全文获取类型
收费全文 | 3360篇 |
免费 | 265篇 |
国内免费 | 407篇 |
专业分类
化学 | 1762篇 |
晶体学 | 22篇 |
力学 | 762篇 |
综合类 | 71篇 |
数学 | 649篇 |
物理学 | 766篇 |
出版年
2023年 | 47篇 |
2022年 | 83篇 |
2021年 | 127篇 |
2020年 | 97篇 |
2019年 | 65篇 |
2018年 | 67篇 |
2017年 | 79篇 |
2016年 | 133篇 |
2015年 | 104篇 |
2014年 | 131篇 |
2013年 | 210篇 |
2012年 | 130篇 |
2011年 | 195篇 |
2010年 | 140篇 |
2009年 | 199篇 |
2008年 | 178篇 |
2007年 | 205篇 |
2006年 | 223篇 |
2005年 | 178篇 |
2004年 | 164篇 |
2003年 | 158篇 |
2002年 | 136篇 |
2001年 | 109篇 |
2000年 | 83篇 |
1999年 | 115篇 |
1998年 | 105篇 |
1997年 | 79篇 |
1996年 | 60篇 |
1995年 | 55篇 |
1994年 | 53篇 |
1993年 | 47篇 |
1992年 | 41篇 |
1991年 | 30篇 |
1990年 | 38篇 |
1989年 | 20篇 |
1988年 | 24篇 |
1987年 | 18篇 |
1986年 | 15篇 |
1985年 | 16篇 |
1984年 | 10篇 |
1983年 | 4篇 |
1982年 | 13篇 |
1981年 | 7篇 |
1980年 | 8篇 |
1979年 | 10篇 |
1978年 | 4篇 |
1976年 | 5篇 |
1973年 | 4篇 |
1972年 | 4篇 |
1969年 | 1篇 |
排序方式: 共有4032条查询结果,搜索用时 24 毫秒
91.
Apparent equilibrium constants and calorimetric enthalpies of reaction have been measured for the reaction L-tryptophan(aq) + H2O(l) = indole(aq) + pyruvate(aq) + ammonia(aq) which is catalyzed by L-tryptophanase. High-pressure liquid-chromatography and microcalorimetery were used to perform these measurements. The equilibrium measurements were performed as a function of pH, temperature, and ionic strength. The results have been interpreted with a chemical equilibrium model to obtain thermodynamic quantities for the reference reaction: L-tryptophan(aq) + H2O(l) = indole(aq) + pyruvate–(aq) + NH
4
+
(aq). At T=25°C and Im=O the results for this reaction are: Ko=(1.05±0.13)×10–4,
G°=(22.71±0.33) kJ-mol–1,
H°=(62.0±2.3) kJ-mol–1, and
S°=(132±8) J-K–1-mol–1. These results have been used together with thermodynamic results from the literature to calculate standard Gibbs energies of formation, standard enthalpies of formation, standard molar entropies, standard molar heat capacities, and standard transformed formation properties for the substances participating in this reaction.Presented at the Symposium, 76th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65th birthday. 相似文献
92.
González-Pérez A. Galán J. J. Rodríguez J. R. 《Journal of Thermal Analysis and Calorimetry》2003,72(2):741-749
The specific conductivities of dodecyldimethylbenzylammonium bromide (C12BBr) have been determined in aqueous butanol and
aqueous benzyl alcohol solutions in the temperature range of 5-40°C. From these data the temperature dependent critical micelle
concentration (cmc) was determined. The molar fraction of alcohol in the micelle was estimated using the theory suggested by Motomura et al. for surfactant binary mixtures. The thermal properties such as standard Gibbs free energy, enthalpy and entropy of solubilization
of alcohols in the micelles were estimated for the phase separation model. The change in heat capacity upon solubilization
of alcohol in the micelle has been estimated form the above properties.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
93.
O. Nilsson 《Journal of separation science》1979,2(12):720-722
Kaiser's “abt” concept rests on the experimental establishment of a linear relation between band width at half height, b0.5, and capacity ratio, k, according to His column specification quantity, hreal, is dependent on the square of the slope a, obtained from a linear regression analysis based on this relation. It is shown in the present paper that an improvement of the experimental conditions leading to a lower extra-column contribution to band broadening, b, introduces a tendency towards a negative curvature in the plot at low k values. The mean slope increases, and an uncritical linear regression would yield an hreal-value which is higher than before and which would be in the opposite direction to the requirements of a reliable column specification. Generally the linear regression analysis has to be moved to higher k regions in cases of curvature, especially as it is also shown that hreal is an estimation of the traditional HETP value, H∞, that would be obtained when k approaches infinity. This theoretically expected relation is a strong motivation for the use of hreal as a column specification, since the b0.5-value associated with H∞ is expected to be practically independent of b. 相似文献
94.
