全文获取类型
收费全文 | 5732篇 |
免费 | 1000篇 |
国内免费 | 557篇 |
专业分类
化学 | 3693篇 |
晶体学 | 53篇 |
力学 | 255篇 |
综合类 | 30篇 |
数学 | 735篇 |
物理学 | 2523篇 |
出版年
2024年 | 23篇 |
2023年 | 130篇 |
2022年 | 197篇 |
2021年 | 213篇 |
2020年 | 226篇 |
2019年 | 196篇 |
2018年 | 180篇 |
2017年 | 174篇 |
2016年 | 287篇 |
2015年 | 251篇 |
2014年 | 316篇 |
2013年 | 385篇 |
2012年 | 478篇 |
2011年 | 547篇 |
2010年 | 331篇 |
2009年 | 328篇 |
2008年 | 355篇 |
2007年 | 327篇 |
2006年 | 313篇 |
2005年 | 260篇 |
2004年 | 193篇 |
2003年 | 168篇 |
2002年 | 193篇 |
2001年 | 150篇 |
2000年 | 124篇 |
1999年 | 155篇 |
1998年 | 127篇 |
1997年 | 108篇 |
1996年 | 105篇 |
1995年 | 71篇 |
1994年 | 53篇 |
1993年 | 52篇 |
1992年 | 47篇 |
1991年 | 59篇 |
1990年 | 31篇 |
1989年 | 27篇 |
1988年 | 22篇 |
1987年 | 17篇 |
1986年 | 22篇 |
1985年 | 17篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 6篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有7289条查询结果,搜索用时 15 毫秒
221.
Prof. Dr. Ji‐Jiang Wang Pei‐Xiang Cao Mei‐Li Zhang Lou‐Jun Gao Xiang‐Yang Hou 《无机化学与普通化学杂志》2012,638(10):1531-1534
A new 3D metal‐organic framework {[Ag4(btc)(bix)2] · H2O}n ( 1 ) [H4btc = biphenyl‐2, 2′,4, 4′‐tetracarboxylic acid, bix = 1, 4‐bis(imidazol‐1‐ylmethyl)benzene] was synthesized under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, infrared (IR) spectroscopy, thermal gravimetric analysis (TGA), and luminescence studies. The most remarkable structural feature of 1 is that the 1D chain and 2D network interpenetrated structures are further linked by parallel aligned 1D AgI chains to generate 3D metal‐organic framework. 相似文献
222.
以天然高分子壳聚糖(CS)、羧甲基纤维素(CMC)和温度敏感性单体N-异丙基丙烯酰胺(NIPAM)为原料,通过自组装制备了温度敏感性聚电解质复合纳米粒子CS-g-PNIPAM/CMC-g-PNIPAM,并以5-氟尿嘧啶(5-FU)为模型药物研究了纳米粒子对药物的负载与可控释放性能。当CMC-g-PNIPAM与CS-g-PNIPAM的质量比为3:7时,形成的纳米粒子结构最稳定,动态光散射(DLS)测得其平均粒径为116nm,粒径分布较窄。载药纳米粒子对5-FU具有较高的载药量和包封率。在磷酸盐缓冲溶液中的释药行为表明,其累积药物释放量随pH和温度的增加而增大,表现出良好的pH与温度可控性能。 相似文献
223.
The reaction of propionyl radical with oxygen has been studied using the full coupled cluster theory with the complete basis set. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for this important reaction in detail. The reaction takes place via a chemical activation mechanism. The barrierless association of propionyl with oxygen produces the propionylperoxy radical, which decomposes to form the hydroxyl radical and the three-center alpha-lactone predominantly or the four-center beta-propiolactone. The oxidation of propionyl radical to carbon monoxide or carbon dioxide is not straightforward rather via the secondary decomposition of alpha-lactone and beta-propiolactone. Kinetically, the overall rate constant is almost pressure independent and it approaches the high-pressure limit around tens of torr of helium. At temperatures below 600 K, the rate constant shows negative temperature dependence. The experimental yields of the hydroxyl radical can be well reproduced, with the average energy transferred per collision -DeltaE=20-25 cm(-1) at 213 and 295 K (helium bath gas). At low pressures, together with the hydroxy radical, alpha-lactone is the major product, while beta-propiolactone only accounts for about one-fifth of alpha-lactone. At the high-pressure limit, the production of the propionylperoxy radical is dominant together with a fraction of the isomers. The infrared spectroscopy or the mass spectroscopy techniques are suggested to be employed in the future experimental study of the C2H5CO+O2 reaction. 相似文献
224.
