全文获取类型
收费全文 | 39119篇 |
免费 | 3964篇 |
国内免费 | 4601篇 |
专业分类
化学 | 34257篇 |
晶体学 | 450篇 |
力学 | 1633篇 |
综合类 | 287篇 |
数学 | 3282篇 |
物理学 | 7775篇 |
出版年
2024年 | 49篇 |
2023年 | 443篇 |
2022年 | 817篇 |
2021年 | 1169篇 |
2020年 | 1426篇 |
2019年 | 1330篇 |
2018年 | 1120篇 |
2017年 | 1368篇 |
2016年 | 1570篇 |
2015年 | 1498篇 |
2014年 | 1816篇 |
2013年 | 2753篇 |
2012年 | 2421篇 |
2011年 | 2520篇 |
2010年 | 2141篇 |
2009年 | 2603篇 |
2008年 | 2430篇 |
2007年 | 2465篇 |
2006年 | 2288篇 |
2005年 | 2062篇 |
2004年 | 1987篇 |
2003年 | 1560篇 |
2002年 | 1760篇 |
2001年 | 1093篇 |
2000年 | 863篇 |
1999年 | 738篇 |
1998年 | 606篇 |
1997年 | 551篇 |
1996年 | 568篇 |
1995年 | 530篇 |
1994年 | 502篇 |
1993年 | 345篇 |
1992年 | 347篇 |
1991年 | 211篇 |
1990年 | 175篇 |
1989年 | 165篇 |
1988年 | 174篇 |
1987年 | 132篇 |
1986年 | 108篇 |
1985年 | 91篇 |
1984年 | 90篇 |
1983年 | 34篇 |
1982年 | 78篇 |
1981年 | 105篇 |
1980年 | 117篇 |
1979年 | 121篇 |
1978年 | 96篇 |
1977年 | 71篇 |
1976年 | 65篇 |
1973年 | 32篇 |
排序方式: 共有10000条查询结果,搜索用时 203 毫秒
941.
The kinetics of catalytic decomposition of NO over Cu/ZSM-5 catalyst has been studied in an integral flow reactor at atmospheric
pressure. Kinetic analysis is based on the assumption that the surface reaction represents the rate-determining step. On the
basis of theoretical considerations of different interactions between reactants and catalyst, and experimental evidences,
three different mechanistic kinetic models were chosen. Also a power-law model was tested. The best agreement has been achieved
with the model
相似文献
942.
Goryunov E. I. Petrovskii P. V. Shcherbina T. M. Zakharov L. S. 《Russian Chemical Bulletin》2001,50(6):1085-1087
Catalytic phosphorylation of -trifluoromethylbenzyl alcohols with POCl3 taken in a ratio of 3 : 1 under particular temperature conditions afforded predominantly symmetrical tris(-trifluoromethylbenzyl) phosphates. The latter were obtained as mixtures of two diastereomers with a statistical ratio of the components. 相似文献
943.
This paper summarizes our research in the preparation of chain end functionalized isotactic polypropylene (PP) having a terminal functional group, such as Cl, OH, and NH2. The chemistry involves metallocene-mediated propylene polymerization using rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2/MAO complex in the presence of styrene derivatives (St-f) and hydrogen, which serve as the chain transfer agents. The molecular weight of the resulting PP polymers with a terminal Cl, OH and NH2 group (i.e., PP-t-Cl, PP-t-OH and PP-t-NH2) are inversely proportional to the molar ratio of [St-f]/[propylene]. Despite the extremely low concentration of functional group, the high molecular weight chain end functionalized PP-t-OH and exhibit a distinctive advantage over other functional PP polymers containing side chain functional groups or long functional blocks. The terminal hydrophilic OH and cations, with good mobility and reactivity, effectively hydrogen bond and ion-exchange the cations (Li+, Na+, etc.) located between the clay interlayers, respectively. Such interactions anchor the PP chain to the clay surfaces. On the other hand, the remaining rest of the unperturbed end-tethered high molecular weight PP tail exfoliates the clay layers. This exfoliated structure is maintained even after further mixing of the PP-bearing platelets with pure neat PP polymers. 相似文献
944.
Hamdi N. Feutelais Y. Yagoubi N. de Girolamo D. Legendre B. 《Journal of Thermal Analysis and Calorimetry》2004,76(3):985-1001
Indomethacin is known to exhibit polymorphism and solvates, the different forms obtained do not exhibit the same solubility
and their bioavailabilities are different. It is of a prime importance to identify the various polymorphic and solvated forms.