The apparent molar heat capacities of dilute aqueous solutions of acetic, propanoic and succinic acid and sodium salts of the two monofunctional acids were measured at 300 Kp,2
o
. After subtracting the heat capacity of a point mass, the remaining heat capacity was successfully decomposed into functional group contributions at all temperatures. Together with the results of our previous paper on alcohols and diols the heat capacity contributions of the CH2, CH3, OH, COOH, (COOH)2, and COONa groups are now available and these allow reasonably accurate predictions of the heat capacities of all compounds composed of these groups in this temperature range. 相似文献
95.
By high-precision dynamic calorimetry the temperature dependences of heat capacity of dimethylene urethane (DMU) between 320 and 370 K and partially crystalline poly(dimethylene urethane) (PDMU) in the range 326-490 K at standard pressure have been determined within ±1.5%. The thermodynamic characteristics of fusion of the substances, namely the temperature interval of melting, temperature, enthalpy and entropy of fusion, as well as the characteristics of devitrification and glassy state for poly(dimethylene urethane) have been estimated. The first and the second cryoscopic constants have been calculated for dimethylene urethane. The experimental data obtained in the present work and literature findings on the heat capacity of the substances were used to calculate their thermodynamic functions: the heat capacity C°p (T), enthalpy H°(T)−H°(0), entropy S°(T) and Gibbs function G°(T)−H°(0) over the range from T→0 to (370-480) K. Based on the data, the thermodynamic characteristics of polymerization process with five-membered ring opening ΔpolH°, ΔpolS° and ΔpolG° of dimethylene urethane with the formation of linear partially crystalline poly(dimethylene urethane) have been evaluated. 相似文献
96.
研究了低于300 ℃时两种氧化铈对稀燃阶段NOx存储性能的影响,催化剂由2%(w)Pt/Al2O3(PA)与CeO2-X(X=S,I)机械混合制备. X射线衍射(XRD),BET表面积和扫描电子显微镜(SEM)用于表征材料的物理结构. X射线光电子能谱(XPS)和H2程序升温还原(H2-TPR)用于表面Ce3+和活性氧定量. 原位漫反射傅里叶变换红外光谱(in-situ DRIFTS)用于分析表面NOx吸附物种. 相比于CeO2-I,CeO2-S 具有优良的物理化学性能,包括高比表面积、丰富的空隙结构、较高的抗老化能力及表面Ce3+浓度. 因而,Pt/Al2O3+CeO2-S 表现出优异的NOx存储能力. 此外,PA+CeO2-X(X=S,I)上存在Pt 与CeO2之间的相互作用,可提高表面氧物种的活性进而促进NO氧化及NOx存储. PA+CeO2-S上的这种相互作用要强于PA+CeO2-I. 研究表明,表面Ce3+浓度和活性氧含量对NOx存储起到重要作用. 然而经过水热处理后,Pt 与老化的氧化铈(ACS,ACI)之间的相互作用降低,并且两种氧化铈NOx存储性能显著下降. 另外,与PA+ACS(ACI)相比,PA+PACS(PACI)样品NOx存储能力得到改善,这归因于表面氧物种活性增加能促进硝酸盐的形成. 相似文献
97.
Poly(ethylene glycol) (PEG)-supported dendrimers have been synthesized using 2.4,6-trichloro-1,3,5-triazine (TCT) as dendrons and tris(hydroxymethyl)aminomethane as tinkers with high loading capacity, excellent solubility and thermal stability by divergent method. The new synthesized PEG-supported G2.0 dendrimer has 10 times as large functional group loading capacity as commercial PEG3400 with overall yield 44.0%. 相似文献
98.
Low-temperature heat capacities of the compound Na(C4H7O5)·H2O(s) have been measured with an automated adiabatic calorimeter. A solid-solid phase transition and dehydration occur at 290-318 K and 367-373 K, respectively. The enthalpy and entropy of the solid-solid transition are ΔtransHm = (5.75 ± 0.01) kJ mol−1 and ΔtransSm = (18.47 ± 0.02) J K−1 mol−1. The enthalpy and entropy of the dehydration are ΔdHm = (15.35 ± 0.03) kJ mol−1 and ΔdSm = (41.35 ± 0.08) J K−1 mol−1. Experimental values of heat capacities for the solids (I and II) and the solid-liquid mixture (III) have been fitted to polynomial equations. 相似文献
99.
This paper addresses the problem of stabilizing an uncertain linear system. The uncertaintyq(·) which enters the dynamics is nonstistical in nature. That is, noa priori statistics forq(·) are assumed; only boundsQ on the admissible variations ofq(·) are taken as given. The results given here applied to so-called matched systems differ from previous results in two ways. Firstly, the stabilizing control in this paper is linear; for this same class of problems, many of the existing results would require a nonlinear control. Furthermore, those results which do in fact yield linear controls are only valid when a certain matrix (q) (formed using the given data) is negative definite for allq Q. In contrast, the theory given here only requires compactness of the bounding setQ. Secondly, we show that the so-called matching conditions (used in earlier work) can be generalized so as to encompass a larger class of dynamical systems.This research was supported by the US Department of Energy under Contract No. ET-78-S-01-3390. 相似文献
100.