全文获取类型
收费全文 | 84312篇 |
免费 | 605篇 |
国内免费 | 428篇 |
专业分类
化学 | 28635篇 |
晶体学 | 840篇 |
力学 | 6969篇 |
综合类 | 1篇 |
数学 | 32664篇 |
物理学 | 16236篇 |
出版年
2023年 | 55篇 |
2022年 | 505篇 |
2021年 | 389篇 |
2020年 | 272篇 |
2019年 | 245篇 |
2018年 | 10607篇 |
2017年 | 10402篇 |
2016年 | 6326篇 |
2015年 | 1074篇 |
2014年 | 539篇 |
2013年 | 834篇 |
2012年 | 4171篇 |
2011年 | 10882篇 |
2010年 | 5848篇 |
2009年 | 6253篇 |
2008年 | 6820篇 |
2007年 | 8992篇 |
2006年 | 433篇 |
2005年 | 1503篇 |
2004年 | 1670篇 |
2003年 | 2101篇 |
2002年 | 1123篇 |
2001年 | 341篇 |
2000年 | 356篇 |
1999年 | 228篇 |
1998年 | 224篇 |
1997年 | 178篇 |
1996年 | 254篇 |
1995年 | 166篇 |
1994年 | 114篇 |
1993年 | 137篇 |
1992年 | 105篇 |
1991年 | 116篇 |
1990年 | 78篇 |
1989年 | 81篇 |
1988年 | 91篇 |
1987年 | 89篇 |
1986年 | 94篇 |
1985年 | 95篇 |
1984年 | 73篇 |
1983年 | 72篇 |
1982年 | 78篇 |
1981年 | 54篇 |
1980年 | 86篇 |
1979年 | 74篇 |
1978年 | 69篇 |
1977年 | 48篇 |
1914年 | 45篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 93 毫秒
991.
Zhou YanXia Tan HongWei Yang ZuoYin Jia ZongChao Liu RuoZhuang Chen GuangJu 《中国科学B辑(英文版)》2007,50(2):266-271
The insect spruce budworm(Choristoneura fumiferana) produces antifreeze protein(AFP) to assist in the protection of the over-wintering larval stage and contains multiple isoforms. Structures for two isoforms,known as CfAFP-501 and CfAFP-337,show that both possess similar left-handed β-helical structure,although thermal hysteresis activity of the longer isoform CfAFP-501 is three times that of CfAFP-337. The markedly enhanced activity of CfAFP-501 is not proportional to,and cannot be simply accounted for,by the increased ice-binding site resulting from the two extra coils in CfAFP-501. In or-der to investigate the molecular basis for the activity difference and gain better understanding of AFPs in general,we have employed several different computational methods to systematically study the structural properties and ice interactions of the AFPs and their deletion models. In the context of intact AFPs,a majority of the coils in CfAFP-501 has better ice interaction and causes stronger ice lattice disruption than CfAFP-337,strongly suggesting a cooperative or synergistic effect among β-helical coils. The synergistic effect would play a critical role and make significant contributions to the anti-freeze activity β-helical antifreeze proteins. This is the first time that synergistic effect and its implica-tion for antifreeze activity are reported for β-helical antifreeze proteins. 相似文献
992.
Boudjahem AG Monteverdi S Mercy M Bettahar MM 《Langmuir : the ACS journal of surfaces and colloids》2004,20(1):208-213
We have studied the effect of silica of quartz-type on the reducibility of nickel acetate in aqueous hydrazine (80 degrees C, pH = 10-12) and metal particle formation. The obtained materials were characterized by X-ray diffraction, transmission electron microscopy, and thermodesorption experiments. With nickel acetate alone, the reduction was partial (45%) and a metal film at the liquid-gas interface or a powdered metal precipitate with an average particle size of 120 nm was obtained. In the presence of silica as the surfactant, the reduction of nickel acetate was total and the nickel phase deposited as a film on the support with an average particle size of 25 nm. Supported nickel acetate was also totally reduced. Crystallites of a mean particle size of about 3 nm were obtained. Decreasing the nickel content or increasing the hydrazine/nickel ratio decreased the metal particle size. Whiskers were formed for low nickel loadings. Hydrogen thermal treatment of the reduced phase showed that the organic acetate fragment, belonging to the precursor salt, still remained strongly attached to the nickel phase. The amount of the retained organic matrix depended on the metal particle size. Surface defects are suggested as active sites, which enhanced nickel ion reduction in the presence of silica as the surfactant or support. Metal-support interactions and the nucleation/ growth rate were the main factors determining the size and morphology of the supported metal particles formed. The organic matrix covered the reduced nickel phase. 相似文献
993.
