全文获取类型
收费全文 | 2254篇 |
免费 | 382篇 |
国内免费 | 206篇 |
专业分类
化学 | 1178篇 |
晶体学 | 15篇 |
力学 | 400篇 |
综合类 | 45篇 |
数学 | 226篇 |
物理学 | 978篇 |
出版年
2024年 | 7篇 |
2023年 | 68篇 |
2022年 | 100篇 |
2021年 | 108篇 |
2020年 | 82篇 |
2019年 | 64篇 |
2018年 | 68篇 |
2017年 | 85篇 |
2016年 | 78篇 |
2015年 | 86篇 |
2014年 | 129篇 |
2013年 | 201篇 |
2012年 | 114篇 |
2011年 | 180篇 |
2010年 | 125篇 |
2009年 | 138篇 |
2008年 | 162篇 |
2007年 | 156篇 |
2006年 | 162篇 |
2005年 | 111篇 |
2004年 | 100篇 |
2003年 | 85篇 |
2002年 | 60篇 |
2001年 | 46篇 |
2000年 | 45篇 |
1999年 | 34篇 |
1998年 | 35篇 |
1997年 | 29篇 |
1996年 | 27篇 |
1995年 | 32篇 |
1994年 | 16篇 |
1993年 | 19篇 |
1992年 | 12篇 |
1991年 | 11篇 |
1990年 | 13篇 |
1989年 | 5篇 |
1988年 | 11篇 |
1987年 | 6篇 |
1986年 | 3篇 |
1985年 | 7篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1969年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有2842条查询结果,搜索用时 15 毫秒
51.
Rollie J. Myers 《Journal of solution chemistry》2007,36(3):395-403
We have measured the second acid dissociation constant, K
2a
, at several ionic strengths for hydrogen telluride (H2Te) using the Charge Transfer to Solvent (CTTS) uv spectra of its anions HTe− and Te2−. Since it is produced in our solutions, we have also determined the spectra of Te2
2− both in the uv and in the visible regions. At 25 ∘C, K
2a
= (1.28 ± 0.02) × 10−12 by extrapolation to zero ionic strength. Its value at an ionic strength equal to 0.5 mol.dm-3 was estimated to be (8.7 ± 0.2) × 10−12. The solution thermodynamics of these species are also discussed and comparisons are made to related acids. 相似文献
52.
Kamel Guedri Tahmoor Bashir A. Abbasi Waseh Farooq Sami Ullah Khan M. Ijaz Khan Mohammed Jameel Ahmed M. Galal 《印度化学会志》2022,99(9):100614
The electroosmotic peristaltic flow of modified hybrid nanofluid in presence of entropy generation has been presented in this thermal model. The Hall impact and thermal radiation with help of nonlinear relations has also been used to modify the analysis. The assumed flow is considered due to a non-uniform trapped channel. The properties of modified hybrid nanofluid model are focused with interaction of three distinct types of nanoparticles namely copper (, silver () and aluminum oxide ( The mathematical modeling and significances of entropy generation and Bejan number are identified. With certain flow assumptions, the governing equations are attained for optimized peristaltic electroosmotic problem. Widely used assumptions of long wave length and low Reynolds number reduced the governing equations in ordinary differential equations. The ND solver is flowed for the solution process. The physical significant of results is observed by assigning the numerical values to parameters. 相似文献
53.
Jin-long Wu Zhen-ya Zeng Lan-hua Wei Ling-zhi Meng Ting-xian Yang 《Tetrahedron》2004,60(19):4309-4314
Three new neutral receptors (1, 2 and 3) containing thiourea and amide groups were synthesized by simple steps in good yields. The binding properties for anions of 1, 2 and 3 were examined by UV-vis, fluorescence, and 1H NMR spectroscopy. Receptors 1, 2 and 3 all had a better adipate anion selectivity by comparison with other dicarboxylate anions. The association constants of 1, 2 and 3 with adipate were higher as compared to other anions (malonate, succinate, glutarate). In particular, a distinct color change was observed from light yellow to orange-red upon addition of adipate to the solution of 1 in DMSO. The UV-vis and fluorescence data indicate that a 1:1 stoichiometry complex is formed between compound 1, 2 or 3 and dicarboxylate anions through hydrogen bonding interactions. 相似文献
54.
This paper reports the results on a study of ion chromatography (IC) behaviour on strong cationic exchange column of CH3-(CH2)n−1-NH2 (n=1-6) type linear monoamines. The eluents were mixtures of HCl-NaCl, HNO3-NaNO3, HClO4-NaClO4, H2SO4-Na2SO4, HClO4-NaClO4-CH3CN. Amines were revealed with an amperometric detector. The influence of different counter-ions on retention factors, k′, is discussed. Relationships between k′ and pE (E=sum of Na+ and H+ concentrations), and length of alkylic chain, and sensitivity coefficient S, are reported and discussed. The addition of acetonitrile (ACN) in the eluent was also taken into account. Suitable considerations are derived from these data. An example of monoamines separation is given. 相似文献
55.
van de Waterbeemd H Smith DA Jones BC 《Journal of computer-aided molecular design》2001,15(3):273-286
Lipophilicity, often expressed as distribution coefficients (log D) in octanol/water, is an important physicochemical parameter influencing processes such as oral absorption, brain uptake and various pharmacokinetic (PK) properties. Increasing log D values increases oral absorption, plasma protein binding and volume of distribution. However, more lipophilic compounds also become more vulnerable to P450 metabolism, leading to higher clearance. Molecular size and hydrogen bonding capacity are two other properties often considered as important for membrane permeation and pharmacokinetics. Interrelationships among these physicochemical properties are discussed. Increasing size (molecular weight) often gives higher potency, but inevitably also leads to either higher lipophilicity, and hence poorer dissolution/solubility, or to more hydrogen bonding capacity, which limits oral absorption. Differences in optimal properties between gastrointestinal absorption and uptake into the brain are addressed. Special attention is given to the desired lipophilicity of CNS drugs. In examples using -blockers, Ca channel antagonists and peptidic renin inhibitors we will demonstrate how potency and pharmacokinetic properties need to be balanced. 相似文献
56.
