全文获取类型
收费全文 | 6284篇 |
免费 | 754篇 |
国内免费 | 1432篇 |
专业分类
化学 | 5770篇 |
晶体学 | 41篇 |
力学 | 467篇 |
综合类 | 67篇 |
数学 | 994篇 |
物理学 | 1131篇 |
出版年
2024年 | 42篇 |
2023年 | 141篇 |
2022年 | 284篇 |
2021年 | 354篇 |
2020年 | 524篇 |
2019年 | 324篇 |
2018年 | 280篇 |
2017年 | 262篇 |
2016年 | 352篇 |
2015年 | 282篇 |
2014年 | 417篇 |
2013年 | 561篇 |
2012年 | 361篇 |
2011年 | 374篇 |
2010年 | 297篇 |
2009年 | 330篇 |
2008年 | 346篇 |
2007年 | 333篇 |
2006年 | 317篇 |
2005年 | 276篇 |
2004年 | 253篇 |
2003年 | 305篇 |
2002年 | 298篇 |
2001年 | 180篇 |
2000年 | 141篇 |
1999年 | 114篇 |
1998年 | 108篇 |
1997年 | 76篇 |
1996年 | 93篇 |
1995年 | 66篇 |
1994年 | 64篇 |
1993年 | 44篇 |
1992年 | 57篇 |
1991年 | 22篇 |
1990年 | 22篇 |
1989年 | 19篇 |
1988年 | 23篇 |
1987年 | 16篇 |
1986年 | 21篇 |
1985年 | 30篇 |
1984年 | 17篇 |
1983年 | 6篇 |
1982年 | 17篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1975年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有8470条查询结果,搜索用时 0 毫秒
101.
以1-甲基吡咯为原料,通过酰化、硝化、酯化、还原、成盐等五步反应,合 成得到1-甲基-2-甲氧羰基-4-氨基吡咯盐酸盐,总产率20%左右。该法具有 原料便宜易得、操作简单、产物易于分离提纯等优点,有利于该化合物的大量制备 和应用。 相似文献
102.
103.
痕量砷流动注射在线还原氢化物发生原子吸收测定 总被引:5,自引:0,他引:5
方法采用流动注射停流技术使水及土壤浸出液中As(V)在线还原为As(Ⅲ),不经手工还原,用氢化物发生原子吸收光谱法直接测定砷的含量。含4mol/L HCl的样品溶液与30%碘化钾溶液在编结式反应器中混合,并在采样环中停流40s,达完全还原后注入到载流中与硼氢化钠反应,采样速度55次/h,检出限(3δ)0.1μg/L,对自来水和土壤浸出液的加标回收结果满意。 相似文献
104.
Refat M. Hassan 《Journal of polymer science. Part A, Polymer chemistry》1993,31(5):1147-1151
The kinetics of decomposition of [Alg · Mn VIO42?] intermediate complex have been investigated spectrophotometrically at a constant ionic strength of 0.5 mol dm?3. The decomposition reaction was found to be first-order in the intermediate concentration. The results showed that the rate of reaction was base-catalyzed. The kinetic parameters have been evaluated and found to be ΔS? = ?103.88±6.18 J mol?1 K?1, ΔH? = 51.61 ± 1.02 kJ mol?1, and ΔG? = 82.57 ± 2.86 kJ mol?1, respectively. A reaction mechanism consistent with the results is discussed. © 1993 John Wiley & Sons, Inc. 相似文献
105.
Masaru Kojima 《Tetrahedron letters》2007,48(25):4431-4436
A new fluorous benzylidene acetal protecting group was regioselectively introduced into carbohydrates, deprotected under acidic conditions, and reused. Oligosaccharides were synthesized via regioselective conversion of the fluorous acetal group to the benzyl group by traditional reaction conditions. The fluorous compounds were easily separated from non-fluorous by-products by fluorous solid phase extraction. 相似文献
106.
