首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   3926篇
  免费   218篇
  国内免费   2篇
化学   3257篇
晶体学   23篇
力学   40篇
数学   486篇
物理学   340篇
  2024年   4篇
  2023年   48篇
  2022年   30篇
  2021年   59篇
  2020年   72篇
  2019年   79篇
  2018年   88篇
  2017年   85篇
  2016年   169篇
  2015年   165篇
  2014年   152篇
  2013年   248篇
  2012年   319篇
  2011年   351篇
  2010年   199篇
  2009年   154篇
  2008年   297篇
  2007年   295篇
  2006年   264篇
  2005年   220篇
  2004年   158篇
  2003年   172篇
  2002年   122篇
  2001年   44篇
  2000年   32篇
  1999年   25篇
  1998年   13篇
  1997年   27篇
  1996年   40篇
  1995年   14篇
  1994年   14篇
  1993年   15篇
  1992年   17篇
  1991年   12篇
  1990年   7篇
  1989年   6篇
  1988年   8篇
  1987年   9篇
  1986年   11篇
  1985年   15篇
  1984年   15篇
  1983年   8篇
  1982年   4篇
  1981年   4篇
  1980年   10篇
  1978年   4篇
  1977年   4篇
  1976年   6篇
  1974年   5篇
  1973年   7篇
排序方式: 共有4146条查询结果,搜索用时 31 毫秒
941.

Bacterial cellulose (BC) is a polymer with interesting conformation and properties. BC can be obtained in different shapes and is easily modified by chemical and physical means, so its applications in the production of new materials and nanocomposites for different purposes have been in the focus of many research projects. However, one of the major challenges to address in bacterium-derived polymer technology is to find suitable carbon sources as substrates that are cheap and do not compete with food production for achieving large scale industrial applications. Agricultural wastes are defined as the residues from the growing and processing of raw agricultural products such as crops, fruits, vegetables and dairy products. Their composition can vary depending on the type of agricultural activity and harvesting conditions, but these residues are suitable for the production of BC. The aim of this review is to give insight into the production of BC using agro-wastes and an overview of the most interesting and novel applications of this biopolymer in different areas i.e. environmental applications, optoelectronic and conductive devices, food ingredients and packaging, biomedicine, and 3D printing technology.

Graphic abstract
  相似文献   
942.
Two novel analytical methodologies using capillary electrophoresis (CE) and liquid chromatography (LC) were developed and compared for the determination of diclofenac sodium in commercial and simulated tablet formulations. The CE analysis was performed in a bare fused-silica capillary with 75 microm id and total length of 50 cm (28 cm to the detector) with a buffer solution of 20 mM sodium tetraborate, pH 9.23. The applied voltage was 20 kV, and acetaminophen was used as the internal standard (IS). The LC analysis was performed with a LiChrospher 100 RP-18 (5 microm) column and a mobile phase of methanol-diluted glacial acetic acid (0.3 parts in 2500; 75 + 25) at a flow rate of 0.9 mL/min with propylparaben as the IS. In both analyses, detection was by ultraviolet absorption at 276 nm. Under optimized conditions, the CE migration times for the diclofenac sodium standard and acetaminophen (IS) were 2.07 and 1.59 min, respectively, and the LC retention times for the diclofenac sodium standard and propylparaben (IS) were 3.98 and 2.26 min, respectively. The resolution and efficiency for CE were 14.2 and 1.6 x 10(5) plates/m, respectively, and for LC, 5.0 and 8.6 x 10(3) plates/m, respectively. Calibration curves of peak area versus concentration gave correlation coefficients of 0.9992 for CE and 0.9994 for LC. The limits of detection and quantitation were 8.40 and 25.46 microg/mL, respectively, for CE and 4.60 and 13.93 microg/mL, respectively, for LC. Coefficients of variation were 1.68 and 0.37% for CE and LC, respectively. Average recoveries obtained with CE and LC were 103.12+/-0.90 and 99.59+/-0.21%, respectively. Although both methodologies were shown to be suitable for the determination of diclofenac sodium in tablets, performing in a similar manner with regard to several aspects (linearity, recovery, and specificity), CE provided faster analysis and better column efficiency, whereas LC provided superior repeatability and sensitivity.  相似文献   
943.
Summary A method is described for the speciation of Sb(III) and Sb(V) using HG-AAS. The efficiency of stibine generation using different pH, from Sb(III) and Sb(V) solutions, was tested. At high pH-values Sb(V) is not reduced to form stibine, Sb(III) being selectively determined. The three acids HCl, H2SO4 and H3PO4 at controlled pH were used to generate stibine, H3PO4 being the most satisfactory for antimony speciation. The interference of Sb(V) was studied for the case of Sb(III) determination with stibine generation in H3PO4 medium (pH 1.81). The speciation of Sb(III) and Sb(V) is possible up to a ratio of 1:9.  相似文献   
944.