This study was carried out by: DSC (different scanning calorimetry), TG (thermogravimetric analysis), X-ray diffraction and
thermomicroscopy. Seven solvates, with acetone, benzene, dichloromethane, tetrahydrofurane, propanol, chloroform and diethylether,
were isolated and studied. Their formulae have been determined by thermogravimetric analysis and their X-ray patterns on powder
are presented, by DSC their behaviour after desolvation is recorded, the temperature and the enthalpy of fusion are measured
and by this way the form obtained is deduced.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
945.
The interaction of ethidium bromide (2,7-diamino-10-ethyl-9-phenylphenanthridinium bromide; EB) with double stranded (ds) calf thymus DNA and thermally denatured single stranded (ss) DNA was studied in solution and at the electrode surface by means of transfer voltammetry using a carbon paste electrode (CPE) as working electrode in 0.2 M acetate buffer, pH 5.0. As a result of intercalation of this dye between the base pairs of dsDNA, the characteristic peak of dsDNA, due to the oxidation of guanine residues, decreased and after a particular concentration of EB a new peak at +0.81 V appeared, probably due to the formation of a complex between dsDNA and EB. The non-intercalated EB gives another peak, but at an increased concentration of the dye. A similar behaviour was observed during the interaction of the dye with ssDNA.Furthermore, the interaction of EB with ds, ss and supercoiled (sc) DNA was studied at the hanging mercury drop electrode (HMDE) surface by means of alternating current voltammetry in 0.3 M NaCl and 50 mM sodium phosphate buffer (pH 8.5) as supporting electrolyte. dsDNA yields a smaller peak at −1.42 V (peak III) compared to the one yielded by ssDNA, since the latter is a relaxed and more accessible form. By addition of EB into the buffer solution an increase of peak III was observed in the dsDNA form as well as in ssDNA resulting from their interaction with EB. Furthermore, the appearance of peak III in covalently closed circular scDNA after exposure to increasing concentrations of EB is a result of the introduction of ‘free ends’ in DNA affecting its structural integrity. 相似文献
946.
Studies on the Interaction of Beryllon Ш with Proteins by Voltammetric Technique and its Application 总被引:1,自引:0,他引:1
A new quantitative determination method of proteins using beryllon Ш by voltammetric technique was developed in this paper. In pH 3.5 Britton-Robinson (B-R) buffer solution, beryllon Ш can bind with human serum albumin (HSA) to form an electro-inactive supermolecular complex. Beryllon Ш has a well-defined voltammetric reduction peak at -0.38 V (vs. SCE) and the addition of protein in this solution can cause the decrease of the reductive peak current. Based on the decrease of the reduction peak current, a new electrochemical method for the determination of HSA was established with linear range of 1.0~40.0 mg/L and the detection limit of 1.0 mg/L. This method is further applied to the determination of real sample of healthy human serum. 相似文献
947.
948.
Macrocycle opening in derivatives of benzocrown ethers under the action of amines is affected by the nature of the heteroatoms in the macrocycle, the nature of the functional group in the benzene ring of the crown ether, and the length, branching, and number of hydrocarbon radicals at the amine nitrogen atom. A distinguishing feature of this reaction is the template effect of MeNH3
+, Me2NH2
+, Na+, and K+ ions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 687–692, March, 1996.For Part I see Ref. 1. 相似文献
949.
A new method for synthesizing nitrogen-containing podands by nucleophilic regioselective cleavage of the macrocycle in formyl derivatives of benzocrown ethers by heating with methylamine and methylammonium chloride has been developed. This reaction is the first example of crown ether opening by a nitrogen-containing nucleophile.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 950–953, May, 1995. 相似文献
950.
Solutions of poly(methyl methacrylate) in styrene are used to produce thin polymer films (1m–20m) saturated with styrene monomer. In the illuminated areas refractive index changes up to 10–2 are achieved by photoinduced polymerisation. The index patterns may be fixed by annealing treatments removing the residual monomer.We thank P. Hertel, M. Kopietz, M. D. Lechner and D. Steinmeier for valuable discussions. Financial support of the Stiftung Volkswagenwerk is gratefully acknowledged. 相似文献