全文获取类型
收费全文 | 65403篇 |
免费 | 13591篇 |
国内免费 | 5127篇 |
专业分类
化学 | 61714篇 |
晶体学 | 691篇 |
力学 | 2225篇 |
综合类 | 267篇 |
数学 | 5954篇 |
物理学 | 13270篇 |
出版年
2024年 | 60篇 |
2023年 | 563篇 |
2022年 | 953篇 |
2021年 | 1088篇 |
2020年 | 2209篇 |
2019年 | 3484篇 |
2018年 | 1860篇 |
2017年 | 1513篇 |
2016年 | 4480篇 |
2015年 | 4672篇 |
2014年 | 4783篇 |
2013年 | 5928篇 |
2012年 | 5383篇 |
2011年 | 4949篇 |
2010年 | 4693篇 |
2009年 | 4582篇 |
2008年 | 4397篇 |
2007年 | 3622篇 |
2006年 | 3149篇 |
2005年 | 3110篇 |
2004年 | 2592篇 |
2003年 | 2211篇 |
2002年 | 2873篇 |
2001年 | 2120篇 |
2000年 | 1896篇 |
1999年 | 1041篇 |
1998年 | 630篇 |
1997年 | 575篇 |
1996年 | 597篇 |
1995年 | 497篇 |
1994年 | 451篇 |
1993年 | 409篇 |
1992年 | 381篇 |
1991年 | 342篇 |
1990年 | 298篇 |
1989年 | 243篇 |
1988年 | 208篇 |
1987年 | 155篇 |
1986年 | 175篇 |
1985年 | 179篇 |
1984年 | 115篇 |
1983年 | 73篇 |
1982年 | 82篇 |
1981年 | 58篇 |
1980年 | 57篇 |
1979年 | 59篇 |
1978年 | 40篇 |
1976年 | 38篇 |
1974年 | 41篇 |
1973年 | 45篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
901.
The applicability of (1R,2R)-1,3-diacetoxy-1-(4-nitrophenyl)-2-propyl isothiocyanate [(R,R)-DANI] as a recently developed chiral derivatizing agent for the enantioseparation of a series of β-blockers is described. The thiourea diastereomers formed were analyzed by reversed-phase high-performance liquid chromatography, mixtures of water and methanol or acetonitrile being used for elution. Conditions of derivatizations (temperature, reagent excess and reaction time) were optimized, and the effects of organic modifiers on the retention and separation were investigated; the diastereomers could readily be baseline separated with methanol-containing mobile phases with resolutions between 1.58 and 2.72. 相似文献
902.
Starting from the para‐phenylenediamine derivative HN(SiMe3)‐C6H4‐NH(SiMe3), a lithiation and subsequent borylation give [(MeO)2B]N(SiMe3)‐C6H4‐N(SiMe3)[B(OMe)2] ( 1 ), the hydridation of which yields Li2[(H3B)N(SiMe3)‐C6H4‐N(SiMe3)(BH3)] ( 2 ). Applying ZrCl4 upon 2 initiates a condensation to give the title compound [‐N(SiMe3)‐p‐C6H4‐N(SiMe3)‐BH‐]2, a hetero[3, 3]paracyclophane with two N‐B‐N chains that connect the para‐phenylene units. The product 3 crystallizes in the orthorhombic space group P212121. 相似文献
903.
利用FT-IR,测定了四种异构丁醇十四氯化碳、+正庚烷, +苯和1,2-二氯乙烷稀溶液在3800—3000 cm~(-1)内的红外吸收光谱。缔合峰与自由羟基峰的面积之比与溶质、溶剂的性质有关, 且在极稀溶液区与溶质的质量百分比浓度之间有良好的直线关系。本文又运用1-n(环状)模型对有关体系进行了对比研究。结果表明, 丁醇分子支链度的增加以及丁醇分子与苯和1,2-二氯乙烷之间的特殊相互作用, 降低了醇分子的缔合能力。稀溶液中, 丁醇分子在苯和1,2-二氯乙烷中主要以单体和环状二聚体形式存在, 在四氯化碳中以单体和环状三聚体形式存在, 而正丁醇分子在正庚烷中主要为单体和环状四聚体, 异、仲、特丁醇主要为环状三聚体和单体。 相似文献
904.
This review aims to provide a summary of the progress in TP small molecule fluorescent probes for enzymes in recent years and displays the main fluorescent mechanisms that have been applied to design probes. 相似文献
905.