KNi(4)(PO(4))(3) has been synthesised following a method previously reported by some of us and studied on the basis of magnetization and neutron powder diffraction (NPD) data. Magnetization measurements suggest the coexistence of ferromagnetic (FM) and antiferromagnetic (AFM) interactions: magnetization versus magnetic field curves present a remanent magnetization of around 2.15 micro(B) at T=2 K. The magnetic structure of the KNi(4)(PO(4))(3) has been determined at low temperature from the NPD data. These measurements show that there are three magnetic sub-lattices of Ni(2+) ions, which interact through common oxygen or phosphate groups, giving rise to FM and AFM couplings. The resulting interactions are FM in nature. Such a complex behaviour could provide an interesting model to analyse magnetic interactions in more condensed systems, such in mixed metal oxides.  相似文献   
945.
(±)-Isoagatholactone 1 and (±)-12α-hydroxyspongia-13(16),14-dien 2b, a fundamental skeleton of spongiadiol 2a and its congeners, have been synthesized from (±)-labda-8(20),13-dien-15-oic acid 3.  相似文献   
946.
A new series of hybrid materials of type [Cp*2M][M'(dca)3] has been prepared by cation templation and structurally characterised (M = Fe(III), Co(III); M'= Mn(II), Fe(II), Co(II), Ni(II), Cd(II); dca-= N(CN)2-). The crystallographic analysis of [Cp*2Fe][Cd(dca)(3)] showed that the [Cd(dca)3]- anionic framework is of a symmetrical 3-D alpha-polonium type, containing octahedral Cd nodes and micro (1,5)-dca bridging ligands. The [Cp*2Fe]+ cations occupy the cube-like cavities within the framework. The cationic and anionic-framework sublattices remain magnetically independent and display susceptibilities, over the range 300 to 2 K, of a Curie-Weiss nature obtained by adding a S= 1/2 (Cp*2Fe+) or a S= 0 (Cp*2Co+) contribution to those of the weakly antiferromagnetically coupled frameworks of M'. These hybrid species do not show any intrinsic long-range magnetic order. The present [Cp*2Fe]M'(dca)3] series display the characteristic, unusually shaped [Cp*2Fe]+ Mossbauer line, in the range 295-5 K, assigned (below 101 K) as the sum of a narrow and a broad line. Relaxation effects were evident. The [Fe(dca)3]- compound showed superimposed low-spin Fe(III) and high-spin Fe(II) lines, the latter giving relaxation broadening effects.  相似文献   
947.
The dynamics of concentration fluctuations of three critical samples of the 3-methylpyridine (3MP)+water+NaBr system have been measured by photon correlation spectroscopy. The collective-diffusion coefficient D shows the usual Ising behavior near the critical temperature T(c). However, as |T-T(c)| increases, the dynamic correlation length calculated from D, xi, takes values higher than the correlation length of the critical fluctuations calculated from static light scattering, xi(s). At the largest |T-T(c)| measured, xi approaches the value, xi(0,d) approximately equal to 1.13 nm, while the amplitude of xi(s) is xi(0,s)=0.38 nm. Pulsed-gradient NMR spectroscopy points out the existence of two dynamic contributions. One of them is consistent with the existence of molecular entities of hydrodynamic radius 0.31 nm, while the other one indicates the existence of aggregates rich in 3MP of radius 1.16 nm. The existence of the aggregates may explain the apparent anomalous behavior of the dynamic light scattering experiments for this system far from the critical point.  相似文献   
948.
A series of cis nitrosyl complexes containing polypyridyl ligands were prepared and characterized as cis-[RuL(bpy)2(NO)](PF6)3 (L = pyridine, 4-picoline, or 4-acetylpyridine), by elemental analysis, u.v.–vis. and i.r. spectroscopy, and by electrochemical techniques such as cyclic voltammetry, differential pulse voltammetry, spectroelectrochemistry, and coulometry. The complexes exhibit stretching frequencies (NO) at ca. 1950 cm–1 indicating that nitrosyl group has a sufficiently high degree of nitrosonium ion (NO+) character. In non-aqueous solution, the reduction of these complexes induce nitrosyl to nitro conversion. In aqueous solution the reduction product is cis-[RuL(bpy)2(NH3)]2+ formed by a six electron mechanism. The nitrosyl compounds are susceptible to nucleophilic attack by hydroxide ion. The equilibrium constants were determined.  相似文献   
949.
The complexes TpxCu (Tpx = homoscorpionate) catalyse the insertion of diazo compounds into nitrogen-hydrogen bonds of amines and amides, under very mild conditions, with quantitative yields being obtained with equimolar ratios of reactants.  相似文献   
950.
Reaction of monofunctional oligoisobutylene with maleic anhydride is described. In a preliminary study, thermal dehydrochlorination of α-chlorooligoisobutylene is examined; the double bond of the resulting olefin can be endo or exo. Ene reaction of maleic anhdride with this oligomer is first studied on a model, 2,4,4-trimethyl-1-pentene; resulting mixture is completely analysed by 13C- and 1H-NMR spectroscopy: two isomeric oligomer anhydrides are formed. Ene synthesis is also carried out on α-(2-methyl-2-propenyl)oligoisobutylene; only exo bonds are able to react; the functionality of the resulting oligomeric anhydride mixture is 0.92. In the presence of a catalyst (dichloromaleic anhydride) disubstitution can take place, because the double bond formed in the first reaction is able to react a second time with maleic anhydride.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号