全文获取类型
收费全文 | 83037篇 |
免费 | 1685篇 |
国内免费 | 2970篇 |
专业分类
化学 | 52152篇 |
晶体学 | 41篇 |
力学 | 1413篇 |
综合类 | 47篇 |
数学 | 2516篇 |
物理学 | 23524篇 |
无线电 | 7999篇 |
出版年
2023年 | 193篇 |
2022年 | 209篇 |
2021年 | 167篇 |
2020年 | 152篇 |
2019年 | 136篇 |
2018年 | 200篇 |
2017年 | 124篇 |
2016年 | 235篇 |
2015年 | 273篇 |
2014年 | 454篇 |
2013年 | 398篇 |
2012年 | 7283篇 |
2011年 | 10122篇 |
2010年 | 1960篇 |
2009年 | 607篇 |
2008年 | 6868篇 |
2007年 | 7291篇 |
2006年 | 7284篇 |
2005年 | 7038篇 |
2004年 | 5723篇 |
2003年 | 3948篇 |
2002年 | 3712篇 |
2001年 | 2649篇 |
2000年 | 2955篇 |
1999年 | 1189篇 |
1998年 | 523篇 |
1997年 | 418篇 |
1996年 | 1242篇 |
1995年 | 1057篇 |
1994年 | 1147篇 |
1993年 | 1441篇 |
1992年 | 1243篇 |
1991年 | 692篇 |
1990年 | 762篇 |
1989年 | 724篇 |
1988年 | 628篇 |
1987年 | 719篇 |
1986年 | 730篇 |
1985年 | 904篇 |
1984年 | 558篇 |
1983年 | 442篇 |
1982年 | 399篇 |
1981年 | 351篇 |
1980年 | 263篇 |
1979年 | 162篇 |
1976年 | 124篇 |
1975年 | 210篇 |
1974年 | 127篇 |
1958年 | 148篇 |
1956年 | 143篇 |
排序方式: 共有10000条查询结果,搜索用时 468 毫秒
981.
The reduction of selenium(VI) to selenium(IV) in 4, 5 and 6M hydrochloric acid was studied at temperatures between 50 and 95 degrees . The reaction rate was determined by measurement of the selenium(IV) formed, by continuous-flow hydride-generation atomic-absorption spectrometry. The most notable feature of the reaction is the strong increase in rate with increasing hydrogen-ion concentration and temperature. The rate increases initially with chloride concentration at constant acidity (mixtures of hydrochloric and perchloric acid) but levels off to an almost constant value at high chloride concentrations. 相似文献
982.
This article reports in detail on the discovery that zirconium(IV) salts of secondary amides and lactams are transformed by Cp(2)ZrHCl to N-substituted imines in one step. The method represents the first controlled reduction of amides and lactams to the corresponding imines, a transformation that is otherwise very difficult to achieve because imines are reduced more rapidly than carboxamides by most metal hydride reagents. No products of reductive cleavage of the carboxamides are observed. Efforts to replace 2 mol equiv of Cp(2)ZrHCl with simpler, less costly alternatives led to the finding that a diisobutylaluminum enolate can be substituted for the initial zirconium enolate. Such aluminum amides are smoothly reduced to the corresponding imine using Cp(2)ZrHCl in good yield. Moreover, aluminum amides are also reduced to imines using either low-valent titanium species or triethylsilane. In these alternative procedures, use of Cp(2)ZrHCl is eliminated altogether in the title transformation. 相似文献
983.
[structure in text] The absolute configurations at 12 chiral centers in amphidinolide C (1), a potent cytotoxic 25-membered macrolide isolated from a marine dinoflagellate Amphidinium sp., were determined to be 3S, 4R, 6R, 7R, 8R, 12R, 13S, 16S, 20R, 23R, 24R, and 29S by combination of NMR analyses, degradation experiments, and synthesis of the C-1-C-7 segment. 相似文献
984.
本文报道新的Tweezer(1)的合成,用^1HNMR研究了新的Tweezer分子和对硝基苯甲酸盐的配位效应,结果表明它兴通过氢键,静电引力和芳环夹心堆叠作用而自动缔合。 相似文献
985.
