全文获取类型
收费全文 | 2343篇 |
免费 | 227篇 |
国内免费 | 521篇 |
专业分类
化学 | 2720篇 |
晶体学 | 58篇 |
力学 | 16篇 |
综合类 | 9篇 |
物理学 | 288篇 |
出版年
2024年 | 3篇 |
2023年 | 32篇 |
2022年 | 46篇 |
2021年 | 87篇 |
2020年 | 94篇 |
2019年 | 75篇 |
2018年 | 82篇 |
2017年 | 113篇 |
2016年 | 95篇 |
2015年 | 107篇 |
2014年 | 98篇 |
2013年 | 250篇 |
2012年 | 152篇 |
2011年 | 106篇 |
2010年 | 112篇 |
2009年 | 127篇 |
2008年 | 131篇 |
2007年 | 136篇 |
2006年 | 131篇 |
2005年 | 121篇 |
2004年 | 119篇 |
2003年 | 94篇 |
2002年 | 81篇 |
2001年 | 78篇 |
2000年 | 63篇 |
1999年 | 68篇 |
1998年 | 67篇 |
1997年 | 53篇 |
1996年 | 50篇 |
1995年 | 50篇 |
1994年 | 56篇 |
1993年 | 43篇 |
1992年 | 44篇 |
1991年 | 32篇 |
1990年 | 22篇 |
1989年 | 17篇 |
1988年 | 15篇 |
1987年 | 5篇 |
1986年 | 10篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 4篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有3091条查询结果,搜索用时 62 毫秒
1.
Jiraya Kiriratnikom Xun Zhang Xiaohan Cao Bo Chu Chengjian Zhang Xinghong Zhang 《Journal of polymer science. Part A, Polymer chemistry》2022,60(15):2262-2268
Facile construction of sulfur-rich polymers using readily available raw chemicals is an area aggressively pursued but challenging. Herein we use common feedstocks of ethylene oxide (EO), propylene oxide (PO), and carbonyl sulfide (COS) to synthesize copoly(thioether)s which are traditionally produced from unpleasant and difficult to store episulfides. In this protocol, the EO/COS coupling selectively generates a pure poly(ethylene sulfide) (PES) with melting temperature (Tm) values up to 172°C and high yields up to 98%. The EO/PO/COS terpolymerization leads to the incorporation of soft poly(propylene sulfide) (PPS) and hard PES segments together, affording a random PES-co-PPS copoly(thioether) with the complete consumption of EO and PO. Additionally, by simply varying the EO/PO feeding ratio, the obtained copoly(thioether)s possess tunable thermal properties, Tm values in the range of 76–144°C, and excellent solubility. These copolymerizations are conducted in one-pot/one-step at industrially favored reaction temperatures of 100–120°C using catalysts of common organic bases, suggesting a facile and practical manner. Especially, the copoly(thioether) exhibits high refractive indices up to 1.68 owing to its high sulfur content, suggesting a broad application prospect in optical materials. 相似文献
2.
水热合成法制备了不同磁性纳米洋葱碳(MCNOs)负载量(0%、1%、3%、5%)的MCNOs/CdS光催化剂。并通过X射线衍射分析(XRD)、扫描电子显微镜(SEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)、紫外可见光光谱(UV-Vis)、磁滞回线测定仪(VSM)对其进行表征,探究了MCNOs负载比例对催化剂在可见光下降解RhB性能及机理的影响。结果表明,MCNOs能有效提高CdS的光催化效果,复合3%MCNOs后降解率为96%,与纯CdS相比降解率提高了30%,磁性分析表明,其具有良好的顺磁性并能实现催化剂的有效回收。MCNOs/CdS在可见光下催化降解RhB的一级反应动力学直线有较好的拟合度,表明制备的催化剂有较好的催化活性。 相似文献
3.
Jong Chan Lee Jin Young Park So Young Yoon Yong Hun Bae Seung Jun Lee 《Tetrahedron letters》2004,45(1):191-193
A novel and direct method for the synthesis of α-halocarbonyl compounds using sequential treatment of carbonyl compounds with [hydroxy(tosyloxy)iodo]benzene followed by magnesium halides under solvent-free microwave irradiation conditions is described. 相似文献
4.
S. V. Semikolenov K. A. Dubkov E. V. Starokon' D. E. Babushkin G. I. Panov 《Russian Chemical Bulletin》2005,54(4):948-956
The kinetics and mechanism of noncatalytic liquid-phase oxidation of but-1-ene and but-2-ene with nitrous oxide in a benzene
solution in the temperature range from 180 to 240°C were studied. Oxidation proceeds via the 1,3-dipolar cycloaddition mechanism to form carbonyl compounds. Both of these reactions occur with close rates and activation
energies and have the first orders with respect to the alkene and N2O. A considerable fraction (39%) of but-1-ene involved in oxidation undergoes cleavage at the double bond yielding propanal
and an equivalent amount of methylene, the latter producing ethylcyclopropane and cycloheptatriene. The oxidation of but-2-ene
proceeds with a minimum bond cleavage and affords methyl ethyl ketone with 84% selectivity. Regularities of the oxidation
of terminal and internal alkenes C2—C8 with nitrous oxide were analyzed using the previously published data.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–933, April, 2005. 相似文献
5.
