全文获取类型
收费全文 | 9323篇 |
免费 | 1403篇 |
国内免费 | 1108篇 |
专业分类
化学 | 6613篇 |
晶体学 | 86篇 |
力学 | 414篇 |
综合类 | 102篇 |
数学 | 1031篇 |
物理学 | 3588篇 |
出版年
2024年 | 23篇 |
2023年 | 201篇 |
2022年 | 341篇 |
2021年 | 351篇 |
2020年 | 395篇 |
2019年 | 383篇 |
2018年 | 318篇 |
2017年 | 311篇 |
2016年 | 447篇 |
2015年 | 435篇 |
2014年 | 550篇 |
2013年 | 652篇 |
2012年 | 829篇 |
2011年 | 799篇 |
2010年 | 530篇 |
2009年 | 480篇 |
2008年 | 608篇 |
2007年 | 586篇 |
2006年 | 479篇 |
2005年 | 434篇 |
2004年 | 296篇 |
2003年 | 244篇 |
2002年 | 234篇 |
2001年 | 212篇 |
2000年 | 221篇 |
1999年 | 186篇 |
1998年 | 176篇 |
1997年 | 146篇 |
1996年 | 160篇 |
1995年 | 145篇 |
1994年 | 109篇 |
1993年 | 98篇 |
1992年 | 80篇 |
1991年 | 62篇 |
1990年 | 63篇 |
1989年 | 40篇 |
1988年 | 37篇 |
1987年 | 32篇 |
1986年 | 26篇 |
1985年 | 35篇 |
1984年 | 15篇 |
1983年 | 14篇 |
1982年 | 15篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 4篇 |
1976年 | 6篇 |
1962年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
41.
Enantioselective transition metal catalysis directed by chiral cations is the amalgamation of chiral cation catalysis and organometallic catalysis. Thus far, three strategies have been revealed: ligand scaffolds incorporated on chiral cations, chiral cations paired with transition metal ‘ate’-type complexes, and ligand scaffolds incorporated on achiral anions. Chiral cation ion-pair catalysis has been successfully applied to alkylation, cycloaddition, dihydroxylation, oxohydroxylation, sulfoxidation, epoxidation and C–H borylation. This development represents an effective approach to promote the cooperation between chiral cations and transition metals, increasing the versatility and capability of both these forms of catalysts. In this review, we present current examples of the three strategies and suggest possible inclusions for the future.Enantioselective transition metal catalysis directed by chiral cations is the amalgamation of chiral cation catalysis and organometallic catalysis. 相似文献
42.
43.
Haralampus-Grynaviski N Ransom C Ye T Rôzanowska M Wrona M Sarna T Simon JD 《Journal of the American Chemical Society》2002,124(13):3461-3468
Urocanic acid, UCA, is characterized by two electronic transitions in the UV-B (280-320 nm) which comprise its broad absorption spectrum and give rise to wavelength-dependent isomerization quantum yields. The absorption spectrum of UCA extends into the UV-A (320-400 nm). Given the UV-A component of sunlight is significantly greater than the UV-B component it is hypothesized even weak UV-A photochemistry of UCA could be important for in vivo responses to UV radiation. Degenerate pump-probe experiments performed on t-UCA at several wavelengths in the UV-A reveal an excited-state absorption that undergoes a rapid, approximately 1 ps decay. Photoacoustic experiments performed on both the cis and trans isomers reveal the formation of a long-lived intermediate following UV-A excitation. The efficiency and action spectra for this latter photoactive process are presented and are similar for both isomers of UCA. Cholesterol hydroperoxide assays designed to investigate the nature of the UV-A photoreactivity of t-UCA confirm the production of reactive oxygen species. The bimolecular rate constant for the quenching of singlet oxygen by t-UCA is determined to be 3.5 x 10(6) M(-1) s(-1). Taking into consideration recent theoretical calculations and jet expansion studies of the electronic structure of gas-phase t-UCA, a model is proposed to explain the isomerization and photoreactivity of t-UCA in solution over the UV-A region. 相似文献
44.
The use of acidic mobile phase additives allows the chiral separation of underivatized phenylalanine analogs on a common amylosic column. In addition to decreasing retention and band-broadening arising from non-ideal interactions, acidic additives may also increase selectivity. This appears to be due to the minimization of non-selective binding in the recognition site. Effects of the additives are related to additive pKa and size. Ethanesulfonic acid was typically the most effective additive with trifluoroacetic acid being one of the least effective. 相似文献
45.
近些年来,无铅低熔点填料日渐引起人们的兴趣,且将得到广泛的应用。Cu-Zn-Sn合金正是无铅低熔点填料的一种基本合金。该体系相图虽有一些报道,但他们的研究只涉及富铜区(>50Wt%)的液相限和等温截面(500℃)。我们颇感兴趣的富Sn区的液相限,尚未见文献报道,因此测定该体系富Sn区的液相限是必要的。关于Cu-Zn-Sn体系的三个相关二元体系,已有文献报道,也较成熟。对于Cu-Zn体系,富Zn区600℃以下存在两个转熔反应,其转熔点分别为Q(~88Wt%Zn,598℃),W(97.5-98.5Wt%Zn,424℃);Cu-Sn体系富Sn区有一个转熔反应,其转熔点 相似文献
46.