Małgorzata Olejnik Teresa Szprengier-Juszkiewicz Piotr Jedziniak Jan Żmudzki 《Accreditation and quality assurance》2007,12(12):637-641
In this paper, the case of FAPAS PT 0270 “Doramectin and Oxfendazole in Sheep Liver” is discussed. During evaluation of the
data received from participants (determination of total, oxidised oxfendazole residue and calculation of the sum of oxfendazole
and oxfendazole sulfone residues), significant differences were observed between the results obtained by use of two analytical
approaches. This phenomenon can be explained by the route of oxfendazole metabolism, which results in the presence of fenbendazole
in the sample. This was not predicted by the provider; consequently, not all the necessary tests on the material were conducted.
Due to the high uncertainty of the z-scores in this test, the results of the PT cannot be used for purposes of evaluation, and the benefits of participation in
PT 0270 are questionable. 相似文献
994.
The use of reduced overlap population (ROP) analysis from EHMO calculations as a means to gauge the presence of metal–metal
bonds in triosmium clusters is examined. A number of triosmium clusters containing bridging ligands have been used as test
cases, including the bis-ethoxy bridged cluster Os3(μ-OEt)2(CO)10, 1b, and some of its group 15 derivatives Os3(μ-OEt)2(CO)9(EPh3), 2. These latter clusters are newly synthesized and have been characterized completely, including by single-crystal X-ray crystallographic
studies.
In honour of Professor Dieter Fenske on his 65th birthday. 相似文献
995.
The evidence for the stabilizing nature of the H–H bonding in planar biphenyl is succinctly reviewed. The stabilizing nature
of the H–H bonding is revealed through a comparison of the atomic energy of every atom in planar biphenyl with the same atom
in the twisted equilibrium structure. It is shown that the barrier to rotation via the planar transition state is the net
resultant of a stabilisation of the four ortho-hydrogen atoms (by 8 kcal/mol each), a stabilisation of the two para-carbon atoms (by 3 kcal/mol each) and by the dominant destabilisation of the two carbon atoms joining the two rings—the two
junction carbon atoms—(by 22 kcal/mol each). The energetic stabilisation of the four ortho-hydrogen atoms is further shown to be in large proportion due to the formation of the hydrogen–hydrogen interatomic surface.
Furthermore, neither the “bond order” between the two junction carbon atoms nor the total electron delocalisation between
the two rings exhibit a significant change in going from the planar to the twisted equilibrium geometry. These findings are
in contrast with the classical view of a balance between “steric non-bonded repulsion” and better electron delocalisation
as a function of the twist dihedral angle. Similar conclusions have been recently reached by Pacios and Gómez through a study
of the electrostatic potential at the position of the hydrogen nuclei.
We dedicate this article to Professor TM Krygowski on the occasion of his 70th birthday wishing him a long and productive
life. 相似文献
996.
A multi-wall carbon nanotube (MWNT)/cetyl pyridine bromine (CPB) composite film modified glassy carbon electrode (GCE) was
developed for the electrochemical determination of hymecromone in phosphonate buffer. Electrochemical behaviour of hymecromone
at the composite film electrode was investigated with voltammetry. Compared with an irreversible oxidation of hymecromone
at the bare GCE, the oxidation peak current was enhanced greatly at the film electrode. Some parameters such as pH, scan rate,
accumulation potential and accumulation time were optimized. Under optimal conditions, an oxidation peak at 0.82 V was employed
to determine hymecromone electrochemically. A linearity between the oxidation peak current and the hymecromone concentration
was obtained in the range of 3.0 × 10−7 − 2.0 × 10−5 mol 1−1 with a detection limit of 8.0 × 10−8 mol 1−1. The proposed procedure was successfully applied to assay hymecromone in pharmaceutical formulation with satisfactory results.
The text was submitted by the authors in English. 相似文献
997.
Zhang De-Qing Wang Shao-Jun Sun Hong-Shan Wang Xiu-Li Cao Mao-Sheng 《Journal of Sol-Gel Science and Technology》2007,41(2):157-161
Lead zirconate titanate nanopowders Pb(Zr0.52Ti0.48)O3 (PZT) were prepared by modified sol-gel process in ethylene glycol system with zirconium nitrate as the zirconium source.
