全文获取类型
收费全文 | 1606篇 |
免费 | 123篇 |
国内免费 | 156篇 |
专业分类
化学 | 1382篇 |
晶体学 | 24篇 |
力学 | 6篇 |
综合类 | 7篇 |
数学 | 351篇 |
物理学 | 115篇 |
出版年
2023年 | 20篇 |
2022年 | 23篇 |
2021年 | 27篇 |
2020年 | 41篇 |
2019年 | 42篇 |
2018年 | 40篇 |
2017年 | 47篇 |
2016年 | 47篇 |
2015年 | 43篇 |
2014年 | 61篇 |
2013年 | 186篇 |
2012年 | 123篇 |
2011年 | 77篇 |
2010年 | 88篇 |
2009年 | 90篇 |
2008年 | 106篇 |
2007年 | 105篇 |
2006年 | 98篇 |
2005年 | 74篇 |
2004年 | 75篇 |
2003年 | 76篇 |
2002年 | 53篇 |
2001年 | 39篇 |
2000年 | 48篇 |
1999年 | 32篇 |
1998年 | 30篇 |
1997年 | 28篇 |
1996年 | 27篇 |
1995年 | 23篇 |
1994年 | 14篇 |
1993年 | 13篇 |
1992年 | 16篇 |
1991年 | 5篇 |
1990年 | 8篇 |
1989年 | 11篇 |
1988年 | 8篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1970年 | 1篇 |
1967年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有1885条查询结果,搜索用时 15 毫秒
31.
The local optimality conditions to polynomial optimization problems are a set of polynomial equations (plus some inequality conditions). With the recent techniques of Gröbner bases one can find all solutions to such systems, and hence also find global optima. We give a short survey of these methods. We also apply them to a set of problems termed with exact solutions unknown in the problem sets of Hock and Schittkowski. To these problems we give exact solutions. 相似文献
32.
A. Zielenkiewicz K. Busserolles G. Roux-Desgranges A. H. Roux J-P. E. Grolier W. Zielenkiewicz 《Journal of solution chemistry》1995,24(7):623-632
Densities and specific heat capacities of ternary aqueous systems containing dipeptides (glycyl-glycine or L--alanyl-L--alanine) and nucleic acid bases (cytosine or thymine) or their alkyl derivatives (1,3-diethylthymine or caffeine) were determined at 25°C by flow calorimetry and flow densimetry. The partial molar volumes and heat capacities of transfer at infinite dilution of the different nucleic acid bases from water to water+dipeptide solutions were obtained therefrom. Except for the case of the transfer of cytosine to aqueous glycyl-glycine solutions where a small positive dependence of the transfer quantities was observed with the dipeptide concentration, the values of the heat capacities of transfer were in general low, positive or negative, depending on the compensation of hydrophobic-hydrophilic interactions between the dipeptide and the base. The volumes of transfer of most of the bases are very small, within the limit of the experimental error. 相似文献
33.
A one-step synthesis of alkylN-(-amidomethyl)glycinates from glycine esters or their salts, formaldehyde, and aroylamides was developed. The effect of the structure of the amide component and the reaction conditions on the yields of the products was investigated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1078–1080, June, 1994. 相似文献
34.
Mireille Regnier 《BIT Numerical Mathematics》1985,25(2):335-357
Grid file algorithms were suggested in [12] to provide multi-key access to records in a dynamically growing file. We specify here two algorithms and derive the average sizes of the corresponding directories. We provide an asymptotic analysis. The growth of the indexes appears to be non-linear for uniform distributions:O(v
c
) orO(v
), wherec=1+b–1, =1+(s-1)/(sb+1),s is the number of attributes being used,v the file size, andb the page capacity of the system. Finally we give corresponding results for biased distributions and compare transient phases. 相似文献
35.
R. I. Kureshy N. H. Khan S. H. R. Abdi P. Iyer A. K. Bhatt 《Journal of molecular catalysis. A, Chemical》1997,120(1-3):101-108
A series of new dissymmetric chiral Schiff base complexes has been obtained by a systematic condensation of (1S,2S)(+)-diaminocyclohexane and 3-acetyl-4-hydroxy-6-methyl-2-pyrone with salicylaldehyde, 5-chloro-, 5-methoxy-and 5-nitrosalicylaldehyde and by subsequent metallation with manganese and ruthenium. The characterization of the complexes 1–8 was accomplished by physico chemical studies viz. microanalysis, IR-, UV/VIS-, and CD spectral studies, optical rotation, molar conductance measurements and cyclic voltammetry. Enantioselective epoxidation of non functionalised olefins, viz. cis-stilbene, trans-3-nonene and trans-4-octene with iodosyl benzene as oxidant was demonstrated in the presence of catalytic amounts of chiral Mn(III) and Ru(III) dissymmetric Schiff base complexes. Good optical yields of epoxides were obtained for the catalyst 4 with the substrates trans-3-nonene and cis-stilbene. 相似文献
36.
