全文获取类型
收费全文 | 2883篇 |
免费 | 104篇 |
国内免费 | 19篇 |
专业分类
化学 | 2018篇 |
晶体学 | 20篇 |
力学 | 65篇 |
数学 | 503篇 |
物理学 | 400篇 |
出版年
2023年 | 24篇 |
2022年 | 79篇 |
2021年 | 104篇 |
2020年 | 62篇 |
2019年 | 60篇 |
2018年 | 58篇 |
2017年 | 47篇 |
2016年 | 103篇 |
2015年 | 92篇 |
2014年 | 107篇 |
2013年 | 184篇 |
2012年 | 177篇 |
2011年 | 246篇 |
2010年 | 153篇 |
2009年 | 129篇 |
2008年 | 181篇 |
2007年 | 186篇 |
2006年 | 147篇 |
2005年 | 132篇 |
2004年 | 123篇 |
2003年 | 85篇 |
2002年 | 89篇 |
2001年 | 34篇 |
2000年 | 30篇 |
1999年 | 26篇 |
1998年 | 21篇 |
1997年 | 22篇 |
1996年 | 21篇 |
1995年 | 20篇 |
1994年 | 27篇 |
1993年 | 21篇 |
1992年 | 15篇 |
1991年 | 16篇 |
1990年 | 16篇 |
1989年 | 14篇 |
1988年 | 9篇 |
1987年 | 11篇 |
1986年 | 10篇 |
1985年 | 15篇 |
1984年 | 15篇 |
1983年 | 14篇 |
1982年 | 21篇 |
1981年 | 12篇 |
1980年 | 4篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1976年 | 4篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1912年 | 2篇 |
排序方式: 共有3006条查询结果,搜索用时 0 毫秒
51.
Michael?J.?Bucknum Eduardo?A.?CastroEmail author 《Journal of mathematical chemistry》2005,38(1):27-42
The present report is an account of the generalization of the dynamic elasticity theory earlier proposed by Bucknum et al. and applied to the cubic diamond and tetragonal glitter lattices. It describes a theory of elasticity in which the elasticity moduli are based upon the microscopic constants of the various structure-types. Such microscopic constants include the force constants of the chemical bonds in the unit of pattern of the material, its associated lattice parameters, and the elastic chemical bond deformation parameters of the material. In developing the outward features of the dynamic elasticity model, it is shown that an integral over the force density in the unit cell of a given material; where the force is modeled based upon the elastic deformation forces of the chemical bonds in the unit of pattern of the material, and the volume is written as a function of the deformations taking place inside the unit cell of the material; generates the terms for calculating its modulus of elasticity at pressure, in components, that are directed along the principal axes of the unit cell. Several potential solutions to the problem of superhardness are discussed and illustrated. 相似文献
52.
Summary The grafting of minerals by alkenylchlorosilanes leads to organomineral derivatives which are superficially covered by unsaturated organic groups. These groups may be of value when the grafted mineral is used as a reinforcing agent in a polymeric matrix. In this case, the unsaturated grafted groups copolymerize with an organic monomer to build up a composite material. It is therefore of importance to preserve the unsaturated character of the alkenyl-silane during the grafting reactions. It is shown that in certain synthesis conditions, the hydrochloric acid present in the reaction medium adds to the alkenyl-groups. For instance, in the grafting of methylvinyl-dichlorosilane, this reaction is of minor importance, whereas in the case of allyldimethylchlorosilane, no allyl groups are grafted as such on the mineral surface.
With 2 figures
Part 1: Nature and role of the hydrolysis products of the methylvinyldichlorosilane in the grafting of silicates in hydrochloric acid and isopropanolThis journal 256, 135 (1978). 相似文献
Zusammenfassung Die Pfropfung von silicatischen Mineralen mit Alkenylchlorosilanen führt zu organischen Derivaten, deren Oberfläche mit ungesättigten organischen Gruppen bedeckt ist. Diese Gruppen können Vorteile bieten, wenn die so behandelten Minerale als Fül-stoffe oder Verstärker in einer Polymermatrix eingesetzt werden. Die ungesättigten Gruppen können miteinem organischen Monomer kopolymerisieren und ein echtes Verbundmaterial bilden. Die Pfropfung muß allerdings so geführt werden, daß der ungesättigte Charakter der Alkenylsilane erhalten bleibt. In der Arbeit werden experimentelle Bedingungen dafür berichtet.
