全文获取类型
收费全文 | 9541篇 |
免费 | 758篇 |
国内免费 | 1728篇 |
专业分类
化学 | 9813篇 |
晶体学 | 221篇 |
力学 | 88篇 |
综合类 | 24篇 |
数学 | 141篇 |
物理学 | 1740篇 |
出版年
2024年 | 40篇 |
2023年 | 287篇 |
2022年 | 319篇 |
2021年 | 362篇 |
2020年 | 379篇 |
2019年 | 336篇 |
2018年 | 296篇 |
2017年 | 322篇 |
2016年 | 323篇 |
2015年 | 327篇 |
2014年 | 452篇 |
2013年 | 689篇 |
2012年 | 602篇 |
2011年 | 578篇 |
2010年 | 472篇 |
2009年 | 633篇 |
2008年 | 688篇 |
2007年 | 659篇 |
2006年 | 594篇 |
2005年 | 497篇 |
2004年 | 484篇 |
2003年 | 351篇 |
2002年 | 568篇 |
2001年 | 247篇 |
2000年 | 215篇 |
1999年 | 191篇 |
1998年 | 182篇 |
1997年 | 134篇 |
1996年 | 129篇 |
1995年 | 123篇 |
1994年 | 113篇 |
1993年 | 72篇 |
1992年 | 63篇 |
1991年 | 60篇 |
1990年 | 38篇 |
1989年 | 27篇 |
1988年 | 28篇 |
1987年 | 19篇 |
1986年 | 18篇 |
1985年 | 21篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 6篇 |
1980年 | 16篇 |
1979年 | 10篇 |
1978年 | 5篇 |
1977年 | 8篇 |
1974年 | 4篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
编写了普适性的多键表自洽场程序,该程序能对单电子轨道展开系数和键表系数同时优化,其中单电子轨道的展开空间可任意定义,实际计算建议采用“杂化”轨道形式,即每个单电子轨道只对一个原子的基函数展开。对H2、Li2及HLi采用不同基组进行计算,结果表明用3个键表自洽计算所得能量与MP2结果相近,且我们的计算对键的共价性和离子性分析非常直观。 相似文献
102.
An enzymatic assay for glucose based on the use of the fluorescent probe for hydrogen peroxide, europium(III) tetracycline (EuTc), is described. The weakly fluorescent EuTc and enzymatically generated H2O2 form a strongly fluorescent complex (EuTc–H2O2) whose fluorescence decay profile is significantly different. Since the decay time of EuTc–H2O2 is in the microseconds time domain, fluorescence can be detected in the time-resolved mode, thus enabling substantial reduction of background fluorescence. The scheme represents the first H2O2-based time-resolved fluorescence assay for glucose not requiring the presence of a peroxidase. The time-resolved assay (with a delay time of 60 s and using endpoint detection) enables glucose to be determined at levels as low as 2.2 mol L–1, with a dynamic range of 2.2–100 mol L–1. The method also was adapted to a kinetic assay in order to cover higher glucose levels (mmol L–1 range). The latter was validated by analyzing spiked serum samples and gave a good linear relationship for glucose levels from 2.5 to 55.5 mmol L–1. Noteworthy features of the assay include easy accessibility of the probe, large Stokes shift, a line-like fluorescence peaking at 616 nm, stability towards oxygen, a working pH of approximately 7, and its suitability for both kinetic and endpoint determination. 相似文献
103.
J. Baran A. J. Barnes M. K. Marchewka A. Pietraszko H. Ratajczak 《Journal of Molecular Structure》1997,416(1-3):33-42
The crystal structure of bis(betaine)-selenic acid has been determined by X-ray diffraction as orthorhombic, space group Pbca, with a = 11.591(2), b = 22.930(5), c = 12.045(2) Å and Z = 8. The crystal comprises hydrogen selenate ions, HSeO−4, and two distinct betaine molecules, which are held together into a complex by short hydrogen bonds. One of the betaine molecules is present as the zwitterion form (CH3)3N+---CH2---COO− and the second occurs as the protonated form (CH3)3N+---CH2---COOH. Powder FTIR and Raman spectra were measured. An assignment of the observed bands to vibrations of the hydrogen bonds and internal vibrations of the hydrogen selenate ion and the betaine molecules is proposed. 相似文献
104.
105.
Qing‐Lun Wang Mao Liang Dai‐Zheng Liao Shi‐Ping Yan Zong‐Hui Jiang Peng Cheng 《无机化学与普通化学杂志》2004,630(4):613-616
A unique neodymium(III) complex, {[Nd(BTC)(H2O)4] · H2O}n (BTC = 1, 3, 5‐benzenetricarboxylate), was obtained from the reaction between Nd(ClO4)3 · xH2O and Na3BTC. Coordination bonds, hydrogen bonds, and π‐π stacking form a supramolecular structure with a novel, two‐dimensional framework. The temperature‐dependent magnetic susceptibilities were analyzed by the Curie‐Weiss law; the following values were found C = 1.32, θ = —18.3 K, respectively. 相似文献
106.
