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   2730篇
  免费   30篇
  国内免费   11篇
化学   1808篇
晶体学   34篇
力学   52篇
数学   310篇
物理学   567篇
  2024年   12篇
  2023年   15篇
  2022年   51篇
  2021年   81篇
  2020年   77篇
  2019年   105篇
  2018年   79篇
  2017年   78篇
  2016年   112篇
  2015年   94篇
  2014年   82篇
  2013年   158篇
  2012年   161篇
  2011年   229篇
  2010年   128篇
  2009年   114篇
  2008年   153篇
  2007年   164篇
  2006年   208篇
  2005年   155篇
  2004年   99篇
  2003年   91篇
  2002年   79篇
  2001年   39篇
  2000年   38篇
  1999年   26篇
  1998年   22篇
  1997年   21篇
  1996年   21篇
  1995年   10篇
  1994年   12篇
  1993年   9篇
  1992年   9篇
  1991年   8篇
  1990年   4篇
  1988年   2篇
  1987年   1篇
  1985年   2篇
  1984年   2篇
  1982年   4篇
  1981年   2篇
  1980年   4篇
  1979年   3篇
  1978年   2篇
  1977年   1篇
  1972年   3篇
  1968年   1篇
排序方式: 共有2771条查询结果,搜索用时 0 毫秒
921.
922.
    
The considered method for obtaining hollow polymer particles is based on the following pathway: (1) preparation of a carboxylated core latex by emulsion copolymerization of acrylic monomers with methacrylic acid, (2) synthesis of a core-shell latex comprising a styrene (co)polymer shell, (3) neutralization of the core carboxylic groups with a base followed by the core ionization and hydration to a high degree, shell expansion and formation of water-filled hollows. A number of approaches to improve the hydrophilic core – hydrophobic shell compatibility and enlarge the hollow volume are considered. The synthesized hollow particles are of a submicron size with the relative hollow volume Vhol : Vpart.= 0.43 – 0.64. Methods for cationic hollow particle latex preparation by anionic latex recharging with a cationic surfactant or acidic melamine resin are discussed. Recharging with a melamine resin is shown to afford hollow particles with an external polymer shell providing a high thermal stability of the particles.  相似文献   
923.
    
Hydrolysis of the new types of iminium salts was used to synthesize О,О‐dialkyl‐S‐(1,1‐dimethyl‐2‐oxoethyl)dithiophosphates or 2‐dialkoxythiophosphorylthio‐substituted aldehydes with carbon isochain. Reactions of aldehydes with N‐, N,N‐, and O,N‐nucleophiles gave new phosphorylated imines containing an acetal group at different positions, perhydro‐1,3‐diazol and oxazol with the diisopropoxythiophosphorylthio group in a side chain, and hydrazone of this aldehyde and diphenylphosphinylacetic acid hydrazide.  相似文献   
924.
    
The mechanism of the reduction of phosphine oxides by PhSiH3 was established on the basis of kinetic measurements and Density Functional Theory (DFT) calculations. In particular, it has been proved that the model reaction between tri‐n‐butylphosphine oxide and phenylsilane occurs via a nonpolar mechanism. The data presented herein allow prediction and verification of the applicability of the new reduction reagents and conditions for industrially attractive processes.  相似文献   
925.
    
The bromodomain‐containing proteins BRD9 and BRD7 are part of the human SWI/SNF chromatin‐remodeling complexes BAF and PBAF. To date, no selective inhibitor for BRD7/9 has been reported despite its potential value as a biological tool or as a lead for future therapeutics. The quinolone‐fused lactam LP99 is now reported as the first potent and selective inhibitor of the BRD7 and BRD9 bromodomains. Development of LP99 from a fragment hit was expedited through balancing structure‐based inhibitor design and biophysical characterization against tractable chemical synthesis: Complexity‐building nitro‐Mannich/lactamization cascade processes allowed for early structure–activity relationship studies whereas an enantioselective organocatalytic nitro‐Mannich reaction enabled the synthesis of the lead scaffold in enantioenriched form and on scale. This epigenetic probe was shown to inhibit the association of BRD7 and BRD9 to acetylated histones in vitro and in cells. Moreover, LP99 was used to demonstrate that BRD7/9 plays a role in regulating pro‐inflammatory cytokine secretion.  相似文献   
926.
    
Oligomeric and protofibrillar aggregates formed by the amyloid‐β peptide (Aβ) are believed to be involved in the pathology of Alzheimer’s disease. Central to Alzheimer pathology is also the fact that the longer Aβ42 peptide is more prone to aggregation than the more prevalent Aβ40. Detailed structural studies of Aβ oligomers and protofibrils have been impeded by aggregate heterogeneity and instability. We previously engineered a variant of Aβ that forms stable protofibrils and here we use solid‐state NMR spectroscopy and molecular modeling to derive a structural model of these. NMR data are consistent with packing of residues 16 to 42 of Aβ protomers into hexameric barrel‐like oligomers within the protofibril. The core of the oligomers consists of all residues of the central and C‐terminal hydrophobic regions of Aβ, and hairpin loops extend from the core. The model accounts for why Aβ42 forms oligomers and protofibrils more easily than Aβ40.  相似文献   
927.
    
The effect of quantum mechanical delocalization of atomic nuclei on the conformation of the six‐membered ring structure in two hydrocarbons, cyclohexane and benzene, is investigated using ab initio path integral approach. A striking feature of benzene species is revealed using ring puckering coordinate representation, which demonstrates that the zero point motion of the heavy atom skeleton dominates over the out‐of‐plane thermal motions of the ring. Even more unexpected is the fact, that this is true not only at low temperature of 150 K, at which such behavior would not be surprising, but also at room temperature, where the nuclear quantum effects are usually of lesser importance, especially in the case of such heavy nuclei as carbon. In view of this finding the planar conformation of benzene, whose equilibrium (T = 0 K) geometry results from the well‐known properties of the electronic structure, can be elucidated also at nonzero temperature. According to our simulations, it appears as a consequence of quantum delocalization of the carbon nuclei rather than a trivial time average over the classical configurations of the puckered ring. This interesting behavior is contrasted with the clearly nonplanar structure of cyclohexane, whose ring puckering states can be unequivocally assigned even if the nuclear delocalization is taken into account. © 2014 Wiley Periodicals, Inc.  相似文献   
928.
929.
    
A two‐step reaction to convert terminal alkynes into triborylalkenes is reported. In the first step, the terminal alkyne and pinacolborane (HBpin) are converted into an alkynylboronate, which is catalyzed by an iridium complex supported by a SiNN pincer ligand. In the second step, treatment of the reaction mixture with CO generates a new catalyst which mediates dehydrogenative diboration of alkynylboronate with pinacolborane. The mechanism of the diboration remains unclear but it does not proceed via intermediacy of hydroboration products or via B2pin2.  相似文献   
930.
The chemistry of firefly bioluminescence is important for numerous applications in biochemistry and analytical chemistry. The emitter of this bioluminescent system, firefly oxyluciferin, is difficult to handle. The cause of its lability was clarified while its synthesis was reinvestigated. A side product was identified and characterized by NMR spectroscopy and X‐ray crystallography. The reason for the lability of oxyluciferin is now ascribed to autodimerization of the coexisting enol and keto forms in a Mannich‐type reaction.  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