Di Li Naoki Ohashi Shunichi Hishita Taras Kolodiazhnyi Hajime Haneda 《Journal of solid state chemistry》2005,178(11):3293-3302
An overall comparative study was carried out on N-doped, F-doped, and N-F-codoped TiO2 powders (NTO, FTO, NFTO) synthesized by spray pyrolysis in order to elucidate the origin of their visible-light-driven photocatalysis. The comparisons in their experimentally obtained characteristics were based on the analysis of XPS, UV-Vis, PL, NH3-TPD and ESR spectra. The comparisons in their theoretically predicted properties were based on the analysis of the calculated electronic structures. As the results, N-doping into TiO2 resulted in not only the improvement in visible-light absorption but also the creation of surface oxygen vacancies. F-doping produced several beneficial effects including the creation of surface oxygen vacancies, the enhancement of surface acidity and the increase of Ti3+ ions. Doped N atoms formed a localized energy state above the valence band of TiO2, whereas doped F atoms themselves had no influence on the band structure. The photocatalytic tests indicated that the NFTO demonstrated the highest visible-light activity for decompositions of both acetaldehyde and trichloroethylene. This high activity was ascribed to a synergetic consequence of several beneficial effects induced by the N-F-codoping. 相似文献
57.
58.
盐酸溶液中阴离子表面活性剂在铝表面上的吸附 总被引:2,自引:0,他引:2
用失重法研究了盐酸溶液中阴离子表面活性剂十二烷基磺酸钠(DSASS),十二烷基苯磺酸钠(DBSAS)以及十二烷基硫酸钠(SDS)在铝表面上的吸附作用,提出这种吸附作用与铝的失重量有关,且符合Lang-muir方程,计算出吸附热,吸附熵和吸附自由能等热力学参数。认为这种吸附主要靠静电作用,根据接触角的变化讨论了阴离子表面活性剂分子在铝表面上的吸附取向。 相似文献
59.
Natalia Fridman Moshe Kapon Yana Sheynin Menahem Kaftory 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(3-4):153-157
1,3-Benzenediamine,N,N′-bis(4,6-dichloro-1,3,5-triazine-2-yl) and 1,3,5-Triazine,2,2′-[2-methyl-1,3-phenylenebis(oxy)] bis(4,6-dichloro) were synthesized as host molecules. The inclusion compound of 1,3-Benzenediamine,N,N′-bis(4,6-dichloro-1,3,5-triazine-2-yl) crystallizes in the monoclinic crystal system in space group C2/c. The host molecule occupies the space group 2-fold special position and packed in the crystal lattice in such a manner as to leave channels running along the c axis of a rectangular cross-section. It crystallizes with two molecules of acetone that are hydrogen bonded to the amino nitrogen atoms. Molecules of 1,3,5-Triazine,2,2′-[2-methyl-1,3-phenylene bis(oxy)]bis(4,6-dichloro) are packed in the crystal in such a manner as to leave channels of a trapezoid cross-section that are running along the a axis. Guest molecules such as metanol, ethanol, and ethyl acetate can be used to fill the channels. The crystal structures of two inclusion compounds are described. 相似文献
60.
M. Jochum R. Bakry I. Wartusch C. W. Huck H. Engelhardt G. K. Bonn 《Chromatographia》2002,56(5-6):263-268
Summary This paper reports on the use of a polymer-based, strong anion-exchange stationary phase for rapid, selective and sensitive
analysis of physiological important mono-, di- and oligosaccharides by high-performance anion-exchange chromatography (HPAEC)
with pulsed amperometric detection (PAD) under alkaline conditions. The adsorbent was obtained by direct nitration of 3 and
5 μm, spherical non-porous highly cross-linked, styrene-divinylbenzene copolymer (PS-DVB) beads, followed by reduction of
superficially introduced nitro groups with nascent hydrogen and quaternization of the resultant amino groups with iodomethane.
Extended exposure to high pressure and strong alkaline conditions did not have any untoward effect on mechanical stability
and chromatographic performance. A comparison of the 3 and 5 μm beads showed, that the synthesized 3 μm highly cross-linked
PS-DVB particles are the preferred phases for the separation of monosaccharides and the 5 μm particles are preferable for
the separation of oligosaccharides. To demonstrate the suitability for the analysis of complex samples, the optimized and
validated system was used for the determination of glucose, fructose and sucrose in apple juice and other soft drinks such
as Coca Cola. Finally, analysis within a few minutes without sample pretreatment down to a lower limit of detection of 0.174–0.504
μg mL−1 at a linearity with R2>0.994 and a repooducibility higher than 98% further confirmed the efficiency of these polymeric sorbents. 相似文献