The complexes between R3Tr (Tr = B, Al, and Ga; R = H, F, Cl, and Br) and H2X (X = O, S, and Se) were theoretically studied. The interaction energies of R3Al⋯H2X and R3Ga⋯H2X are consistent with the electronegativity of the halogen atom R (R ≠ H), but an opposite dependence is found for R3B⋯H2X. The triel bond of R3Tr⋯H2X is weaker for the heavier chalcogen donor. The dependence of triel bonding strength on the triel atom is complicated, depending on the nature of R and X. The methyl substitution of H2X causes a substantial increase in the interaction energy from −5.74 kcal/mol to −22.88 kcal/mol, and its effect is relevant to the nature of Tr, X, and R groups. For the S and Se donors, the increased percentage of interaction energy is almost the same due to the methyl substitution, which is larger than that of the O analogue. In most triel-bonded complexes, electrostatic dominates and polarization has comparable contribution. However, polarization plays a dominant role in R3B⋯ and R3B⋯ (R = Cl and Br; R′ = H and Me). 相似文献
107.
Brandon D. ConleyBurl C. Yearwood Sean ParkinDavid A. Atwood 《Journal of fluorine chemistry》2002,115(2):155-160
The preparation and characterization of the ammonium hexafluorosilicate salts, 2[R]+ [SiF6]2− (where R=piperidinium (2), methylammonium (3), quinolinium (4), acridinium (5), 2,2,6,6-tetramethylpiperidinium (6), and propylammonium (7)) is described.The salts were prepared from the reaction of the corresponding alkylammonium fluoride with silica gel. The compounds were characterized by NMR, IR, mass spectrometry and in the case of 1 (piperidinium fluoride), 2-4 by X-ray crystallography. Compounds 1-3 crystallize in the orthorhombic crystal system (space groups Iba2, Fdd2, and Pnnm, respectively), with Z=8, 14, and 4, respectively. Compound 4 crystallizes in the triclinic space group P-1, with Z=2. Compounds 1-4 exhibit hydrogen bonding. 相似文献
108.
An automatic system that performs two analytical procedures, allowing the evaluation of the relative antioxidant capacity of wine samples, was developed. Automation was carried out using a sequential injection analysis (SIA) system that allowed, thanks to its versatility, the development of two methodologies. One is based on the decolorization assay of the 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical, using a spectrophotometric detector. A second methodology allowed the evaluation of the hydrogen peroxide scavenging activity by measuring the oxidation of homovanylic acid (HVA) to its fluorescent dimer, using a fluorescent detector.The developed automatic methodologies were evaluated using trolox as standard and subsequently using other antioxidant substances as gallic acid, caffeic acid, ascorbic acid, catechin and taxifolin which are abundant in wine and whose antioxidant activities were compared to that shown by trolox. The spectrophotometric and fluorimetric assays showed linearity intervals between 0.001 and 0.01 mM, and 0.001 and 0.008 mM of trolox, respectively.The evaluation of the antioxidant power of 20 white and red wine samples, from different Portuguese wine producing regions, was carried out sequentially, in the automatic system. The results were expressed in trolox equivalent antioxidant capacity (TEAC) and presented, for the ABTS and hydrogen peroxide scavenging activity methodologies, detection limits of 8.4 × 10−7 and 1.4 × 10−4 mM and relative standard deviation (R.S.D. (%)) in the range 0.6-2.4 and 1-1.8, respectively. 相似文献
109.
Chemodynamic therapy(CDT) is an emerging endogenous stimulation activated tumor treatment approach that exploiting iron-containing nanomedicine as catalyst to convert hydrogen peroxide(H_2O_2)into toxic hydroxyl radical(·OH) through Fenton reaction.Due to the unique characteristics(weak acidity and the high H_2O_2 level) of the tumor microenvironment,CDT has advantages of high selectivity and low side effect.However,as an important substrate of Fenton reaction,the endogenous H_2O_2 in tumor is still insufficient,which may be an important factor limiting the efficacy of CDT.In order to optimize CDT,various H_2O_2-generating nanomedicines that can promote the production of H_2O_2 in tumor have been designed and developed for enhanced CDT.In this review,we summarize recently developed nanomedicines based on catalytic enzymes,nanozymes,drugs,metal peroxides and bacteria.Finally,the challenges and possible development directions for further enhancing CDT are prospected. 相似文献
110.
Extremely localized molecular orbitals (ELMOs), namely orbitals strictly localized on molecular fragments, are easily transferable from one molecule to another one. Hence, they provide a natural way to set up the electronic structure of large molecules using a data base of orbitals obtained from model molecules. However, this procedure obviously increases the energy with respect to a traditional MO calculation. To gain accuracy, it is important to introduce a partial electron delocalization. This can be carried out by defining proper optimal virtual orbitals that supply an efficient set for nonorthogonal configurations to be employed in VB-like expansions. 相似文献