全文获取类型
收费全文 | 831篇 |
免费 | 23篇 |
国内免费 | 4篇 |
专业分类
化学 | 618篇 |
晶体学 | 4篇 |
力学 | 11篇 |
数学 | 140篇 |
物理学 | 85篇 |
出版年
2024年 | 1篇 |
2023年 | 5篇 |
2022年 | 24篇 |
2021年 | 25篇 |
2020年 | 13篇 |
2019年 | 20篇 |
2018年 | 14篇 |
2017年 | 15篇 |
2016年 | 20篇 |
2015年 | 27篇 |
2014年 | 34篇 |
2013年 | 51篇 |
2012年 | 53篇 |
2011年 | 63篇 |
2010年 | 35篇 |
2009年 | 37篇 |
2008年 | 62篇 |
2007年 | 45篇 |
2006年 | 50篇 |
2005年 | 40篇 |
2004年 | 41篇 |
2003年 | 31篇 |
2002年 | 26篇 |
2001年 | 6篇 |
2000年 | 6篇 |
1999年 | 6篇 |
1998年 | 8篇 |
1997年 | 13篇 |
1996年 | 8篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 7篇 |
1983年 | 4篇 |
1982年 | 6篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有858条查询结果,搜索用时 281 毫秒
1.
Attila Kovács 《International journal of quantum chemistry》2020,120(1):e26051
Lanthanide dinitrogen complexes, Ln(N2) x (x = 1-8), were investigated by Density Functional Theory computations using the B3LYP exchange-correlation functional in conjunction with quasirelativistic pseudopotentials for Ln. After a recent study on the lanthanum complexes (A. Kovács, Structural Chemistry 2018 , 29, 1825), the present study aimed to probe the changes upon variously filled 4f subshells of Ln on the structures, stabilities, and bonding properties in related complexes of Nd, Ho, and Lu. The bonding properties were assessed on the basis of natural atomic charges, Ln valence orbital populations, and analysis of bonding molecular orbitals. 相似文献
2.
Julien Ferrari Christian Terreaux Tibor Kurtn Attila Szikszai‐Kiss Sndor Antus JeromeD. Msonthi Kurt Hostettmann 《Helvetica chimica acta》2003,86(8):2768-2778
Investigation of the methanol extract of the roots of Gnidia involucrata (Thymelaeaceae) led to the isolation and characterization of two new 3,8″‐biflavonoid diastereoisomers, named GB‐4 ( 6a ) and GB‐4a ( 6b ). Their absolute configurations were determined in mixture by on‐line LC/CD measurements, which also allowed the revision of absolute configurations of the biflavanoids GB‐1 and GB‐2, and the configurational assignment of GB‐3. 相似文献
3.
The concept of rigid sphericalt-designs was introduced by Bannai. He conjectured that there is a functionf(t, d) such that ifX is a sphericalt design in thed-dimensional Euclidean space so that |X|>f(t, d), theX is non-rigid. Furthermore, he asked to find examples of rigid but not tight sperical designs. In the present article we shall investigate the case whenX is an orbit of a finite reflection group and prove thatX is rigid iff tight for the groupsA
n
,B
n
,C
n
,D
n
,E
6,E
7,F
4,I
3.Research was partially supported by Hungarian National Research fund Grant No. 4267. 相似文献
4.
In this paper the effects of surface roughness and annealing temperature (T) of latex coating films on adhesion are discussed for the different stages of the film formation process. The surface free energy of latex films was assessed in terms of practical work of adhesion (W) (or adherence) using a custom-built adhesion-testing device (ATD), atomic force microscopy (AFM), and contact angle measurements. For preannealed latex films surface roughness averages (Ra) were determined from AFM height images and were related to the values of W obtained from ATD measurements at room temperature. The results obtained using these tests exhibiting surface behavior on different length scales indicate a dependence of the measured adhesion on surface roughness and temperature, as well as on the length scale of the measurements.First preannealed samples were studied, which were obtained by heat treatment above the respective glass transition temperatures (Tg). Increasing the temperature of preannealing resulted in a decrease of the adherence observed in ATD experiments at room temperature. However, on the nanoscale, using AFM, no significant variation of the adherence was observed. This observation can be explained by roughness arguments. Preannealing decreases roughness which results in lower adherence values measured by ATD while for essentially single asperity AFM experiments roughness has an insignificant effect. Specimens were also annealed over a constant period of time (90 min) at different temperatures. At the end of the heat treatment, adhesion was measured at the treatment temperature by ATD. The amplified effect of temperature observed in this case on adherence is attributed to the combination of roughness decrease and increasing test temperature. In a third set of experiments completely annealed samples were studied by ATD as well as by AFM as a function of temperature. With increasing T values ATD showed a decrease in adherence, which is attributed to a decreasing surface free energy of the annealed films at elevated T values. AFM, on the other hand, showed an opposite trend which is assigned to increasing penetration of the tip into the tip/wetting polymer samples versus increasing temperature. Finally, annealing isotherms as a function of time were investigated by ATD in situ at different temperatures. This last set of experiments allowed us to optimize annealing time and temperature to achieve complete curing. 相似文献
5.
