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   17885篇
  免费   1497篇
  国内免费   2683篇
化学   16002篇
晶体学   157篇
力学   473篇
综合类   84篇
数学   667篇
物理学   1870篇
无线电   2812篇
  2024年   63篇
  2023年   194篇
  2022年   298篇
  2021年   466篇
  2020年   635篇
  2019年   600篇
  2018年   562篇
  2017年   835篇
  2016年   923篇
  2015年   792篇
  2014年   942篇
  2013年   1548篇
  2012年   1209篇
  2011年   1084篇
  2010年   927篇
  2009年   988篇
  2008年   1032篇
  2007年   1066篇
  2006年   991篇
  2005年   919篇
  2004年   841篇
  2003年   688篇
  2002年   571篇
  2001年   519篇
  2000年   501篇
  1999年   434篇
  1998年   388篇
  1997年   360篇
  1996年   320篇
  1995年   281篇
  1994年   267篇
  1993年   243篇
  1992年   153篇
  1991年   84篇
  1990年   67篇
  1989年   53篇
  1988年   46篇
  1987年   26篇
  1986年   27篇
  1985年   30篇
  1984年   27篇
  1983年   13篇
  1982年   29篇
  1981年   15篇
  1980年   3篇
  1979年   2篇
  1978年   1篇
  1974年   1篇
  1969年   1篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
961.
Polymer dispersed liquid crystal (PDLC) films are fabricated by well-known polymerization-induced phase separation method. In this paper, the dispersion of multi-walled carbon nanotubes (MWCNT) in liquid crystals has been enhanced by chemical modification and we have investigated their effects on the morphology, electro-optical properties and conductivity of the PDLC films. Results indicated that the threshold voltage and the saturation voltage of PDLC films decreased with the increase of the doping concentration of MWCNT or chemically modified MWCNT, because carbon nanotubes can enhance the electric field by reducing the resistivity of the medium and increasing the capacitance of the cells. It can be viewed obviously that the contrast ratio of the PDLC films doped with the chemically modified MWCNT is higher than that of the MWCNT.  相似文献   
962.
Effects of the content of fluorinated alkene-terminated liquid crystal (LC) molecules on the physical properties of the fluorinated alkene-terminated LC/E8 mixture were studied. The morphology and electro-optical properties as they doped in polymer-dispersed liquid crystal (PDLC) films were investigated. The detailed discussion of the obtained results is given. As a result, comparing with the physical properties of the series of LC mixtures with the same content of the analogous fully saturated compounds doped with E8, we find that the birefringence is significantly larger for the LC mixture with the alkene-terminated materials. Both fluorinated alkene-terminated LC molecules and the analogous fully saturated compounds doped with E8 reduce the driving voltage of PDLC films. Moreover, PDLC films with the fluorinated alkene-terminated LC molecules possessed higher contrast ratio and faster response time than that of the PDLC films prepared by adding the same mass fraction of the analogous fully saturated compounds. Thus, the ability to manipulate physical properties of LC mixture and electro-optical properties of PDLC films by changing the LC molecular structures may have future relevance for new LC structures design and applications of PDLC films.  相似文献   
963.
The one‐step synthesis of well‐defined CO2‐based diblock copolymers was achieved by simultaneous ring‐opening copolymerization (ROCOP) of CO2/epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC‐COOH) as the bifunctional chain transfer agent (CTA). The double chain‐transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09–1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC‐COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO2‐based polycarbonates.  相似文献   
964.
Shape‐memory polymers (SMPs) are an intriguing class of smart materials possessing reversible shape change and recovery capabilities. Effective routes to shape‐memory porous films (SMPFs) are few and limited in scope owing to the difficulty in manipulating the shape change of pores by conventional methods. Herein we report an unconventional strategy for crafting light‐driven SMPFs by judiciously constructing highly ordered porous films via a facile “breath figure” approach, followed by sequential vapor crosslinking and nondestructive directional light manipulation. Micropores can thus be transformed into other shapes including rectangle, rhombus and size‐reduced micropores at room temperature. The transformed micropores can be reverted to their original shapes by either thermal annealing or UV irradiation. As such, this strategy expands the rich diversity of SMPs accessible.  相似文献   
965.
Carriers that can afford tunable physical and structural changes are envisioned to address critical issues in controlled drug delivery applications. Herein, photo‐responsive conjugated polymer nanoparticles (CPNs) functionalized with donor–acceptor Stenhouse adduct (DASA) and folic acid units for controlled drug delivery and imaging are reported. Upon visible‐light (λ=550 nm) irradiation, CPNs simultaneously undergo structure, color, and polarity changes that release encapsulated drugs into the cells. The backbone of CPNs favors FRET to DASA units boosting their fluorescence. Notably, drug‐loaded CPNs exhibit excellent biocompatibility in the dark, indicating perfect control of the light trigger over drug release. Delivery of both hydrophilic and hydrophobic drugs with good loading efficiency was demonstrated. This strategy enables remotely controlled drug delivery with visible‐light irradiation, which sets an example for designing delivery vehicles for non‐invasive therapeutics.  相似文献   
966.
