNA with the silver nanoparticle-oligonucleotide DNA probe, followed by the release of the silver metal atoms anchored on the hybrids by oxidative metal dissolution and the indirect determination of the solubilized Ag(I) ions by anodic stripping voltammetry (ASV) at a carbon fiber ultramicroelectrode. The influence of the relevant experimental variables, including the surface coverage of the target oligonucleotide, the duration of the silver dissolution steps and the parameters of the electrochemical stripping measurement of the silver(I) ions, is examined and optimized. The combination of the remarkable sensitivity of the stripping metal analysis at the microelectrode with the large number of silver(I) ions released from each DNA hybrid allows detection at levels as low as 0.5 pmol L(-1) of the target oligonucleotides. 相似文献
104.
The direct reactions of (C5H5)2LnCl with LiN=C(NMe2)2 proceeded at room temperature in THF under pure nitrogen to yield the lanthanocene guanidinate complexes [(C5H5)2Ln(mu-eta1:eta2-N=C(NMe2)2)]2 (Ln = Gd (1), Er (2)). Treatment of phenyl isocyanate with complexes 1 and 2 results in monoinsertion of phenyl isocyanate into the Ln-N(mu-Gua) bond to yield the corresponding insertion products [(C5H5)2Ln(mu-eta1:eta2-OC(N=C(NMe2)2)NPh)]2 (Ln = Gd (3), Er (4)), presenting the first example of unsaturated organic small molecule insertion into the metal-guanidinate ligand bond. Further investigations indicate that N,N'-diisopropylcarbodiimide does not react with complexes 1 and 2 under the same conditions; however, it readily inserts into the lithium-guanidinate ligand bond of LiN=C(NMe2)2. As a synthon of the insertion product Li[(iPrN)2C(N=C(NMe2)2)], its reaction with (C5H5)2LnCl gives the novel organolanthanide complexes containing the guanidinoacetamidinate ligand, (C5H5)2Ln[(iPrN)2C(N=C(NMe2)2)] (Ln = Yb (5), Er (6), Dy (7)). All complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 1, 3, 5 and 7 were determined through X-ray single-crystal diffraction analysis. 相似文献
105.
106.
Yan Li HAO Ying Jie DENG Yan CHEN You Cai HU 《中国化学快报》2005,16(8):1004-1006
Novel hexadecyl 3- { 4-[2-hydroxy-3(isopropylamino)propoxy]phenyl }propionate (HPP)was synthesized and its effect on delivery of liposomes into cultured cardiomyocytes was examined. The structure of HPP was characterized by IH NMR, 1R and MS. The amount of cardiomyocytes uptake of HPP-liposome was 3.9-fold higher than plain-liposome, and the increase was 6.2-fold when hypoxia happens. It indicated that HPP was a potential ligand for liposome targeting to ischemic myocardium. 相似文献
107.
[reaction: see text] Trifluoropropanoic acid reacts with 1 equiv of POCl3 in DMF to generate the trifluoromethyl enamine (7). At this stage, two reaction manifolds are available. The expected reaction with additional POCl3 generates the 2-trifluoromethyl vinamidinium salt (3c). However, thermally driven loss of fluoride generates an iminium ion, which sets the stage for a [2 + 2] cycloaddition to ultimately generate the dimethylaminomethylene vinamidinium salt (1). 相似文献
108.
We have determined tributyltin and dibutyltin species in various environmental sediment samples (marine, harbour and river sediment) using the in situ aqueous ethylation-gas chromatography-atomic absorption spectrometry method subsequent to extraction by methanol containing O.5M HCl. The present technique provides a significantly lower detection limit than previous methods, so that tributyltin can for the first time be measured in some of the samples. Thus, the method described is well suited for the determination of tributyltin and dibutyltin compounds in sediments with low levels of butyltin species (e.g., Main River, 1.7 ng of tributyltin as Sn/g dry sediment). 相似文献
109.
Promotion of Ionic Liquid to Dimethyl Carbonate Synthesis from Methanol and Carbcn Dioxide 总被引:2,自引:0,他引:2
Promotion of ionic liquid, 1-ethyl-3-methylimidazolium bromide (emimBr), to the synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in the presence of potassium carbonate and less amount of methyl iodide under mild conditions was investigated. The results showed that the high selectivity and raised yield of DMC was achieved due to the addition of emimBr in the reaction system. And effect of several reaction conditions such as temperature, pressure and amount of emimBr was discussed. 相似文献
110.
Raska CS Parker CE Huang C Han J Glish GL Pope M Borchers CH 《Journal of the American Society for Mass Spectrometry》2002,13(9):1034-1041
Both the matrix selected and the laser fluence play important roles in MALDI-quadrupole/time of flight (QqTOF) fragmentation processes. "Hot" matrices, such as alpha-cyano4-hydroxycinnamic acid (HCCA), can increase fragmentation in MS spectra. Higher laser fluence also increases fragmentation. Typical peptide fragment ions observed in the QqTOF are a, b, and y ion series, which resemble low-energy CID product ions. This fragmentation may occur in the high-pressure region before the first mass-analyzing quadrupole. Fragment ions can be selected by the first quadrupole (Q1), and further sequenced by conventional MS/MS. This allows pseudo-MS3 experiments to be performed. For peptides of higher molecular weight, pseudo-MS3 can extend the mass range beyond what is usually accessible for sequencing, by allowing one to sequence a fragment ion of lower molecular weight instead of the full-length peptide. Peptides that predominantly show a single product ion after MS/MS yield improved sequence information when this technique is applied. This method was applied to the analysis of an in vitro phosphorylated peptide, where the intact enzymatically-generated peptide showed poor dissociation via MS/MS. Sequencing a fragment ion from the phosphopeptide enabled the phosphorylation site to be unambiguously determined. 相似文献