With 2 figures
Part 1: Nature and role of the hydrolysis products of the methylvinyldichlorosilane in the grafting of silicates in hydrochloric acid and isopropanolThis journal 256, 135 (1978). 相似文献
53.
The chiral compounds (R)‐ and (S)‐1‐benzoyl‐2,3,5,6‐tetrahydro‐3‐methyl‐2‐(1‐methylethyl)pyrimidin‐4(1H)‐one ((R)‐ and (S)‐ 1 ), derived from (R)‐ and (S)‐asparagine, respectively, were used as convenient starting materials for the preparation of the enantiomerically pure α‐alkylated (alkyl=Me, Et, Bn) α,β‐diamino acids (R)‐ and (S)‐ 11 – 13 . The chiral lithium enolates of (R)‐ and (S)‐ 1 were first alkylated, and the resulting diasteroisomeric products 5 – 7 were aminated with ‘di(tert‐butyl) azodicarboxylate’ (DBAD), giving rise to the diastereoisomerically pure (≥98%) compounds 8 – 10 . The target compounds (R)‐ and (S)‐ 11 – 13 could then be obtained in good yields and high purities by a hydrolysis/hydrogenolysis/hydrolysis sequence. 相似文献
54.
Barluenga J Ballesteros A Bernardo De La Rúa R Santamaría J Rubio E Tomás M 《Journal of the American Chemical Society》2003,125(7):1834-1842
Cyclization reactions of group 6 Fischer carbene complexes with cyclopentanone and cyclohexanone enamines are described. Enamine 3a undergoes thermal alpha,beta,beta'-annulation with alkenylcarbene complexes 1 and 2 (THF, 60 degrees C), affording semibullvalenes 5. The metalate intermediates 6, resulting from beta,beta'-annulation of the enamines 3a and 4a, were quantitatively formed by running the reaction in hexane at room temperature. Acid-promoted demetalation of 6 afforded endo-2-bicyclo[3.2.1]octen-8-ones 7 and endo/exo-2-bicyclo[3.3.1]nonen-9-ones 8 (endo/exo = 5:1). Using (S)-methoxymethylpyrrolidine-derived enamines 3b and 4b,c allowed highly enantioenriched cycloadducts endo-(+)-7 as well as endo-(-)-8 and exo-(-)-8 to be accessed. The non-heteroatom-stabilized carbene complex 10 was formed from complex 6 by Me(3)SiOTf-promoted elimination of the methoxy group, characterized by (13)C NMR, and transformed into the organic compounds 7, 7-d, and 11 as well as into bicyclo[3.2.1]octan-2,8-diones 14 and cycloheptanones 15. On the basis of this sequence, enantioenriched cycloheptanones (+)-15 were efficiently prepared in one pot from carbene complexes 2 and enamine 3b (51-55% yield, 91-96% ee). Extension of this work to simple Fischer carbene complexes 16 allowed an appropriate way to generate the nonstabilized pentacarbonyl[(phenyl(alkyl)carbene]tungsten complex 17 to be designed, for which the thermal and chemical behavior leading to compounds 18-21 is described. 相似文献
55.
Jose′ L. F. C. Lima Antoacutenio O. S. S. Rangel M. Renata S. Souto 《Fresenius' Journal of Analytical Chemistry》1997,358(5):657-662
A flow injection system was developed for the sequential determination of total nitrogen and phosphorus in digests of vegetables
using potentiometric and spectrophotometric detection systems, respectively. A tubular ammonium selective electrode with a
sensor system composed of nonactin/monactin in tris(2-ethylhexyl) phosphate was used. The selectivity limitations of this
electrode were overcome by the inclusion of a gas-diffusion unit in the system that separated ammonium from the rest of the
sample matrix and allowed the determination of total nitrogen and phosphorus by the partition of the sample plug between two
streams.