6.
During nitroxide-mediated polymerization (NMP) in the presence of a nitroxide R2(R1)NO*, the reversible formation of N-alkoxyamines [P-ON(R1)R2] reduces significantly the concentration of polymer radicals (P*) and their involvement in termination reactions. The control of the livingness and polydispersity of the resulting polymer depends strongly on the magnitude of the bond dissociation energy (BDE) of the C-ON(R1)R2 bond. In this study, theoretical BDEs of a large series of model N-alkoxyamines are calculated with the PM3 method. In order to provide a predictive tool, correlations between the calculated BDEs and the cleavage temperature (T(c)), and the dissociation rate constant (k(d)), of the N-alkoxyamines are established. The homolytic cleavage of the N-OC bond is also investigated at the B3P86/6-311++G(d,p)//B3LYP/6-31G(d), level. Furthermore, a natural bond orbital analysis is carried out for some N-alkoxyamines with a O-C-ON(R1)R2 fragment, and the strengthening of their C-ON(R1)R2 bond is interpreted in terms of stabilizing anomeric interactions. 相似文献
7.
Let {ø n (dμ)} be a system of orthonormal polynomials on the unit circle with respect to a measuredμ. Szegö's theory is concerned with the asymptotic behavior ofø n (dμ) when logμ′∈L 1. In what follows we will discuss the asymptotic behavior of the ratioø n (dμ 2)/ø n (dμ 1) on the unit circle whendμ 1 anddμ 2 are close in a sense (e.g.,dμ 2=gdμ 1, where g≥0 is such thatQ(e it )g(t) andQ(e it )/g(t) are bounded for a suitable polynomialQ) and μ 1 ′ >0 almost everywhere or (a somewhat weaker requirement) lim n→∞Φ n (dμ 1,0)=0 for the monic polynomial Φ n . The asymptotic behavior of the same fraction outside the unit circle was discussed in an earlier paper. 相似文献
8.
The fluorescence spectrum of crystals grown from newly synthesized 4-(dimethylamino)benzonitrile (DMABN), measured from 25 down to −112 °C, consists of a single emission band originating from a locally excited (LE) state. The fluorescence decay of the DMABN crystals is single exponential at all temperatures investigated. These results show that intramolecular charge transfer (ICT) does not occur in crystalline DMABN. The additional red-shifted emission bands and multiexponential fluorescence decays previously reported for DMABN crystals are attributed to a minor amount of the impurity 4-(dimethylamino)benzaldehyde, the synthetic precursor of commercial DMABN. 相似文献
9.
The conformational space of (4)C(1) alpha- and beta-d-glucuronic acid was scanned by HF/3-21G(p) calculations followed by optimization of the 15 most stable structures for each, using the B3LYP density functional theory method in conjunction with a diffuse polarized valence triple-zeta basis set. We found a general preference of the alpha anomers in the isolated molecules in agreement with the large endo-anomeric hyperconjugation effects in these structures. From the other intramolecular interactions (exo-anomeric hyperconjugation, hydrogen-bonding, dipole-dipole, and steric interactions), the effect of the hydrogen bonding is the most pronounced and plays a major role in determining the stability order within the alpha and beta series. The most stable conformer of both alpha and beta (4)C(1) d-glucuronic acid is the structure with the maximum number (5) of intramolecular hydrogen bonds. Introduction of solvent (water) effects by the SCI-PCM model resulted in two characteristic changes of the energetic properties: the gas-phase stability order changed considerably, and the energy range of the 15 most stable conformers decreased from 30 to 15 kJ/mol. The geometrical parameters reflect well the superimposed effects of hyperconjugation and hydrogen-bonding interactions. Most characteristics are the variations of the C-O bond distances (within a range of 0.04 A) upon the combined intramolecular effects. 相似文献
10.
A general stochastic theory of size exclusion chromatography (SEC) able to account for size dependence on both pore ingress and egress processes, moving zone dispersion and pore size distribution, was developed. The relationship between stochastic-chromatographic and batch equilibrium conditions are discussed and the fundamental role of the 'ergodic' hypothesis in establishing a link between them is emphasized. SEC models are solved by means of the characteristic function method and chromatographic parameters like plate height, peak skewness and excess are derived. The peak shapes are obtained by numerical inversion of the characteristic function under the most general conditions of the exploited models. Separate size effects on pore ingress and pore egress processes are investigated and their effects on both retention selectivity and efficiency are clearly shown. The peak splitting phenomenon and peak tailing due to incomplete sample sorption near to the exclusion limit is discussed. An SEC model for columns with two types of pores is discussed and several effects on retention selectivity and efficiency coming from pore size differences and their relative abundance are singled out. The relevance of moving zone dispersion on separation is investigated. The present approach proves to be general and able to account for more complex SEC conditions such as continuous pore size distributions and mixed retention mechanism. 相似文献