全文获取类型
收费全文 | 14995篇 |
免费 | 1943篇 |
国内免费 | 1975篇 |
专业分类
化学 | 5629篇 |
晶体学 | 229篇 |
力学 | 508篇 |
综合类 | 162篇 |
数学 | 912篇 |
物理学 | 3255篇 |
综合类 | 8218篇 |
出版年
2024年 | 63篇 |
2023年 | 203篇 |
2022年 | 447篇 |
2021年 | 489篇 |
2020年 | 510篇 |
2019年 | 494篇 |
2018年 | 452篇 |
2017年 | 536篇 |
2016年 | 622篇 |
2015年 | 840篇 |
2014年 | 980篇 |
2013年 | 1135篇 |
2012年 | 1316篇 |
2011年 | 1262篇 |
2010年 | 1117篇 |
2009年 | 1141篇 |
2008年 | 1201篇 |
2007年 | 1063篇 |
2006年 | 919篇 |
2005年 | 778篇 |
2004年 | 598篇 |
2003年 | 410篇 |
2002年 | 450篇 |
2001年 | 374篇 |
2000年 | 361篇 |
1999年 | 255篇 |
1998年 | 139篇 |
1997年 | 126篇 |
1996年 | 116篇 |
1995年 | 98篇 |
1994年 | 74篇 |
1993年 | 68篇 |
1992年 | 51篇 |
1991年 | 33篇 |
1990年 | 41篇 |
1989年 | 44篇 |
1988年 | 25篇 |
1987年 | 13篇 |
1986年 | 9篇 |
1985年 | 13篇 |
1984年 | 6篇 |
1983年 | 12篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 8篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1959年 | 1篇 |
1955年 | 1篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
201.
枸杞多糖对白血病细胞作用热化学特征研究 总被引:3,自引:0,他引:3
用微量热法研究了枸杞多糖对小鼠白血病细胞L1210代谢作用的热化学特征。结果表明,枸杞多糖对L1210细胞代谢有明显的抑制作用,为枸杞在防治肿瘤中的应用提供了可靠的信息。 相似文献
202.
核磁共振法研究CH2=CHSi(OET)3的水化反应 总被引:1,自引:0,他引:1
高强水泥的生产近年来巳成为许多国家发展水泥生产的一个主要方向。在水泥中加入有机单体可以改善混凝土的质量,如加重量比为3%的有机硅烷偶联剂乙烯基三乙氧基硅烷CH_2=CHSi(OEt)_3(简称VTES)于水泥中,即可在较大程度上增加水泥石的强度。 相似文献
203.
The reaction of PdCl2 in water with 2-hydroxypropane-1, 3-diaminetetraacetic acid (HPDTA) gave the complex Pd (C11H16N2O9)·1. 5H2O, which was characterized by elemental analysis, IR, NMR and single-crystal X-ray diffraction. The spectroscopic and X-ray diffraction data show that Pd ( Ⅱ ) is coordinated by two nitrogen atoms and two car-boxylic oxygen atoms. The complex crystallizes in monoclinic space group Pc with a = 1. 1240(2), b=1. 1183(2), c=1. 2597(3) nm, β=96. 33(2)°V=1. 5737(6) nm3, Z = 4, R= 0.038. The structure contains two crystallographically independent molecules which have slightly different orientations and are connected by hydrogen bonds. 相似文献
204.
In this work, the electrochemical behavior of ferrocene (Fc) was investigated by cyclic voltammetry (CV) in room temperature ionic liquids (RTILs) of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIBF4) on glass carbon (GC), edge plane pyrolytic graphite (EPPG) and multi‐walled carbon nanotube (MWCNTs)‐modified EPPG electrodes, respectively. The results demonstrated that on GC electrode, pairs of well‐defined reversible peaks were observed, while for the electrode of EPPG, the peak potential separation (ΔEp) is obviously larger than the theoretical value of 59 mV, hinting that the electrode of EPPG is distinguished from the commonly used electrode, consistent with the previous proposition that EPPG has many “defects”. To obtain an improved electrochemical response, multi‐walled carbon nanotubes (MWCNTs) were modified on the electrode of EPPG; the increased peak current and promoted peak potential separation not only proved the existence of “defects” in MWCNTs, but also supported that “creating active points” on an electrode is the main contribution of MWCNTs. Initiating the electrochemical research of Fc on the MWCNTs‐modified EPPG electrode in RTILs and verifying the presence of “defects” on both EPPG and MWCNTs using cyclic voltammograms (CVs) of Fc obtained in RTILs of EMIBF4, is the main contribution of this preliminary work. 相似文献
205.
Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate Monohydrate 总被引:1,自引:0,他引:1
Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is (28.795 ± 0.182) kJ/mol (298.15 K), and the standard molar enthalpy of formation of the title complex is (-2185.43 ± 13.80) kJ/mol (298.15 K). Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction: an nth-order reaction (Fn) with n=4.28, E1=147.35 kJ/mol, A1=3.63×10^13 s^-1 is followed by a second-order reaction (F2) with E2=212.71 kJ/mol, A2= 1.82 × 10^18 s^-1. 相似文献
206.
