全文获取类型
收费全文 | 2382篇 |
免费 | 367篇 |
国内免费 | 244篇 |
专业分类
化学 | 1868篇 |
晶体学 | 16篇 |
力学 | 132篇 |
综合类 | 26篇 |
数学 | 172篇 |
物理学 | 779篇 |
出版年
2024年 | 7篇 |
2023年 | 29篇 |
2022年 | 54篇 |
2021年 | 75篇 |
2020年 | 85篇 |
2019年 | 83篇 |
2018年 | 59篇 |
2017年 | 58篇 |
2016年 | 75篇 |
2015年 | 97篇 |
2014年 | 133篇 |
2013年 | 174篇 |
2012年 | 205篇 |
2011年 | 208篇 |
2010年 | 159篇 |
2009年 | 151篇 |
2008年 | 158篇 |
2007年 | 147篇 |
2006年 | 123篇 |
2005年 | 96篇 |
2004年 | 90篇 |
2003年 | 78篇 |
2002年 | 76篇 |
2001年 | 82篇 |
2000年 | 78篇 |
1999年 | 57篇 |
1998年 | 63篇 |
1997年 | 50篇 |
1996年 | 47篇 |
1995年 | 31篇 |
1994年 | 21篇 |
1993年 | 24篇 |
1992年 | 13篇 |
1991年 | 18篇 |
1990年 | 9篇 |
1989年 | 11篇 |
1988年 | 12篇 |
1987年 | 11篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 7篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1966年 | 2篇 |
1931年 | 1篇 |
1924年 | 1篇 |
1884年 | 1篇 |
排序方式: 共有2993条查询结果,搜索用时 265 毫秒
41.
Zhuang Hong Cheng Tiexin Bi Yingli Zhou Guangdong Zhen Kaiji 《Reaction Kinetics and Catalysis Letters》2004,81(1):13-20
Factors (reaction temperature, reaction time, flow rate of oxygen, amount of catalyst, etc.) influencing the catalytic properties of Co3O4/SiO2catalyst in the oxidation octadecan-1-ol to octadecanoic acid were investigated. The catalysts were characterized by means of XRD, FT-IR and N2-adsorption. The experimental results indicate that under the optimal condition the selectivity to octadecanoic acid reached 97.5 % over 5 % Co3O4/SiO2 catalyst.This revised version was published online in December 2005 with corrections to the Cover Date. 相似文献
42.
In weakly acidic buffer medium, the interaction of amikacin with calf thymus DNA, yeast RNA and denatured DNA has been investigated by using resonance Rayleigh scattering (RRS) technique. The result shows that calf thymus DNA is capable of enhancing the RRS intensity of the amikacin, while yeast RNA and denatured DNA have very little enhancement effect. Based on the characteristics, a sensitive assay for detecting double-stranded DNA in the presence of denatured DNA and yeast RNA has been developed. The enhancement of the RRS signal is directly proportional to the concentration of double-stranded DNA in the range 0.02-12.0 μg ml−1 for calf thymus DNA and its detection limit (3σ) is 2.5 ng ml−1. The method shows a wide linear range and high sensitivity, and almost no interference can be observed from RNA, denatured DNA, amino acid and most of the metal ions. The trace amounts of nucleic acid in synthetic samples and practical samples are determined with satisfactory results. Therefore, the proposed method is promising for as an effect means for recognition in vivo and determination in situ of double-stranded DNA. 相似文献
43.
The biological effects of aluminium have received much attention in recent years. Speciation of Al is of basic relevance as it concerns its reactivity and bioavailability. A differential pulse voltammetry (DPV) procedure is proposed for speciation analysis of Al(III) in natural waters and biological fluids using six catechols (L-dopa, dopamine, epinephrine, norepinephrine, caffeic acid and o-benzenediol) as electroactive ligands. The decrease of the DPV anodic peak current for each catechol ligand is linear with the increase of Al concentration. This speciation analysis idea is based on the measurement of the complexation capacity, namely, different affinities of Al(III) for catechols and organic ligands under two pH conditions. The labile monomeric Al fraction (mainly inorganic aluminium) is determined at pH 4.6, while the total monomeric Al fraction is determined at pH 8.5. The principle for Al(III) speciation analysis by an electrochemical method is discussed. This sensitive and simple fractionation method is successfully applied to the speciation analysis of Al in natural waters and the results agree well with those of Driscoll's method. The speciation analysis of Al in biological fluids is also explored and the results are compared with those obtained by ultrafiltration and dialysis. Compared with other speciation protocols the electrochemical method possesses some remarkable advantages: rapidity, high sensitivity, cheap instrumentation and a simple operation procedure. 相似文献
44.
Analytical methodologies for aluminium speciation in environmental and biological samples--a review 总被引:1,自引:0,他引:1
Bi SP Yang XD Zhang FP Wang XL Zou GW 《Fresenius' Journal of Analytical Chemistry》2001,370(8):984-996
It is recognized that aluminium (Al) is a potential environmental hazard. Acidic deposition has been linked to increased Al concentrations in natural waters. Elevated levels of Al might have serious consequences for biological communities. Of particular interest is the speciation of Al in aquatic environments, because Al toxicity depends on its forms and concentrations. In this paper, advances in analytical methodologies for Al speciation in environmental and biological samples during the past five years are reviewed. Concerns about the specific problems of Al speciation and highlights of some important methods are elucidated in sections devoted to hybrid techniques (HPLC or FPLC coupled with ET-AAS, ICP-AES, or ICP-MS), flow-injection analysis (FIA), nuclear magnetic resonance (27Al NMR), electrochemical analysis, and computer simulation. More than 130 references are cited. 相似文献
45.