Teng-Yuan Dong Chienlin Huang Chiao-Pei Chen Ming-Cheng Lin 《Journal of organometallic chemistry》2007,692(23):5147-5155
We describe the formation of stable dithiol-bifunctionalized Ru(II)-terpyridine monolayer onto gold electrode. The coverage-dependent behavior onto gold electrode has been studied by electrochemical technique. The stability, surface charge coverage, and electron-transfer kinetics were assessed by cyclic voltammetry. Functionalized monolayer-protected Au clusters (MPCs) were also prepared. The spectroscopic characterization data of MPCs using UV-Vis and TEM techniques are discussed. TEM images showed that functionalized spherical nanoclusters of 4.7 ± 0.3 and 4.3 ± 0.2 nm were produced. The particle sizes are uniform with a narrow size distribution. The morphology of Au(1 1 1) metal surface modified with MPCs was imaged using atomic force microscopy (AFM). The nanoparticle layer exhibits a distinct surface morphology, irregularly shaped domains with dimensions from 20 to 60 nm and root mean square heights of 2.401 nm. 相似文献
906.
R.-L. Yun Y.-M. Chang C.-H. Lin K.-H. Hu C.-M. Shu 《Journal of Thermal Analysis and Calorimetry》2006,85(1):107-113
In industrial processes, information
on the safety property of chemicals is essentially crucial for safe handling
during unit operations. Ensuring the safe use of combustible or flammable
substances in processes is unlikely without detailed investigations of their
flammability characteristics and related hazards. We studied 3-methyl pyridine
(3-picoline), e.g., flammability limits (LFL/UFL), maximum explosion pressure
(P
max), maximum
explosion pressure rise (dP/dt)max, minimum oxygen concentration
(MOC), vapor deflagration index (K
g),
and characterized the influence of inert steam (H2O)
on critical parameters for 3-picoline/water mixtures at 270°C, 1 atm,
various oxygen concentrations, and vapor mixing ratios (100/0, 30/70, 10/90
and 5/95 vol.%) with a 20-L-Apparatus in simulated conditions, respectively.
The results showed that the flammability characteristics
of 3-picoline(aq) all increased with the oxygen concentration.
However, as the composition of inert steam increased, the flammability parameters
and the degree of fire and explosion hazards were significantly reduced, instead.
This study elucidated the flammability properties of 3-picoline mixed with
inert steam. The conclusions could be applied to proactively prevent the relevant
processes from incurring fire and explosion accidents. 相似文献
907.
In this paper, the chronoamperometry was used to study the charging processes of polyethylenedioxythiophene (PEDOT) modified electrodes in the potential range where PEDOT was in the oxidized state. The results show that the charging behaviors of the PEDOT films are well agreed with the exhausted finite diffusion model. The dependence of the capacitance values of the films on potential and concentration of solution was also studied in this potential range. 相似文献
908.
In this work, a new ligand, 2,9-bis[N,N-bis(carboxymethyl)-aminomethyl]-1,10-phenanthroline (BBCAP), was synthesized and
used to establish a novel fluorimetric method for the determination of trace amounts of terbium in a binary system. Its luminescence
mechanism was studied. The excitation and emission wavelengths are 284 nm and 547 nm, respectively. Other rare-earth metal
ions in 100-fold excess caused no interference. The fluorescence intensity was a linear function of the concentration of terbium
in the range of 5.0 × 10−10–1.0 × 10−6 mol/L. The detection limit was 2.0 × 10−11 mol/L (n = 12). The standard addition method was used to determine the terbium in a synthetic rare-earth sample with satisfactory
results. This method represents a direct, rapid, selective and sensitive analytical procedure with a widely linear range.
Received November 29, 2001 Revision February 9, 2002 相似文献
909.
异咯嗪蒙脱石修饰电极的电化学行为 总被引:1,自引:0,他引:1
应用十六烷基三甲基溴化铵对蒙脱石进行改性,成功地制备稳定性良好的异咯嗪蒙脱石修饰电采,用循环伏安法对此修饰电极的电化学行为进行了研究。测定了异咯嗪在蒙脱石膜内的化学扩散系数,对异咯嗪在改性蒙脱石中电极反应机制进行了探讨。 相似文献
910.
Summary A theoretical treatment is presented which considers differences between the composition of the mobile phase and solvents
that are incorporated into the bonded phase via preferential sorption. Equations are derived and used to analyze retention
data for various homologs chromatographed under reversed-phase conditions using alkyl bonded phases and combinations of water-methanol,
water-acetonitrile and watertetrahydrofuran as mobile phases. In the case of water-methanol the surface phase and bulk mobile
phase compositions are similar. However, significant differences in composition between the two phases are observed when binary
combinations of water-acetonitrile and water-tetrahydrofuran are used as the cluents. 相似文献