In this paper, elastic behaviors of non-Gaussian polymethylene (PM) chains with chain length N=100 are investigated by rotational isomeric state model. Here the tetrahedral lattice of PM chain and the non-local interaction of Sutherland potential are adopted. In the metropolis movement of PM chain, a four-bond movement model is used. The average energy and average Helmholtz free energy with various elongation ratios λ are calculated by Monte Carlo simulation method. The average energy increases with elongation ratio λ and the average Helmholtz free energy decreases with elongation ratio λ. The elastic force f and the energy contribution to elastic force fu can be obtained from f=∂〈A〉/∂r and f=∂〈U〉/∂r. We find that the elastic force f increases with elongation ratio λ and the energy contribution fu decreases with elongation ratio λ, and fu is less than zero. The ratio fu/f is close to −0.21 for λ?1.25, and −0.04 to −0.35 for λ>1.25 at T=364 K. In our calculation, the rubber elasticity may be discussed in terms of the chemical structure of polymer chains. 相似文献
47.
The amino acid analog azaproline (azPro) contains a nitrogen atom in place of the C(alpha) of proline. Peptides containing azPro were shown to stabilize the cis-amide conformer for the acyl-azPro bond and prefer type VI beta-turns both in crystals and in organic solvents by NMR. The increased stability for cis-amide conformers was relatively minor with respect to the trans-conformers. Further, their conformational preferences were depended on solvent. To elucidate the impact of azPro substitution on amide cis-trans isomerism and peptide conformation, this paper reports ab initio studies on azPro derivatives and a comparison with their cognate Pro derivatives: 1-acetyl-2-methyl pyrrolidine (1), 1-acetyl-2-methyl pyrazolidine (2), Ac-Pro-NHMe (3), Ac-azPro-NHMe (4), Ac-azPro-NMe(2) (5), Ac-azAzc-NHMe (6), and Ac-azPip-NHMe (7). Conformational preferences were explored at the MP2/6-31+G** level of theory in vacuo. Solvation effects for 1 and 2 were studied implicitly using the polarizable continuum model and explicitly represented by interactions with a single water molecule. An increase in the conformational preference for the cis-amide conformer of azPro was clearly seen. An intramolecular hydrogen bond occurred solely in the trans-amide conformer that reduced the preference for the cis-conformer by 2.2 kcal/mol. The larger ring homolog aza-pipecolic acid (azPip), in which this internal hydrogen bond was diminished, significantly augmented stabilization of the cis-amide conformer. In aqueous solution, the preference for the cis-amide conformers was greatly reduced, mainly as a result of interaction between water and the lone pair of the alpha-nitrogen in the trans-amide conformer that was 3.8 kcal/mol greater than that in the cis-conformer. In the azPro analog, the energy barrier for cis-trans amide isomerization was 6 kcal/mol less than that in the cognate Pro derivative. Because the azPro derivatives can stabilize the cis-amide bond and mimic a type VI beta-turn without incorporation of additional steric bulk, such a simple chemical modification of the peptide backbone provides a useful conformational constraint when incorporated into the structure of selected bioactive peptides. Such modifications can scan receptors for biological recognition of reverse turns containing cis-amide bonds by the incorporation of type VI beta-turn scaffolds with oriented appended side chains. 相似文献
48.
A novel mode of affinity chromatography (AC) based on an open tubular capillary column (OTAC) is demonstrated. The OTAC column is prepared by immobilizing Cibacron blue F3GA onto the inner surface of a 50-microm-i.d. capillary column. The AC experiment is performed on a capillary electrophoresis instrument by using its pressure system as the driving force. Bovine serum albumin and lysozyme (Lys) are successfully separated with stepwise gradient elution. The relative standard deviation (RSD) for the elution time of the retained Lys is 0.08%, and good repeatability of its peak area and peak height with an RSD value lower than 2.12% for 10 consecutive runs is observed. The loading capacity and detection limit for the retained Lys are approximately 36 ng and 8.6 ng, respectively. It is also found that the amount of protein adsorbed is unaffected by the flow rate of the loading buffer, and OTAC can be used for the fast determination of biopolymers. Some of the advantages of OTAC over conventional modes of open tubular capillary liquid chromatography are that the detection sensitivity and loading capacity of a sample can be greatly improved, because the relatively large inner diameter of the capillary can be adopted and the whole capillary column can be used to adsorb the solute in OTAC. 相似文献
49.
50.
The alkylation of ethylenethiourea with alcohols and aqueous acids (HCl, HBr, and HI) allows the synthesis of the respective S-alkyl-isothioureas in high yield and purity. Consistently high yields (91-98%) were obtained with 56% HI, the yields for 48% HBr (48-93%) and 37% HCl (36-85%) were lower and varied with the type of alcohol. The method is a convenient low-cost alternative to the use of alkyl iodides and an easy access to the S-tert-butyl isothiourea. 相似文献