Liancai Wang Xiangjun Bi Aiying Zhang Jianye Zhou 《Polymer Degradation and Stability》2006,91(9):2220-2228
A series of biodegradable aliphatic/aromatic copolyesters, poly(butylene terephthalate)-co-poly(butylene cyclohexanedicarboxylate)-b-poly(ethylene glycol) (PTCG), were prepared by a two-step melt polycondensation method and characterized by means of GPC, FTIR, NMR, DSC, TGA, etc. The effects of aliphatic ester content on the physical, mechanical and thermal properties, as well as in vitro and in vivo degradation behaviors were investigated. The decrease in mechanical strength was observed with an increase in poly(butylene cyclohexanedicarboxylate) (PBC) molar fraction. DSC results showed one melting point and two glass transition temperatures in all samples, and the melting temperature was found to go down gradually as more cyclohexanedicarboxylic acid (CHDA) was added. During the in vitro and in vivo degradation processes, erosion of the surface was dominant as evidenced by scanning electron microscopic observations. The copolyesters containing many CHDA units were featured by the higher water uptake and faster degradation due to much richer amorphous phase within them. 相似文献
46.
JunJieKANG ShiBiFANG 《中国化学快报》2004,15(1):87-89
Network polymer electrolytes with free oligo(oxyethylene) chains as internal plasticizers were prepared by cross-linking poly(ethylene glycol) acrylates. The effects of salt concentration and properties of internal plasticizers on ionic conductivity were studied. 相似文献
47.
The interaction of ammonium trioxovanadate(V) with cysteine in aqueous solution was studied by cyclic voltammetry and absorption spectroscopy techniques. In the absence of cysteine, the cyclic voltammogram (CV) of ammonium trioxovanadate(V) solution in 0.1 M phosphate buffer (pH 7) gave two peaks at -0.130 V (reversible) and -0.400 V (irreversible). These peaks (-0.130 V, -0.400 V) can be attributed to V(V)/V(IV) and V(IV)/V(III) redox processes, respectively. In the presence of cysteine at low scan rate (40 mV/s), the peak at -0.780 V, which is assigned to the irreversible reduction of free cystine, was observed. In addition, the reduction peak of the disulfidic anion S(2)(2-) was seen at -0.650 V. Under aerobic conditions, the peaks of the disulfidic anion S(2)(2-) and free cystine are well separated. From electronic spectra of ammonium trioxovanadate(V) and cysteine mixtures, LMCT transition associated with V(V)-cyteine complex was obtained at 743 nm. The stoichiometry (ML(2)) and stability constant (log beta(1:2)=6.67) of V(V)-cysteine complex were determined by means of mole ratio method. 相似文献
48.
采用大环抗生素类万古霉素手性固定相高效液相色谱法研究了一系列曼尼希碱类化合物的手性分离情况,并讨论了流动相中有机相的种类和比例、缓冲盐的种类和浓度、pH和柱温对该类化合物手性分离的影响。最佳实验条件为:乙腈:硝酸铵(35mmol/L,pH3.8)=15∶85(V/V),柱温15℃,流速0.6mL/min,检测波长300nm;四氢呋喃:硝酸铵(20mmol/L,pH4)=15∶85(V/V),柱温15℃,流速0.6mL/min,检测波长350nm。通过对比研究8种曼尼希碱类化合物的色谱行为,从结构上讨论了化合物中各种官能团对手性分离的影响,并探讨了手性分离的内在机制。 相似文献
49.
Wender PA Baryza JL Bennett CE Bi FC Brenner SE Clarke MO Horan JC Kan C Lacôte E Lippa B Nell PG Turner TM 《Journal of the American Chemical Society》2002,124(46):13648-13649
Macrocycle 1 is a new highly potent analogue of bryostatin 1, a promising anti-cancer agent currently in human clinical trials. In vitro, 1 displays picomolar affinity for PKC and exhibits over 100-fold greater potency than bryostatin 1 when tested against various human cancer cell lines. Macrocycle 1 can be generated in clinically required amounts by chemical synthesis in only 19 steps (LLS) and represents a new clinical lead for the treatment of cancer. 相似文献
50.
Bi Xian Tonghua Li Chen Kai Tongcheng Cao Jianrong Huang Yunpeng Qi 《Journal of mathematical chemistry》2004,36(2):129-138
Orthogonal signal correction (OSC) was a data preprocessing algorithm. It ensured that the filtered information was irrelevant to concentration data while using it to filter the noise from the original data. This paper extended the OSC application range from two-way data to three-way data. Two drug data sets, Enoxacin, Norfloxacin, Ciprofloxacin and Betamethasone, cortisone acetate, prednisone acetate, showed that the application of the OSC algorithm to three-way HPLC data was feasible and needed further research. 相似文献