全文获取类型
收费全文 | 9741篇 |
免费 | 1683篇 |
国内免费 | 1896篇 |
专业分类
化学 | 8375篇 |
晶体学 | 155篇 |
力学 | 450篇 |
综合类 | 110篇 |
数学 | 1197篇 |
物理学 | 3033篇 |
出版年
2024年 | 2篇 |
2023年 | 81篇 |
2022年 | 211篇 |
2021年 | 225篇 |
2020年 | 257篇 |
2019年 | 374篇 |
2018年 | 290篇 |
2017年 | 317篇 |
2016年 | 424篇 |
2015年 | 523篇 |
2014年 | 610篇 |
2013年 | 780篇 |
2012年 | 941篇 |
2011年 | 956篇 |
2010年 | 724篇 |
2009年 | 720篇 |
2008年 | 826篇 |
2007年 | 720篇 |
2006年 | 632篇 |
2005年 | 618篇 |
2004年 | 535篇 |
2003年 | 393篇 |
2002年 | 447篇 |
2001年 | 363篇 |
2000年 | 272篇 |
1999年 | 183篇 |
1998年 | 161篇 |
1997年 | 126篇 |
1996年 | 98篇 |
1995年 | 74篇 |
1994年 | 82篇 |
1993年 | 57篇 |
1992年 | 51篇 |
1991年 | 47篇 |
1990年 | 49篇 |
1989年 | 28篇 |
1988年 | 34篇 |
1987年 | 17篇 |
1986年 | 18篇 |
1985年 | 14篇 |
1984年 | 6篇 |
1983年 | 7篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1977年 | 3篇 |
1959年 | 1篇 |
1939年 | 1篇 |
1936年 | 7篇 |
1935年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 109 毫秒
161.
A highly sensitive and selective catalytic adsorptive cathodic striping procedure for the determination of trace germanium is presented. The method is based on adsorptive accumulation of the Ge(IV)‐gallic acid (GA) complex onto a hanging mercury drop electrode, followed by reduction of the adsorbed species. The reduction current is enhanced catalytically by addition of vanadium(IV)‐EDTA. The optimal experimental conditions include the use of 0.03 mol/L HClO4 (pH1.6), 6.0×10?3 mol/L GA, 3.0×10?3 mol/L V(IV), 4.0×10?3 mol/L EDTA, an accumulation potential of ?0.10 V(vs. Ag/AgCl), an accumulation time of 120 s and a differential pulse potential scan mode. The peak current is proportional to the concentration of Ge(IV) over the range of 3.0×10?11 to 1.0×10?8 mol/L and the detection limit is 2×10?11 mol/L for a 120 s adsorption time. The relative standard deviation at 5.0×10?10 mol/L level is 3.1%. No serious interferences were found. The method was applied to the determination of germanium in ore, mineral water and vegetable samples with satisfactory results. 相似文献
162.
旋光性高分子的合成(下)刘引烽,华家栋(上海科技大学化学系,上海,201800)4不对称聚合由外消旋手性单体制备旋光性高分子必须通过选择性聚合才能实现。选择性聚合是指外消旋的两个对映异构单体进行聚合时,由于体系中存在着某种不对称的诱导因素,其中之一比... 相似文献
163.
Time-resolved surface-enhanced Raman scattering (SERS) was applied to study the response of Raman bands from 4-cyanopyridine (PyCN) adsorbed on a Ag electrode to variation of the potential; the temporal resolution was 0.1 s. The response of the SERS signals of PyCN was instantaneous to the oxidation potential of Ag electrode. However, delay of the SERS signals was observed while AgCl was reducing. The decay and growth of the SERS bands look place within 1 s in the cases of desorption and adsorption of PyCN on the electrode. It took much longer for PyCN to alter from one adsorption geometry to another on the electrode. 相似文献
164.
采用自组装单层膜(SAMs)技术在压电石英晶体的金电极表面组装巯基丙酸SAMs,以盐酸1-乙基-3-(3-二甲基氨基丙基)碳二亚胺(EDC)和N-羟基琥珀酰亚胺(NHS)作偶联剂,以共价键合方式固定高密度脂蛋白抗体,研制成一种高灵敏的压电免疫传感器用于检测人血清中低含量的高密度脂蛋白。利用压电装置的实时监测功能,考察了巯基丙酸在金电极表面的自组装成膜过程与机制;研究了晶振固定抗体及其反应结合抗原的液相振荡行为和传感特性。传感器采用初始速率法测定高密度脂蛋白的线性浓度范围为1.63~18.8 mg.L-1,检出限为0.82 mg.L-1。 相似文献
165.
Guo Jin-xin Sun Si-xiu Zhu Rong-xiu Yin Zhi-lei Yu Hai-yun Li Da-zhi Zhang Wei-min Xu Xian-gang Sun Xuan Shao Hua 《Journal of Radioanalytical and Nuclear Chemistry》2004,261(1):221-224
The 222Rn emanation fraction (EF) released from the technically enhanced naturally occurring radioactive material (TE-NORM) wastes
at certain sites of petroleum and gas production was determined. The samples were analyzed by γ-ray spectrometry to determine
the activity concentration of the 226Ra content, of which the 222Rn emanation fraction was calculated. The results showed that the 222Rn emanation fraction differs in the oil and gas production sites and it is independent of the activity concentration of 226Ra.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
166.