Wang D Yang P Cheng Z Wang W Hou Z Dai Y Li C Lin J 《Journal of colloid and interface science》2012,365(1):320-325
Gd(2)(WO(4))(3) doped with Eu(3+) or Tb(3+) thin phosphor films with dot patterns have been prepared by a combinational method of sol-gel process and microcontact printing. This process utilizes a PDMS elastomeric mold as the stamp to create heterogeneous pattern on quartz substrates firstly and then combined with a Pechini-type sol-gel process to selectively deposit the luminescent phosphors on hydrophilic regions, in which a Gd(2)(WO(4))(3):Ln(3+) (Ln=Eu, Tb) precursor solutions were employed as ink. X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectra, as well as low voltage cathodoluminescence (CL) spectra were carried out to characterize the obtained samples. Under ultraviolet excitation and low-voltage electron beams excitation, the Gd(2)(WO(4))(3):Eu(3+) samples exhibit a strong red emission arising from Eu(3+)(5)D(0,1,2)-(7)F(1,2) transitions, while the Gd(2)(WO(4))(3):Tb(3+) samples show the green emission coming from the characteristic emission of Tb(3+) corresponding to (5)D(4)-(7)F(6,5,4,3) transitions. The results show that the patterning of rare earth-doped phosphors through combining microcontact printing with a Pechini-type sol-gel route has potential for field emission displays (FEDs) applications. 相似文献
225.
Lewis acid/base addition between Ln(NO3)3 · 6H2O (Ln = Pr, Nd, Sm, Eu, Tb and Lu) and H2salen [H2salen = N,N′-ethylenebis(salicylideneimine)] gives rise to an array of coordination polymeric structures. Crystal structural analysis reveals that Salen effectively functions as a bridging ligand in these compounds. The size of the lanthanide ions controls the structures of these Salen lanthanide complexes. Two representative structures with one dimensional and two dimensional topologies, viz. [Pr(H2salen)(NO3)3(CH3OH)2]n (1) and [Ln(H2salen)1.5(NO3)3]n [Ln = Pr (2), Nd (3), Sm (4), Eu (5), Tb (6) and Lu (7)] are reported. Luminescent spectra of complexes 4 and 5 exhibit characteristic metal-centered emission lines. However, the characteristic luminescence of the terbium(III) ion is not observed either in solution or in the solid state of complex 6. 相似文献
226.
Bo Zhen Xinyue Suo Jun Dang Huilan Yue Yanduo Tao Jia-Jia Wang Li Li Ming-Bao Lin Qi Hou Wei-Ping Wang Xiao-Liang Wang Jian-Dong Jiang Teng-Fei Ji 《中国化学快报》2021,32(7):2338-2341
Hyperterpenoid A (1) and B (2), two pairs of enantiomers, with an unprecedented 6/6/4/6/6 polycyclic skeleton, along with one known compoud hypermonone A (3) were isolated from Hypericum beanii. The racemate (±)-1 and (±)-2 were successfully separated into the two optically pure enantiomers (ee ≥ 99%) using a preparative HPLC system. Their absolute configurations were elucidated by extensive spectroscopic analyses and single-crystal X-ray diffraction method. The related plausible biogenetic pathways were presented. Compound 1-3 showed significant neuroprotective activity and potential anti-inflammatory activity. The result that (+)-2 and (-)-2 presented different anti-inflammatory properties, may lead us to new discovery of structure activity relationship between racemates, enantiomers, and diastereomers, as well as further research regarding the binding of drugs to target proteins. 相似文献
227.