《Electroanalysis》2003,15(1):19-25
The electrochemical behavior of 2‐(5‐amino‐ 1,3,4‐oxadiazolyl)‐5‐nitrofuran (NF359) and its comparison with well‐known drugs such as nifurtimox (NFX) and nitrofurazone (NFZ) in protic, mixed and aprotic media by cyclic voltammetry, tast and differential pulse polarography was studied. All the compounds were electrochemically reducible in all media being the reduction of the nitrofuran group the main voltammetric signal. The one‐electron reduction couple due to the nitro radical anion formation was visualized in mixed (for NF359 and NFZ) and aprotic media (for all compounds). By applying a cyclic voltammetric methodology we have calculated the decay constants (k2) of the corresponding nitro radical anions in mixed and aprotic media. In mixed medium data fit well with a disproportionation reaction of the nitro radical anion but in aprotic medium fit better with a dimerization reaction. Also, considering cyclic voltammetric measurements in aprotic media we have estimated the reduction potential of the RNO2/RNO2.? couple in aqueous medium, pH 7 (E17 values) finding very good correlation with E17 values obtained by pulse radiolysis. Furthermore we have calculated the equilibrium constants from the electron transfer from nitro radical anion to oxygen (kO2) finding that nitro radical anion from NF359 is thermodynamically favored to react with oxygen in respect to both NFZ and NFX. 相似文献
107.
The capacity for anaerobic decolorization of a sulfonated azo dye, Congo Red, by a strain of a sulfate-reducing bacterium
was evaluated. After optimizing the growth rate of the bacteria on a simple carbon source and terminal electron acceptor pair,
lactate and sulfate, respectively, the effect of the dye concentration on their growth rate was analyzed. The decolorization
rate was affected by the dye concentration in the growth medium. The azo-bond cleavage mechanism of reductive decolorization
with the formation of benzidine was consistent with the results, as this metabolite was identified by high-performance liquid
chromatography. Several fractions of the culture medium, including lysed cell extracts, were examined for the capacity to
reduce the azo dye. This reduction capacity was found in the culture medium in which the cells had previously grown. The results
showed that the mechanism of reductive decolorization of this sulfonated azo dye was extracellular and nonenzymatic, consistent
with the production of sulfide anion by the microorganisms while growing on lactate and sulfate. The sulfide anions were the
cause of the reduction leading to the disappearance of color in the medium. To increase the rate of decolorization, the presence
of ferrous ion was also necessary together with the lactate and sulfate substrates. 相似文献
108.
金属/氮/碳催化剂(M/N/C,M=Fe、Co等)是最有发展前景的非贵金属电催化剂之一,其性能依赖于催化剂表面的活性物种密度.通过常规的热解含氮前驱物与金属盐的方法制得的催化剂往往存在金属活性物种被包埋而不能有效利用的缺点.考虑到石墨相氮化碳(g-C3N4)富含类吡啶氮和亚纳米孔腔结构,将g-C3N4包覆在高导电性碳纳米笼(hCNC)表面,进而利用表层g-C3N4的配位和限域作用锚定大量Co2+离子,获得的Co/g-C3N4/hCNC复合物经热解后形成了活性位高度暴露、导电性好、孔结构丰富的Co/N/C催化剂.800℃热解得到的最优化催化剂在碱性介质中展现出优异氧还原活性,其起始电位(0.97 V)与商业Pt/C催化剂相当,且抗甲醇干扰性能和稳定性优异.此项研究提供了一种构建具有高度暴露活性位的M/N/C催化剂的有效策略. 相似文献
109.
The reduction of prochiral ketones using chiral reducing reagents, prepared from lithium aluminum hydride and (-)-(1R, 2S, 3S, 5R)-10-anilinopinanediol (5) and (-)-(1R, 2S, 3S, 5R)-10-N-methylanilinopinanediol (6), affords chiral secondary alcohols in useful chemical yields (70 ~ 93%) but in low optical purity (8 ~ 33% ee). Modifiers 5 and 6 are synthesized from (lR)-(-)-β-pinene in three steps. 相似文献
110.
In recent years, many optically active β-amino alcohols, mostly derived from naturally occurring α-amino acids, have been incorporated into the asymmetric synthesis as chiral auxiliaries or ligands.1 An effective asymmetric catalysts, the oxazaborolidine-borane reagents, which were originally pioneered by Itsuno and Corey,2 were generally prepared from chiral β-amino alcohols by the reaction with boric acid or formed in situ in the presence of borane. These reagents provide excellent enanti… 相似文献