The research showed that it was critical to add lead acetate after the reaction of zirconium nitrate and tetrabutyl titanate
in ethylene glycol system for preparing PZT of exact titanium content. The reaction mechanisms of the sol synthesis, preparation
of xerogel and agglutinating process were characterized through using FT-IR, NMR, TG-FTIR, and GC-MS. The experiment proved
that ethylene glycol system did not rely on hydrolysis and condensation reactions in the process of the sol formation, but
on the formation of chain or network large molecules from complexation of ethylene glycol and all Ti and minor Pd, Zr. In
the preparation of xerogel, the complexation reaction was so completed that it formed large molecules network composed of
metal and dioxyethyl. Bulk weight loss happened before 350°C in the process of sintering xerogel to prepare PZT nanopowders.
Volatile matters and vapor phase decomposition resultants were primarily oxy-compounds including ethylene glycol, aldehyde-ketone
compounds, carbon dioxide and nitrate radical conversion matters. After 350°C, primary vapor phase decomposition resultants
were carbon dioxide and minor carbonyl compound. 相似文献
998.
The chiroptical properties and transient rheological behavior of (acetyl)(ethyl)cellulose (AEC) m-cresol liquid crystalline solutions have been investigated. Chiroptical properties were manipulated through (i) increasing degree of acetylation of ethyl cellulose (EC), and (ii) blending AEC with EC. At the same average degree of acetylation (DA), the chiroptical properties of pure AEC were different from those of the EC/AEC mixtures. However, at the same DA, the AEC and mixed AEC/EC solutions showed similar steady state flow and oscillatory behaviors, but the transient behaviors were different. At high flow rates the mixed AEC/EC solutions exhibited double recoil after cessation of steady-state flow, whereas the AEC solutions showed double recoil only in the high DA AEC solutions. All solutions, pure and mixed, had the same stress relaxation behavior. Both pitch and handedness affected the transient behavior. After cessation of high shear rate flow, the rate of modulus evolution decreased with increasing pitch, and was faster in right-handed mesophases than in left-handed ones at a similar pitch. 相似文献
999.
Jian-yun Du 《Transition Metal Chemistry》2004,29(7):699-702
Two novel complexes, [Zn(dmatrz)2]Cl2
(1) and [Zn(dmatrz)2(SCN)2] (2), have been prepared and characterized by X-ray crystallography, absorption and luminescence spectrometries (dmatrz=3,5-dimethy-4-amino-1,2,4-triazole). The coordination environment of the zinc(II) ions in (1) and (2) has a distorted tetrahedral geometry completed via two independent nitrogen atoms of two triazole ligands and two anions, respectively. Both (1) and (2) show strong blue luminescence properties. Furthermore, (1) displays stronger blue photoluminescence than (2) as the result of different anions (Cl- and SCN-) coordinated to the zinc(II) ions. 相似文献
1000.
Young-a Lee Sang Myung jung Shin Won kang Ok-sang Jung 《Transition Metal Chemistry》2004,29(7):710-713
A facile procedure for synthesizing the mono(hydroxo)tris(carboxylato)platinum(IV) species has been achieved. The reaction of [PtII(OH)2(dmpda)] (dmpda=2,2-dimethyl-1,3-propanediamine) with a 30% aqueous solution of H2O2 in the presence of a carboxylic acid produces a stable [PtIV(OOCR)3(OH)(dmpda)] (R=Me, Et) complex in high yield. The crystal structures of [PtIV(OOCMe)3(OH)(dmpda)] . H2O (triclinic P1 bar, a=8.761(2) Å, b=9.245(3) Å, c=10.659(2) Å, =106.25(2)°, =93.90(2)°, =98.92(2)°, V=813.1(3) Å3, Z=2, R= 0.0474) and [PtIV(OOCEt)3(OH)(dmpda)] (monoclinic P21/c, a=12.777(4) Å, b=10.514(2) Å, c=14.971(3) Å, =107.40(2)°, V=1919.2(8) Å3, Z=4, R=0.0611) show that the hydroxyl group has been selectively positioned at an axial site. The intramolecular hydrogen bond between the OH and C=O moiety exists (O(H)...=C, 2.83 Å for [PtIV(OOCMe)3(OH)(dmpda)] · H2O; 2.72 Å for [PtIV(OOCEt)3(OH)(dmpda)]. Formation of the axial-mono(hydroxo)tris(carboxylato)platinum(IV) species may be ascribed to a combination of `reactive-equatorial effects' with `cis-addition' in the carboxylic acid. 相似文献