5-Perfluorophenyl 4,5-dihydro-1H-pyrazoles were synthesized from 1,3-dipolar cycloaddition reaction of perfluorobenyl 2,4,6-triisopropylbenzenesulfonylhydrazone and α,β-unsaturated carbonyl compounds or acrylonitrile in THF or water. It was worthy to note that better results were obtained when water was employed as the solvent, which was considered as an effective, economic and environmentally friendly method to synthesize these pyrazole derivatives. 相似文献
6.
Shuichi Oi Mitsutoshi MoroHiroe Fukuhara Takanori KawanishiYoshio Inoue 《Tetrahedron》2003,59(24):4351-4361
The addition of arylstannanes to the carbon-heteroatom double bond in the presence of a catalytic amount of a cationic rhodium complex ([Rh(cod)(MeCN)2]BF4) was examined. The reactions of aldehydes, α-dicarbonyl compounds, and N-substituted aldimines with the arylstannanes gave corresponding alcohols, α-hydroxy carbonyl compounds, and amines, respectively. An arylrhodium complex generated by the transmetalation with the arylstannane was probably the active catalytic species. 相似文献
7.
Changes in thin zinc-sulfide films under the action of the γ-radiation of Co60 are studied by investigating electroluminescence spectra of terbium embedded in these films as a luminescent probe. It is
shown that changes in the relation of the intensities of bands, a decrease in their halfwidth and the background component,
and simplification of the spectrum are observed in a short-wave region of the Tb radiation spectrum that corresponds to5D3→7Fj transitions. The same modification of the radiation spectrum is characteristic of ZnS films whose crystalline structure is
ordered in the course of thermal annealing at a temperature of 350°C. Based on the analysis of the data obtained it is inferred
that irradiating the ZnS films with small radiation doses of 104–105 rad leads to the ordering of their crystalline structure due to the elimination of one of the types of structural defects.
Institute of Physics of Semiconductors, National Academy of Sciences of Ukraine, 45, Nauka Ave., Kiev-28, 252650. Translated
from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 3, pp. 338–341, May–June, 1997. 相似文献
8.
Dendritic nanocrystalline CdS film was deposited at liquid-liquid interface of surfactants and an electrolyte containing 4 mmol L−1 cadmium chloride (CdCl2) and 16 mmol L−1 thioacetamide (CH3CSNH2) with an initial pH value of 5 at 15 °C by electrochemical synthesis. The nanofilm was characterized by transmission electron microscopy (TEM), field emission scanning electron microscope (FE-SEM), atomic force microscopy (AFM), ultraviolet visible (UV-vis) absorption spectroscopy and fluorescence spectroscopy. The surface morphology and particle size of the nanofilm were investigated by AFM, SEM and TEM, and the crystalline size was 30-50 nm. The thickness of the nanofilm calculated by optical absorption spectrum was 80 nm. The microstructure and composition of the nanofilm was investigated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), showing its polycrystalline structure consisting of CdS and Cd. Optical properties of the nanofilm were investigated systematically by UV-vis absorption and fluorescence spectroscopy. A λonset blue shift compared with bulk CdS was observed in the absorption spectra. Fluorescence spectra of the nanofilm indicated that the CdS nanofilm emitted blue and green light. The nanocomposites film electrode will bring about anodic photocurrent during illumination, showing that the transfer of cavities produces photocurrent. 相似文献
9.
Yuri L. Mikhlin Alexander S. Romanchenko Alexander A. Shagaev 《Applied Surface Science》2006,252(16):5645-5658
Natural n-type PbS single crystals have been studied using AFM, STM and STS after long-term oxidation in air at ambient temperatures and extensive etching in aqueous acid solutions, in contrast to previous work devoted to initial corrosion of fresh surfaces. The exposure of PbS to atmosphere at high relative humidity for several days yields widespread loose oxidation products; the process is much slower at low humidity. Surface morphologies diverge after the treatment in 1 M perchloric and hydrochloric acid solutions at room temperature and become widely different at elevated temperatures, displaying commonly etch pits up to several micrometers in size and depth along with rather uniformly distributed 20-100 nm protrusions of PbS phase. The changes both in topography and semiconducting properties of PbS found by tunneling spectroscopy have been explained in terms of the non-uniform distribution of donor- and acceptor-type defects D+/D− in the metal depleted surface layer, which are generated by chemical reactions and, in turn, determine the rates of the PbS corrosion. In particular, the D− centers exhibit a self-catalyzing effect on the non-oxidative local dissolution of PbS in HCl media, resulting in the deep etch pits. 相似文献
10.
Jan-Martin Heldt Michèle Salmain Gérard Jaouen 《Journal of organometallic chemistry》2004,689(25):4775-4782
The first poly(amidoamine) (PAMAM) dendrimers tethered with both (η5-cyclopentadienyl) rhenium tricarbonyl (CpRe(CO)3) units and polyethylene glycol (PEG) chains were prepared and characterized by combining NMR spectroscopy and Fourier-transform IR spectroscopy. Grafting of CpRe(CO)3 units was achieved by reductive amination of formyl-CpRe(CO)3 with the peripheral amines of generation 3 and 4 PAMAMs to yield dendrimers labeled with a variable number of CpRe(CO)3 units, ranging from 8 to 14 for PAMAM-G3 and 17-30 for PAMAM-G4. PEG chains of different lengths were then attached to some of the remaining peripheral amines, and their respective ability to improve the solubility of the metallodendrimers in aqueous buffered media was evaluated. These metallodendrimers represent new infrared probes designed to be coupled to immunological reagents for the amplification of the IR signal in carbonyl metallo immunoassay (CMIA). 相似文献