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   1179篇
  免费   143篇
  国内免费   120篇
化学   947篇
晶体学   40篇
力学   48篇
综合类   4篇
数学   146篇
物理学   257篇
  2023年   13篇
  2022年   21篇
  2021年   29篇
  2020年   17篇
  2019年   31篇
  2018年   21篇
  2017年   25篇
  2016年   51篇
  2015年   58篇
  2014年   62篇
  2013年   86篇
  2012年   81篇
  2011年   92篇
  2010年   49篇
  2009年   40篇
  2008年   78篇
  2007年   58篇
  2006年   60篇
  2005年   49篇
  2004年   56篇
  2003年   44篇
  2002年   61篇
  2001年   47篇
  2000年   30篇
  1999年   28篇
  1998年   22篇
  1997年   12篇
  1996年   15篇
  1995年   11篇
  1994年   17篇
  1993年   16篇
  1992年   12篇
  1991年   8篇
  1990年   14篇
  1989年   7篇
  1988年   4篇
  1987年   7篇
  1986年   5篇
  1985年   8篇
  1984年   10篇
  1982年   15篇
  1981年   9篇
  1979年   8篇
  1978年   4篇
  1976年   4篇
  1974年   7篇
  1971年   6篇
  1970年   4篇
  1968年   4篇
  1967年   4篇
排序方式: 共有1442条查询结果,搜索用时 15 毫秒
881.
Three polysaccharide-protein complexes of longan pulp (LP1-3) were isolated in this work. Their physicochemical characteristics and immunomodulatory effects on splenocytes, natural killer (NK) cells and macrophages in vitro were investigated. The carbohydrate portions of LP1-3 were principally composed of glucose, arabinose and mannose. LP3 displayed the maximal moisture absorption, and the thermal stability of LP2 was obviously higher than that of LP1 and LP3. All of them showed the characteristic polysaccharide and protein bands in the Fourier Transform Infrared (FTIR) spectrum. For a certain dose, all the fractions could significantly stimulate splenocyte proliferation, macrophage phagocytosis against neutral red, and NK cell cytotoxicity against YAC-1 lymphoma cell (P < 0.05). The results demonstrated that the polysaccharide-protein complexes of longan pulp have medical potential as immunotherapeutic adjuvants due to their immunomodulatory activities.  相似文献   
882.
We perform a systematic investigation on small silicon-doped boron clusters B(n)Si (n=1-7) in both neutral and anionic states using density functional (DFT) and coupled-cluster (CCSD(T)) theories. The global minima of these B(n)Si(0/-) clusters are characterized together with their growth mechanisms. The planar structures are dominant for small B(n)Si clusters with n≤5. The B(6)Si molecule represents a geometrical transition with a quasi-planar geometry, and the first 3D global minimum is found for the B(7)Si cluster. The small neutral B(n)Si clusters can be formed by substituting the single boron atom of B(n+1) by silicon. The Si atom prefers the external position of the skeleton and tends to form bonds with its two neighboring B atoms. The larger B(7)Si cluster is constructed by doping Si-atoms on the symmetry axis of the B(n) host, which leads to the bonding of the silicon to the ring boron atoms through a number of hyper-coordination. Calculations of the thermochemical properties of B(n)Si(0/-) clusters, such as binding energies (BE), heats of formation at 0 K (ΔH(f)(0)) and 298 K (ΔH(f)([298])), adiabatic (ADE) and vertical (VDE) detachment energies, and dissociation energies (D(e)), are performed using the high accuracy G4 and complete basis-set extrapolation (CCSD(T)/CBS) approaches. The differences of heats of formation (at 0 K) between the G4 and CBS approaches for the B(n)Si clusters vary in the range of 0.0-4.6 kcal mol(-1). The largest difference between two approaches for ADE values is 0.15 eV. Our theoretical predictions also indicate that the species B(2)Si, B(4)Si, B(3)Si(-) and B(7)Si(-) are systems with enhanced stability, exhibiting each a double (σ and π) aromaticity. B(5)Si(-) and B(6)Si are doubly antiaromatic (σ and π) with lower stability.  相似文献   
883.