Vrouwe EX Gysler J Tjaden UR van der Greef J 《Rapid communications in mass spectrometry : RCM》2000,14(18):1682-1688
A sheathless and electrodeless nanospray interface has been used to interface a polycarbonate capillary electrophoresis (CE) chip to a mass spectrometer (MS). The chip was made of two flat polycarbonate plates which were bolted together. Channels were imprinted in one of the plates with metal wires, using a hydraulic press. A short tapered capillary connected to the chip was used as the nanospray emitter. The advantage of this electrodeless interface is that it was not necessary to apply a electrospray voltage to the chip or the nanospray emitter. Instead, the CE voltage already applied to the buffer compartment on the chip, to drive the electrophoresis, was used to generate the spray also. A low conductivity buffer of 1.25 mmol/L ammonium acetate in 80% methanol was used to obtain a large electric field across the buffer channel. The performance of the device was evaluated by analyzing a mixture of three beta-agonists Relative standard deviation (RSD) values obtained were between 4.8 and 5.0%. A sample concentration of 40 nmol/L resulted in a signal-to-noise ratio of 2 to 5 for the different components. Compared to a conventional CE analysis in a fused silica capillary with UV detection, only a minor loss of resolution was observed, which can be attributed to the design of the chip. 相似文献
986.
这篇介绍电解法炼铝的教学文章是化学教师教学经验的分析,文献的概括,和本文作者在中学里教学工作的总结。学生学到炼铝时已经学过了电解法制钠的知识,也知道铝的物理性质、化学性质和铝的化合物,在讲解炼铝时应该运用这些已有的知识。教学开始时用谈话法提出各种炼铝的方法,但只有电解熔融的冰晶石-氧化铝这一方法才适于工艺制造。学生讨论过铝的物理性质、化学性质和铝的化合物之后,一般都能推断氧化铝在高温时能被碳还原成铝。教师指出氧化铝是一种极其稳定的化合物,只有加热到2000°才能被碳还原,同时在这种条件下一部分铝和碳化合成碳化铝,一部分铝气化和一氧化碳作用,结果生成的是氧化铝,碳化铝和金属铝的混合物,没有什么用处。用一氧化碳或氢来还原氧化铝也同样不可能。用活泼的金属,象钾或钠来还原铝化合物可以制取铝但在经济上是不合算的。 相似文献
987.
García F García JM García-Acosta B Martínez-Máñez R Sancenón F Soto J 《Chemical communications (Cambridge, England)》2005,(22):2790-2792
A sensory polymeric material for the colorimetric sensing of cyanide in water has been developed based on the reactivity of this anion with the pyrylium cation. 相似文献
988.
989.
In this contribution, the on-line coupling of solid phase extraction (SPE), based on a restricted-access material (RAM), with sequential injection technique (SIA) for the analysis of biological samples, is described. The SIA-RAM system was tested with a new potential antileucotrienic drug (VUFB-19363 (Quinlukast)) for serum analysis. The method is based on SPE with the novel internal-surface reversed-phase column packing material-alkyl-diol silica (ADS). The supports tolerate direct and repetitive injection of proteinaceous fluids (plasma, serum) and allow reversed-phase partitioning at the internal surface. A column packed with a 25 microm C18 alkyl-diol support was used for direct serum injection. Using a 6-port selection valve and the system of three mobile phases, the polar matrix compounds and metabolites are removed by sequentially aspirated mobile phases with lower content of the organic part (methanol-water (2:98) and following acetonitrile-water (20:80)) to the waste, and then, the analyte enriched on the column is eluted by a strong mobile phase (acetonitrile-methanol-water (40:20:40)) to the UV detector without transfer loss. With the fully automated SIA system, a total analysis time of less than 10 min was achieved. The only off-line sample pre-treatment step required to remove particulate matter was centrifugation. The studies showed a range of linearity (2-40 microg ml(-1)) and a high recovery (93.6-96.8%) of drug from the biological matrix with coefficients of variation (RSD) less than 5.0% (n = 6). This paper introduces a new, simple and robust analytical technique suitable for screening determination and direct analysis of drugs in biological materials. 相似文献
990.
One of the major techniques used for the method development of ternary and quaternary high performance liquid chromatography (HPLC) systems has been to use mixture designs, often referred to as "Glajch's Triangle". This technique does not allow for the systematic and simultaneous optimization of other factors such as gradient time, pH and temperature that affect the quality of separations. An alternative approach is to use experimental designs. The condition, however, that the composition of all components of the mobile phase must total 100% presents a problem when trying to mathematically represent ranges of each mobile phase constituent of a ternary or quaternary system. A method is described here, based on spherical coordinate representations, that adheres to the constraints of the mobile phase composition and allows experimental designs, such as central composite and factorial designs, to be applied to the simultaneous optimization of the mobile phase composition. Other factors, in particular temperature and gradient time, can then be included in the design. As a result of applying these designs to the HPLC separation of phenols and corticosteroids, it was found necessary to include three-way interactions between experimental factors in the model. The significance of these interactions shows that they need to be considered in HPLC method development. 相似文献