全文获取类型
收费全文 | 5116篇 |
免费 | 431篇 |
国内免费 | 159篇 |
专业分类
化学 | 3886篇 |
晶体学 | 60篇 |
力学 | 165篇 |
综合类 | 7篇 |
数学 | 348篇 |
物理学 | 1240篇 |
出版年
2023年 | 51篇 |
2022年 | 49篇 |
2021年 | 132篇 |
2020年 | 108篇 |
2019年 | 154篇 |
2018年 | 116篇 |
2017年 | 101篇 |
2016年 | 193篇 |
2015年 | 203篇 |
2014年 | 241篇 |
2013年 | 352篇 |
2012年 | 506篇 |
2011年 | 508篇 |
2010年 | 322篇 |
2009年 | 261篇 |
2008年 | 384篇 |
2007年 | 317篇 |
2006年 | 320篇 |
2005年 | 273篇 |
2004年 | 227篇 |
2003年 | 180篇 |
2002年 | 186篇 |
2001年 | 77篇 |
2000年 | 59篇 |
1999年 | 68篇 |
1998年 | 37篇 |
1997年 | 31篇 |
1996年 | 38篇 |
1995年 | 26篇 |
1994年 | 14篇 |
1993年 | 19篇 |
1992年 | 20篇 |
1991年 | 15篇 |
1990年 | 13篇 |
1989年 | 15篇 |
1988年 | 9篇 |
1987年 | 11篇 |
1986年 | 4篇 |
1985年 | 10篇 |
1984年 | 13篇 |
1983年 | 4篇 |
1981年 | 5篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1974年 | 3篇 |
1969年 | 3篇 |
1968年 | 2篇 |
1938年 | 1篇 |
排序方式: 共有5706条查询结果,搜索用时 15 毫秒
41.
M. Piñeiro-Iglesias M. Miñones-Vázquez E. Vázquez-Blanco S. Muniategui-Lorenzo P. López-Mahía D. Prada-Rodríguez 《Chromatographia》2002,56(7-8):483-488
Summary The aim of this work is to establish the best conditions for concentration and purification steps in the trace analysis of
aliphatic and polycyclic aromatic hydrocarbons (PAH) from atmospheric particulate matter by gas chromatography-flame ionisation
detection (GC-FID) and high performance liquid chromatography with ultraviolet and fluorescence detection (HPLC-UV-FL). The
best results for the more volatile compound were obtained with a combination of rotary evaporation and a stream of nitrogen
(near to 100% for aliphatic hydrocarbons and from 70 to 105% for PAH). Two types of solid phase extraction (SPE)cartridges
(Supelclean
tm
LC-Silica SPE tubes and Sep-Pak? Plus silica cartridges) and glass column were examined for the purification and fractionation step. Blank chromatograms of
both types of cartridges analysed by GC-FID made this study difficult, because a PSS (programmed split-splitless) injector
was employed thereby increasing the sensitivity. This problem was not observed in the HPLC-UV-FL blank chromatograms of these
cartridges. Glass columns filled with silica and alumina were chosen because no interference was found in the GC-FID blank
chromatograms and the best recoveries in the fractionation of both aliphatic hydrocarbons and PAH were achieved. This is especially
important when aliphatic hydrocarbons concentrations are lower than 1 μg mL−1. Finally, the selected conditions were applied to the analysis of hydrocarbons in real atmospheric particulate samples. 相似文献
42.
L—半胱氨酸(L—Cys)是蛋白质的降解产物之一,在体内除参与蛋白质的合成外,还参与毒物的解毒过程。本文用pH电位滴定法测定L—Cys同Fe~(2+)、Ni~(2+)、Zn~(2+)、Pb~(2+)形成配合物的稳定常数,以温度系数法获得配位反应的焓变,根据所得的热力学参数,对配位反应的推动力和配合物的结构进行讨论,并进一步用红外光谱和电子光谱对Pb~(2+)、Ni~(2+)两体系所得的结果予以证实。 相似文献
43.
在酸氧化后的多壁碳纳米管上化学还原镀钯,用水将镀钯后的碳管清洗至中性并配制成悬浊液,将悬浊液旋涂在真空溅射的叉指金电极表面,干燥后作为气敏膜,把气敏膜暴露于一定浓度的苯气体中,检测传感器的电流变化,并计算其灵敏度。镀钯后的多壁碳管在室温下对苯响应和回复迅速,电导变化与苯气体的浓度呈良好的线性关系,其线性回归方程y=0.0041x 0.1288,r=0.9546。Pd颗粒对苯分子和碳管壁结构缺陷间的电子转移的促进作用可能是多壁碳管镀钯后产生良好气敏响应的原因。 相似文献
44.
Co/Rh (Co:Rh = 2:2) heterobimetallic nanoparticles derived from Co(2)Rh(2)(CO)(12) react with alkynes and alpha,beta-unsaturated aldehydes such as acrolein, crotonaldehyde, and cinnamic aldehyde and release products resulting from [2 + 2 + 1]cycloaddition of alkyne, carbon monoxide, and alkene. alpha,beta-Unsaturated aldehydes act as a CO and alkene source. These reactions produce 2-substituted cyclopentenones. 相似文献
45.