Jerzy Lisowski Marta Paluch Tadeusz Lis 《Journal of inclusion phenomena and macrocyclic chemistry》2006,55(1-2):123-129
The template condensation of (R)-2,2′-diamino-1,1′-binaphthyl and 2,6-diformylpyridine leads to lanthanide(III) complexes of the new chiral hexaaza macrocycle L that adopts highly twisted conformation in [LnL](NO3)3 complexes. The complexes have been characterised by ESI MS spectrometry and NMR spectroscopy. The analogous N2O4 chiral crown ether L2 that has the same carbon skeleton as L does not exhibit tendency to bind lanthanide(III) ions. The X-ray crystal structure of L2 exhibit squeezed conformation of the macrocycle and spatial disposition of donor atoms that does not predispose it for coordination of lanthanide(III) ions. 相似文献
37.
The paper represents a further development of our hydrate hypothesis of simplest living matter origination (SLMO) from inorganic and simplest organic mineral substances. It is supposed that the sources of SLMO are simplest aliphatic hydrocarbons, niters, and phosphates. Thermodynamic calculations demonstrating a principal possibility for simultaneous syntheses of different nitrogen bases, d-ribose, and desoxy-d-ribose from these source substances are presented. The most probable principal mechanism of SLMO and the principal conditions necessary for realization of the proposed chemism of SLMO in the framework of the proposed mechanism are considered. A principal means for testing the hypothesis is proposed. 相似文献
38.
The mononuclear macrocyclic polyamine metal complexes 5a-5e have been shown to form stable 1 : 1 complexes with bases and nucleosides. Their binding constants (K) were determined by UV-visible spectrometric titration. The results show that recognition ability of the complexes 5a--5e for uracil, U (Uridine), dT (Thymidine) is higher than that for the other bases or nucleosides (such as Cytidine, Guanosine, Adenosine). The metal ion also plays an important role for the recognition ability of complexes. 相似文献
39.
A.S. Stella Shalini M. Amaladasan N. Prasannabalaji J. Revathi G. Muralitharan 《Arabian Journal of Chemistry》2019,12(7):1176-1185
Asymmetrical macrocyclic complexes of MnII, CoII, NiII, CuII and ZnII have been synthesized by the template process using bis(benzil)ethylenediamine as precursor. Bis(benzil)ethylenediamine reacts with transition metal chlorides and trimethoprim in a 1:1:1 molar ratio in methanol to give several solid metal complexes of the general composition [M(L)X2] (M = MnII, CoII, NiII, CuII and ZnII, L = ligand and X = Cl?). They were characterized by physicochemical and spectroscopic techniques. Based on analytical, spectral and magnetic moments, all the complexes are identified as distorted octahedral structures. All the complexes are of the [M(L)X2] type. The shifts of the ν(CN) (azomethine) stretches have been monitored. To find out the donor sites of the ligands, the activity data show that the metal complexes are more potent than the parent ligand. The [M(L)X2] complexes showed a broad spectrum of antimicrobial activity in vitro against both gram-positive and gram-negative human pathogenic bacterial isolates and the antimicrobial spectrum enhanced only with a combination of metal chlorides and trimethoprim complex. From the results it is imperative that the synthesized macrocyclic [M(L)X2] complexes exhibit potent broad spectrum antibacterial activity. 相似文献
40.
《Chemphyschem》2004,5(2):202-208
We have designed and synthesized a series of Schiff base derivatives, and studied their structural features in two‐dimensional (2D) and three‐dimensional (3D) states by combining scanning tunneling microscopy (STM) and X‐ray diffraction experiments. The Schiff‐base derivatives with short alkyl chains crystallize easily, which allows a detailed structural analysis by X‐ray diffraction. Due to the strong adsorbate–substrate interactions, those bases with long alkyl chains easily form 2D assemblies on highly oriented pyrolytic graphite (HOPG). The STM images indicate also that the introduction of two methoxy groups into the molecule can change the structure of these 2D assemblies as a result of the increased steric hindrances, for example: the Schiff‐base derivative, bearing both methoxy groups and C16H33 tails, forms 2D Moiré patterns, and an alignment of pairing Schiff‐base molecules may be easily resolved. Conversely, the Schiff base derivative, bearing solely C16H33 tails, forms 2D non‐Moiré patterns. It is demonstrated that the 3D structural features result from the compromise of intermolecular interactions of different molecular moieties. However, there is one more factor, which also governs the 2D structure: the adsorbate‐substrate interaction. The 3D crystal structure may thus help to understand many factors involved in the formation of 2D structures, and would be helpful for designing new molecular assemblies with tailoring functions. 相似文献