Nitrile-functionalized pyridinium ionic liquids: synthesis, characterization, and their application in carbon-carbon coupling reactions 总被引:5,自引:0,他引:5
Zhao D Fei Z Geldbach TJ Scopelliti R Dyson PJ 《Journal of the American Chemical Society》2004,126(48):15876-15882
A series of relatively low-cost ionic liquids, based on the N-butyronitrile pyridinium cation [C(3)CNpy](+), designed to improve catalyst retention, have been prepared and evaluated in Suzuki and Stille coupling reactions. Depending on the nature of the anion, these salts react with palladium chloride to form [C(3)CNpy](2)[PdCl(4)] when the anion is Cl(-) and complexes of the formula [PdCl(2)(C(3)CNpy)(2)][anion](2) when the anion is PF(6)(-), BF(4)(-), or N(SO(2)CF(3))(2)(-). The solid-state structures of [C(3)CNpy]Cl and [C(3)CNpy](2)[PdCl(4)] have been established by single-crystal X-ray diffraction. The catalytic activity of these palladium complexes following immobilization in both N-butylpyridinium and nitrile-functionalized ionic liquids has been evaluated in Suzuki and Stille coupling reactions. All of the palladium complexes show good catalytic activity, but recycling and reuse is considerably superior in the nitrile-functionalized ionic liquid. Inductive coupled plasma spectroscopy reveals that the presence of the coordinating nitrile moiety in the ionic liquid leads to a significant decrease in palladium leaching relative to simple N-alkylpyridinium ionic liquids. Palladium nanoparticles have been identified as the active catalyst in the Stille reaction and were characterized using transmission electron microscopy. 相似文献
207.
Pt微粒修饰纳米纤维聚苯胺电极对甲醇氧化电催化 总被引:9,自引:0,他引:9
以脉冲电流法制备的纳米纤维状聚苯胺(PANI)为Pt催化剂载体,用它制备了甲醇阳极氧化的催化电极Pt/(nano-fibular PANI).研究结果表明, Pt/(nano-fibular PANI)电极对甲醇氧化具有很好的电催化活性,并有协同催化作用.在相同的Pt载量条件下, Pt/(nano-fibular PANI)电极比Pt微粒修饰的颗粒状聚苯胺电极Pt/(granular PANI)具有更好的电催化活性.此外, Pt的电沉积修饰方法同样影响Pt/(nano-fibular PANI)电极对甲醇氧化的催化活性.脉冲电流法沉积Pt形成的复合电极较循环伏安法电沉积得到的Pt复合电极具有更优异的催化活性. 相似文献
208.
活性聚苯乙烯膜诱导碳酸钙异相成核结晶 总被引:4,自引:0,他引:4
0引言生物矿物材料(如骨、牙齿、贝壳等)的优异性能[1]使得无机材料的仿生合成(又称有机模板合成)成为近年来研究的热点之一[2]。该合成技术的优点是,通过有机物分子与无机离子的相互作用,能够在温和的条件下合成出具有多级结构、特殊形貌和优异性能的有机/无机复合材料。CaCO3 相似文献
209.
The influence of cetyltrimethyl ammonium bromide on electrochemical properties of thyroxine reduction at carbon nanotubes modified electrode 总被引:2,自引:0,他引:2
The effect of cetyltrimethyl ammonium bromide (CTAB) on the electrochemical behaviors of thyroxine at a glassy carbon electrode (GCE) modified with single-walled carbon nanotubes (SWNTs) was investigated. At the SWNTs film-coated GCE, a well-defined oxidation peak of thyroxine at 0.78 V was obtained, but the reduction peak of thyroxine was indiscernible. When trace CTAB was added to the working solution, the reduction current could be greatly enhanced and the oxidation current remained stable. The reaction mechanisms for the reduction of thyroxine were explored by chronocoulometry. Thyroxine might form particular ion complex with CTAB via the interaction between iodine atoms on thyroxine and bromide ions in CTAB, which made the concentration of thyroxine at the surface of the modified electrode increased and the electron transfer rate enhanced. The proper mechanisms for the enhanced reduction of thyroxine in the present of CTAB were explored by several electrochemical techniques including cycle voltammetry linear sweep voltammetry and others. It was concluded that the special interactions between the thyroxine CTAB and SWNTs resulted in the increase of the reduction peak current. All results indicated that two iodine atoms on the thyroxine and four electrons were involved the reduction process which was irreversible and two iodine ions produced. In this system, the sensitive reduction peak of thyroxine at 0.3 V was employed to determine thyroxine and a low detection limit of 2x10(-8) mol/L was obtained for 2 min accumulation at 0.9 V. The SWNTs coated GCE had good stability and reproducibility. 相似文献
210.