Novel click reactions are of continued interest in fields as diverse as bio‐conjugation, polymer science and surface chemistry. Qualification as a proper “click” reaction requires stringent criteria, including fast kinetics and high conversion, to be met. Herein, we report a novel strain‐promoted cycloaddition between cyclopropenes and o‐quinones in solution and on a surface. We demonstrate the “click character” of the reaction in solution and on surfaces for both monolayer and polymer brush functionalization.  相似文献   
967.
Ambient‐temperature sodium–sulfur (Na–S) batteries are considered a promising energy storage system due to their high theoretical energy density and low costs. However, great challenges remain in achieving a high rechargeable capacity and long cycle life. Herein we report a stable quasi‐solid‐state Na‐S battery enabled by a poly(S‐pentaerythritol tetraacrylate (PETEA))‐based cathode and a (PETEA‐tris[2‐(acryloyloxy)ethyl] isocyanurate (THEICTA))‐based gel polymer electrolyte. The polymeric sulfur electrode strongly anchors sulfur through chemical binding and inhibits the shuttle effect. Meanwhile, the in situ formed polymer electrolyte with high ionic conductivity and enhanced safety successfully stabilizes the Na anode/electrolyte interface, and simultaneously immobilizes soluble Na polysulfides. The as‐developed quasi‐solid‐state Na‐S cells exhibit a high reversible capacity of 877 mA h g?1 at 0.1 C and an extended cycling stability.  相似文献   
968.
Two nickel(II) coordination polymers, namely, {[Ni1/2(TPO)1/3(bib)1/2(H2O)] · H2O}n ( 1 ), and [Ni(HTPO)(bpy)(H2O)2]n ( 2 ), were assembled from tripodal ligand of tripodal tri(p‐carboxyphenyl) phosphane oxide (H3TPO) and two N‐donors [bib = 1,4‐bis(imidazolyl)benzene, and bpy = 4,4′‐bipyridine]. Their structures were determined by single‐crystal X‐ray diffraction analysis and further characterized by elemental analysis, IR spectra, powder X‐ray diffraction (PXRD), and thermogravimetric analysis (TGA). Structural analysis reveals that complex 1 is an interestingly 3D (3,4)‐connected {103}2{106}3 net, whereas complex 2 is a 1D polymeric chain, which was further expanded into a 3D supramolecular structure through hydrogen bonds. Luminescent sensing measurements show two nickel CPs can selectively and sensitively detect for acetone from normal solvents (DMF, DMA, DMSO, MeOH, EtOH, CH3CN, H2O, and N‐butanol).  相似文献   
969.
A polydentate ligand bridged by a fluorene group, namely 9,9‐bis(2‐hydroxyethyl)‐2,7‐bis(pyridin‐4‐yl)fluorene (L), has been prepared under solvothermal conditions in acetonitrile. Crystals of the three‐dimensional metal–organic framework (MOF) poly[[[μ3‐9,9‐bis(2‐hydroxyethyl)‐2,7‐bis(pyridin‐4‐yl)fluorene‐κ3N:N′:O]bis(methanol‐κO)(μ‐sulfato‐κ2O:O′)nickel(II)] methanol disolvate], {[Ni(SO4)(C27H24N2O2)(CH3OH)]·2CH3OH}n, (I), were obtained by the solvothermal reaction of L and NiSO4 in methanol. The ligand L forms a two‐dimensional network in the crystallographic bc plane via two groups of O—H…N hydrogen bonds and neighbouring two‐dimensional planes are completely parallel and stack to form a three‐dimensional structure. In (I), the NiII ions are linked by sulfate ions through Ni—O bonds to form inorganic chains and these Ni‐containing chains are linked into a three‐dimensional framework via Ni—O and Ni—N bonds involving the polydentate ligand L. With one of the hydroxy groups of L coordinating to the NiII atom, the torsion angle of the hydroxyethyl group changes from that of the uncoordinated molecule. In addition, the adsorption properties of (I) with carbon dioxide were investigated.  相似文献   
970.
A new cobalt(II) coordination polymer (CP), poly[[bis[μ6‐4‐(4‐carboxylatophenoxy)benzene‐1,3‐dicarboxylato‐κ6O1:O1:O3:O3′:O4:O4′]bis(1,10‐phenanthroline‐κ2N,N′)tricobalt(II)] 0.72‐hydrate], {[Co3(C15H7O7)2(C12H8N2)2]·0.72H2O}n, (I), is constructed from CoII ions and 4‐(4‐carboxyphenoxy)isophthalate (cpoia3−) and 1,10‐phenanthroline (phen) ligands. Based on centrosymmetric trinuclear [Co3(phen)2(COO)6] secondary building units (SBUs), the structure of (I) is a three‐dimensional CP with a (3,6)‐connected net and point symbol (42.6)2(44.62.87.102). The positions of four [Co3(phen)2(COO)6] SBUs and four cpoia3− ligands reproduce a Chinese‐knot‐shaped arrangement along the ab plane. (I) has been characterized by single‐crystal X‐ray diffraction, IR spectroscopy, powder X‐ray diffraction (PXRD) and thermostability analysis. It shows a good thermal stability from room temperature to 673 K. In addition, the temperature dependence of the magnetic properties was measured.  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