Kwak WJ Han CK Chang HW Kim HP Kang SS Son KH 《Chemical & pharmaceutical bulletin》2003,51(3):333-335
A new triterpenoid saponin, loniceroside C was isolated from the aerial parts of Lonicera japonica. Its structure was established to be 3-O-beta-D-glucopyranosyl hederagenin 28-O-alpha-L-rhamnopyranosyl (1-->2)-[beta-D-xylopyranosyl(1-->6)]-beta-D-glucopyranosyl ester by spectroscopic techniques and chemical transformations. Loniceroside C showed in vivo antiinflammatory activity against mouse ear edema provoked by croton oil. 相似文献
46.
Osteoprotegerin (OPG), a member of the tumor necrosis factor receptor superfamily, is known to inhibit osteoclastogenesis by acting as a soluble decoy receptor for the receptor activator of NF-kappaB ligand (RANKL). We report the presence of OPG on the membrane of osteoclasts and the possibility of the direct action of OPG on them. Highly pure osteoclast precursors were isolated from mouse long bones and induced to differentiate into mature osteoclasts by M-CSF and soluble RANKL (sRANKL). The presence of OPG on the membrane of these cells was confirmed by western blotting and immunostaining. Furthermore, sRANKL was found to be bound to the OPG on the osteoclast precursors. These results suggest that OPG might have a new role during the differentiation of osteoclasts beyond its role as a soluble decoy receptor. The mechanism of the existence of OPG on osteoclast precursors remains to be found. 相似文献
47.
Abstract— Irradiation of thin films consisting of 4,5',8-trimethylpsoralen (TMP), adenosine and small amounts of alcohols led to TMP-alcohol photoadducts in addition to TMP-adenosine photoadducts. Four TMP-ethanol and two TMP-methanol adducts have been separated and characterized. Covalent bonds were formed between the 4-carbon of TMP and the α-carbon to the hydroxy group in the alcohols. The TMP-alcohol photoadducts were formed only in the TMP film containing small amounts of alcohol and adenosine. Furthermore, no photoadduct of TMP and ribose was detected upon photolysis of a TMP-ribose film, suggesting that the adenine moiety plays a specific role in the reaction. The interaction of adenosine with psoralens in a dry film may be related to the DNA sequence selectivity observed for the photoreaction of psoralens with DNA. 相似文献
48.
A novel process was developed to fabricate biodegradable polymer scaffolds for tissue engineering applications, without using organic solvents. Solvent residues in scaffolds fabricated by processes involving organic solvents may damage cells transplanted onto the scaffolds or tissue near the transplantation site. Poly(L-lactic acid) (PLLA) powder and NaCl particles in a mold were compressed and subsequently heated at 180 degrees C (near the PLLA melting temperature) for 3 min. The heat treatment caused the polymer particles to fuse and form a continuous matrix containing entrapped NaCl particles. After dissolving the NaCl salts, which served as a porogen, porous biodegradable PLLA scaffolds were formed. The scaffold porosity and pore size were controlled by adjusting the NaCl/PLLA weight ratio and the NaCl particle size. The characteristics of the scaffolds were compared to those of scaffolds fabricated using a conventional solvent casting/particulate leaching (SC/PL) process, in terms of pore structure, pore-size distribution, and mechanical properties. A scanning electron microscopic examination showed highly interconnected and open pore structures in the scaffolds fabricated using the thermal process, whereas the SC/PL process yielded scaffolds with less interconnected and closed pore structures. Mercury intrusion porosimetry revealed that the thermally produced scaffolds had a much more uniform distribution of pore sizes than the SC/PL process. The utility of the thermally produced scaffolds was demonstrated by engineering cartilaginous tissues in vivo. In summary, the thermal process developed in this study yields tissue-engineering scaffolds with more favorable characteristics, with respect to, freedom from organic solvents, pore structure, and size distribution than the SC/PL process. Moreover, the thermal process could also be used to fabricate scaffolds from polymers that are insoluble in organic solvents, such as poly(glycolic acid). Cartilage tissue regenerated from thermally produced PLLA scaffold. 相似文献
49.
50.
Heo YS Ryu JM Park SM Park JH Lee HC Hwang KY Kim J 《Experimental & molecular medicine》2002,34(3):211-223
Protein-tyrosine phosphatases (PTPs) constitute a family of receptor-like, and cytoplasmic enzymes, which catalyze the dephosphorylation of phosphotyrosine residues in a variety of receptors and signaling molecules. Together with protein tyrosine kinases (PTKs), PTPs are critically involved in regulating many cellular signaling processes. In this study, diverse compounds were screened for PTP inhibition and selectively screened for inhibitors with the end product inhibition properties. Among phosphate analogues and their derivatives for PTP inhibition, Keggin compounds phosphomolybdate (PM) and phosphotungstate (PT) strongly inhibited both PTP-1B and SHP-1, with K(i) values of 0.06-1.2 micromM in the presence of EDTA. Unlike the vanadium compounds, inhibition potencies of PM and PT were not significantly affected by EDTA. PM and PT were potent, competitive inhibitors for PTPs, but relatively poor inhibitors of Ser/Thr phosphatase. Interestingly, PM and PT did not inhibit alkaline phosphatase at all. The crystal structure of PTP-1B in complex with PM, at 2.0 A resolution, reveals that MoO(3), derived from PM by hydrolysis, binds at the active site. The molybdenium atom of the inhibitor is coordinated with six ligands: three oxo-ligands, two apical water molecules and a S atom of the catalytic cysteine residue. In support of the crystallographic finding, we observed that molybdenium oxides (MoO(3), MoO(2), and MoO(2)Cl(2)) inhibited PTP-1B with IC(50) in the range 5-15 micromM. 相似文献