We describe a simple technique for fabricating non-emissive colour filters based on the sensitisation of a highly porous nanostructured metal-oxide film with a monolayer of dye molecules. Ultrafast electron transfer at the oxide/dye interface induces efficient quenching of photogenerated excitons in the dye, reducing the photoluminescence quantum yield by many orders of magnitude. The resultant filters exhibit much less autofluorescence than conventional colour filters (where the chromophore is dispersed in a glass or polymer host), and are a viable low cost alternative to interference filters for microfluidic devices and other applications requiring non-emissive filtering.  相似文献   
884.
The synthesis of a new charge-neutral zwitterionic tripodal borate ligand based on 2-hydroxypyridine is reported. (Dimethylaminopyridinium)tris(2-pyridonyl)borate, (DMAP)Thp, has been complexed to copper(I) chloride to give a pseudo-C(3) symmetric complex. The propensity for this ligand and other flexible scorpionates to exhibit such helical chirality upon complexation is discussed.  相似文献   
885.
In this work the controllability of fractional impulsive neutral functional integrodifferential systems in a Banach space has been addressed. Sufficient conditions for the controllability are established using fractional calculus, a semigroup of operators and Krasnoselskii’s fixed point theorem.  相似文献   
886.
This paper deals with the existence of solutions for the problem
{(Фp(u′))′=f(t,u,u′),t∈(0,1),
u′(0)=0,u(1)=∑i=1^n-2aiu(ηi),
where Фp(s)=|s|^p-2s,p〉1.0〈η1〈η2〈…〈ηn-2〈1,ai(i=1,2,…,n-2)are non-negative constants and ∑i=1^n-2ai=1.Some known results are improved under some sign and growth conditions. The proof is based on the Brouwer degree theory.  相似文献   
887.
888.
Composite membranes with a sub-nanoscale homogeneous distribution of CD toroids in the Matrimid matrix were developed for dehydration of aqueous isopropanol. The composite membranes demonstrated separation factor far surpassing that of the neat Matrimid dense membrane. The heart of this innovation is the utilization of a CD derivative, ethylenediamine-β-cyclodextrin (EDA-β-CD), where the amine of CD could react with the imide of Matrimid and efficiently immobilize the CD rings during membrane formation. The superior separation properties for membranes embedded with 2–5% EDA-β-CD were attributed to the additional water channels created by the hydrophilic outer surface of CD and its interactions with the polymer matrix. FT-IR, density measurements and XRD have confirmed these hypotheses. Nevertheless, the separation factor exhibited an increasing then decreasing trend as a function of CD content and the opposite trend was observed with permeation flux. Investigation on the effect of feed water concentration showed that the neat Matrimid membrane possessed almost constant performance, but the Matrimid/EDA-β-CD (0.05) composite membrane exhibited an obvious increase in permeability and a decrease in selectivity at high water content. Even though the composite membrane swelled more at higher water content due to the intensified hydrophilicity ascribed to the introduction of CD structure, it always had much better separation factor. In addition, the Matrimid mixed matrix membranes embedded with 2–5% EDA-β-CD held reasonably tensile strength and modulus. The newly developed mixed matrix membrane approach may open up a new way to prepare next-generation high-performance asymmetric pervaporation membranes for isopropanol separation.  相似文献   
889.
Enantioselective formal hetero‐Diels‐Alder reactions of trifluoromethylated enones and 2‐amino‐1,3‐butadienes generated in situ from aliphatic acyclic enones and chiral primary amines are reported. The corresponding tetrahydropyran‐4‐ones are formed in up to 94 % yield and with up to 94 % ee. The reaction was carried out through a stepwise mechanism, including initial aminocatalytic aldol condensation of 2‐amino‐1,3‐butadiene to the trifluoromethylated carbonyl group followed by an intramolecular oxa‐Michael addition. Both NMR investigation and theoretical calculations on the transition state indicate that the protonated tertiary amine could effectively activate the carbonyl group of the trifluoromethyl ketone to promote the addition process through hydrogen‐bonding interaction of N?H???F and N?H???O simultaneously, and thus provide a chiral environment for the approach of amino‐1,3‐butadienes to the activated trifluoromethyl ketone, resulting in high enantioselectivity.  相似文献   
890.
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