The results obtained with the developed FIA system were in good agreement with those of the reference methods. Sampling rates
from 40 to 60 samples per hour and relative standard deviations below 3.5% were achieved.
Received: 17 October 1996/Revised: 21 November 1996/Accepted: 27 November 1996 相似文献
56.
Cornejo A Fraile JM García JI García-Verdugo E Gil MJ Legarreta G Luis SV Martínez-Merino V Mayoral JA 《Organic letters》2002,4(22):3927-3930
[formula: see text] A chiral pyridine-bis(oxazoline) ligand, functionalized with a vinyl group in the pyridine ring, can be polymerized with styrene and divinylbenzene to obtain supported chiral ligands. As proof of the usefulness of this supported ligands, the corresponding ruthenium complexes are catalysts for the cyclopropanation reaction of styrene with ethyl diazoacetate with up to 85% ee. 相似文献
57.
Flow injection system with gas diffusion for the sequential determination of total nitrogen and phosphorus in vegetables 总被引:1,自引:0,他引:1
Jose´ L. F. C. Lima Antoacutenio O. S. S. Rangel M. Renata S. Souto 《Analytical and bioanalytical chemistry》1997,358(5):657-662
A flow injection system was developed for the sequential determination of total nitrogen and phosphorus in digests of vegetables
using potentiometric and spectrophotometric detection systems, respectively. A tubular ammonium selective electrode with a
sensor system composed of nonactin/monactin in tris(2-ethylhexyl) phosphate was used. The selectivity limitations of this
electrode were overcome by the inclusion of a gas-diffusion unit in the system that separated ammonium from the rest of the
sample matrix and allowed the determination of total nitrogen and phosphorus by the partition of the sample plug between two
streams.
The results obtained with the developed FIA system were in good agreement with those of the reference methods. Sampling rates
from 40 to 60 samples per hour and relative standard deviations below 3.5% were achieved.
Received: 17 October 1996/Revised: 21 November 1996/Accepted: 27 November 1996 相似文献
58.
59.
Arelí Durón-Castellanos Vanesa Zazueta-Novoa Hortencia Silva-Jiménez Yolanda Alvarado-Caudillo Eduardo Peña Cabrera Roberto Zazueta-Sandoval 《Applied biochemistry and biotechnology》2005,121(1-3):279-288
Different soluble NAD+-dependent alcohol dehydrogenase (ADH) isozymes were detected in cell-free homogenates from aerobically grown mycelia of YR-1
strain of Mucor circinelloides isolated from petroleumcontaminated soil samples. Depending on the carbon source present in the growth media, multiple NAD+-dependent ADHs were detected when hexadecane or decane was used as the sole carbon source in the culture media. ADH activities
from aerobically or anaerobically grown mycelium or yeast cells, respectively, were detected when growth medium with glucose
added was the sole carbon source; the enzyme activity exhibited optimum pH for the oxidation of different alcohols (methanol,
ethanol, and hexadecanol) similar to that of the corresponding aldehyde (≈7.0). Zymogram analysis conducted with partially
purified fractions of extracts from aerobic mycelium or anaerobic yeast cells of the YR-1 strain grown in glucose as the sole
carbon source indicated the presence of a single NAD+-dependent ADH enzyme in each case, and the activity level was higher in the yeast cells. ADH enzyme from mycelium grown in
different carbon sources showed high activity using ethanol as substrate, although higher activity was displayed when the
cells were grown in hexadecane as the sole carbon source. Zymogram analysis with these extracts showed that this particular
strain of M. circinelloides has four different isozymes with ADH activity and, interestingly, one of them, ADH4, was identified also as phenanthrene-diol-dehydrogenase,
an enzyme that possibly participates in the aromatic hydrocarbon biodegradation pathway. 相似文献
60.
Reaction of a (237)Np(V) stock solution in the presence of oxalic acid, calcium chloride, and sodium hydroxide under hydrothermal conditions produces single crystals of a neptunium(V) oxalate, Na(2)NpO(2)(C(2)O(4))OH.H(2)O. The structure consists of one-dimensional chains running down the a axis and is the first example of a neptunium(V) oxalate compound containing hydroxide anions. 相似文献