The CHCl3 extract of dried roots of Hemerocallis fulva (L.) L. afforded a novel diterpene named hemerocallal A ( 1 ), which is the second reported naturally occurring diterpene with a trans‐bicyclo[5.1.0]octane system. The BuOH extract afforded a new glycoside named hemerocalloside ( 2 ). Their structures were established on the basis of spectroscopic and chemical studies. 相似文献
167.
The conversion of phosphoenolpyruvate (PEP) to phosphonopyruvate (P-pyr) is catalyzed by PEP mutase via a dissociative mechanism. In this work, we investigate the uncatalyzed reaction using ab initio methods, density functional theory, and the semiempirical MNDO/d method. Comparisons of geometries and relative energies of stationary points (minima and transition states) with density functional results indicate that the semiempirical method is reasonably accurate. Solvent effects are examined using implicit solvent models, including the recently extended smooth conductor-like screening model. Due to the large negative charge carried by the system, solvation is found to drastically alter the location and energy of stationary points along the dissociative reaction pathways. The influence of substituting a nonbridging phosphoryl oxygen by sulfur (thio effects) was also investigated. Implications of these results for the enzymatic reaction are discussed. 相似文献
168.
The liquid chromatographic enantiomer separation of N-fluorenylmethoxycarbonyl (FMOC) protected alpha-amino acids and their ethyl ester derivatives was performed on polysaccharide-derived chiral stationary phases, Chiralcel OD, Chiralpak AD, and Chiralpak AS. In general, Chiralcel OD and Chiralpak AD showed good performance for resolution of N-FMOC alpha-amino acids and their ethyl esters, respectively. All investigated N-FMOC alpha-amino acid enantiomers were baseline separated on Chiralcel OD or Chiralpak AD, whereas N-FMOC alpha-amino acid ethyl ester enantiomers were baseline resolved (alpha = 1.15-3.03) on Chiralpak AD, except for two analytes. The L-enantiomers of all examined FMOC alpha-amino acid ethyl ester derivatives are preferentially retained on Chiralpak AD, while the elution orders of the other enantiomer separations are not consistent. 相似文献
169.
Meyers CY Chan-Yu-King R Hua DH Kolb VM Matthews WS Parady TE Horii T Sandrock PB Hou Y Xie S 《The Journal of organic chemistry》2003,68(2):500-511
Most alkyl phenyl sulfones are readily alpha-chlorinated with CCl(4) and alpha-brominated with CBrCl3 in KOH-t-BuOH via radical-anion radical pair (RARP) reactions. While isopropyl mesityl sulfone (4) is easily alpha-chlorinated with CCl(4), it was completely recovered when treated with the more reactive CBrCl3. Subsequent investigations showed the latter result to be due to the poor acidity of 4 together with the rapid depletion of CBrCl3 and KOH by their reaction with each other, and led to a variety of other important results. 4-Hydroxyphenyl isopropyl sulfone (6) is unreactive with either CCl4 or CBrCl3 in KOH-t-BuOH, its phenoxide anion strongly reducing the electronegativity of the sulfonyl group, thereby inhibiting alpha-anion formation. This effect is reversed by the electron-withdrawing influence of two alpha-phenyls, so that benzhydryl 4-hydroxyphenyl sulfone (8) is readily alpha-halogenated in KOH-t-BuOH with CCl4 or CBrCl3. On further contact with KOH-t-BuOH the alpha-halogenated sulfones from 8 are decomposed into benzophenone and phenol. While the alpha-halogenated derivatives of 4-methoxyphenyl benzhydryl sulfone (9) are stable to base, they are decomposed even under mildly acidic conditions into 4-methoxyphenyl 4-methoxybenzenethiolsulfonate (9c), phenol, and benzophenone. Mono-alpha-halogenation of benzyl phenyl sulfone (10) enhances the rate of the subsequent halogenation, so that alpha,alpha-dihalogenation is attained while much substrate is still present and the mono-alpha-halogenated product is not detected. The ease of reductive debromination of alpha-bromo sulfones with Cl3C- was correlated with the stability of the formed alpha-anions, explaining the success with alpha-bromobenzylic sulfones but failure with alpha-bromoalkyl sulfones. In the presence of air and the absence of competing halogenation, formation of the alpha-anions of alkyl aryl sulfones is quickly accompanied by oxidative cleavage by atmospheric O2, leading to the formation of arenesulfonyl alcohols, arenesulfonyl halides, and haloarenes. 相似文献
170.
Yao Zu Liao Mei Hua Xin Ming Chun Li Sheng Su College of Materials Science Engineering Huaqiao University Quanzhou China 《中国化学快报》2007,18(2):213-216
O-Lauroyl chitosan/poly(L-lactide) (OCS/PLLA) blend membranes with different compositions were prepared by solution-casting approach using chloroform as common solvent. The experimental results of FT-IR, DSC and WAXD indicated that inter-association hydrogen-bond interactions existed between OCS and PLLA in the blend membranes. And SEM observation confirmed that the blend membranes with suitable compositions were compatible. 相似文献