Enzyme Design from the Bottom Up: An Active Nickel Electrocatalyst with a Structured Peptide Outer Coordination Sphere 下载免费PDF全文
Dr. Matthew L. Reback Dr. Garry W. Buchko Dr. Brandon L. Kier Bojana Ginovska‐Pangovska Dr. Yijia Xiong Dr. Sheri Lense Dr. Jianbo Hou Dr. John A. S. Roberts Dr. Christina M. Sorensen Dr. Simone Raugei Dr. Thomas C. Squier Dr. Wendy J. Shaw 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(6):1510-1514
Catalytic, peptide‐containing metal complexes with a well‐defined peptide structure have the potential to enhance molecular catalysts through an enzyme‐like outer coordination sphere. Here, we report the synthesis and characterization of an active, peptide‐based metal complex built upon the well‐characterized hydrogen production catalyst [Ni(PPh2NPh)2]2+ (PPh2NPh=1,3,6‐triphenyl‐1‐aza‐3,6‐diphosphacycloheptane). The incorporated peptide maintains its β‐hairpin structure when appended to the metal core, and the electrocatalytic activity of the peptide‐based metal complex (≈100,000 s?1) is enhanced compared to the parent complex ([Ni(PPh2NAPPA)2]2+; ≈50,500 s‐1). The combination of an active molecular catalyst with a structured peptide provides a scaffold that permits the incorporation of features of an enzyme‐like outer‐coordination sphere necessary to create molecular electrocatalysts with enhanced functionality. 相似文献
228.
Facile One‐Pot,One‐Step Synthesis of a Carbon Nanoarchitecture for an Advanced Multifunctonal Electrocatalyst 下载免费PDF全文
Dr. Yang Hou Prof. Junhong Chen 《Angewandte Chemie (International ed. in English)》2014,53(25):6496-6500
A one‐pot/one‐step synthesis strategy was developed for the preparation of a nitrogen‐doped carbon nanoarchitecture with graphene‐nanosheet growth on the inner surface of carbon nanotubes (CNTs). The N‐graphene/CNT hybrids exhibit outstanding electrocatalytic activity for several important electrochemical reactions as a result of their unique morphology and defect structures, such as high but uniform nitrogen doping, graphene insertion into CNTs, considerable surface area, and the presence of iron nanoparticles. The high‐yield synthetic process features high efficiency, low‐cost, straightforward operation, and simple equipment. 相似文献
229.
A Bioorthogonal Small‐Molecule‐Switch System for Controlling Protein Function in Live Cells 下载免费PDF全文
Dr. Peng Liu Abram Calderon Dr. Georgios Konstantinidis Dr. Jian Hou Dipl. Stephanie Voss Dr. Xi Chen Fu Li Soumya Banerjee Dr. Jan‐Erik Hoffmann Christiane Theiss Dr. Leif Dehmelt Dr. Yao‐Wen Wu 《Angewandte Chemie (International ed. in English)》2014,53(38):10049-10055
Chemically induced dimerization (CID) has proven to be a powerful tool for modulating protein interactions. However, the traditional dimerizer rapamycin has limitations in certain in vivo applications because of its slow reversibility and its affinity for endogenous proteins. Described herein is a bioorthogonal system for rapidly reversible CID. A novel dimerizer with synthetic ligand of FKBP′ (SLF′) linked to trimethoprim (TMP). The SLF′ moiety binds to the F36V mutant of FK506‐binding protein (FKBP) and the TMP moiety binds to E. coli dihydrofolate reductase (eDHFR). SLF′‐TMP‐induced heterodimerization of FKBP(F36V) and eDHFR with a dissociation constant of 0.12 μM . Addition of TMP alone was sufficient to rapidly disrupt this heterodimerization. Two examples are presented to demonstrate that this system is an invaluable tool, which can be widely used to rapidly and reversibly control protein function in vivo. 相似文献
230.
Integration of [(Co(bpy)3]2+ Electron Mediator with Heterogeneous Photocatalysts for CO2 Conversion 下载免费PDF全文
An efficient chemical system for electron generation and transfer is constructed by the integration of an electron mediator ([Co(bpy)3]2+; bpy=2,2′‐bipyridine) with semiconductor photocatalysts. The introduction of [Co(bpy)3]2+ remarkably enhances the photocatalytic activity of pristine semiconductor photocatalysts for heterogeneous CO2 conversion; this is attributable to the acceleration of charge separation. Of particular interest is that the excellent photocatalytic activity of heterogeneous catalysts can be developed as a universal photocatalytic CO2 reduction system. The present findings clearly demonstrate that the integration of an electron mediator with semiconductors is a feasible process for the design and development of efficient photochemical systems for CO2 conversion. 相似文献