全文获取类型
收费全文 | 10145篇 |
免费 | 1479篇 |
国内免费 | 810篇 |
专业分类
化学 | 2496篇 |
晶体学 | 330篇 |
力学 | 631篇 |
综合类 | 65篇 |
数学 | 372篇 |
物理学 | 2625篇 |
综合类 | 5915篇 |
出版年
2024年 | 51篇 |
2023年 | 156篇 |
2022年 | 293篇 |
2021年 | 304篇 |
2020年 | 310篇 |
2019年 | 213篇 |
2018年 | 222篇 |
2017年 | 302篇 |
2016年 | 333篇 |
2015年 | 416篇 |
2014年 | 626篇 |
2013年 | 597篇 |
2012年 | 649篇 |
2011年 | 735篇 |
2010年 | 606篇 |
2009年 | 609篇 |
2008年 | 562篇 |
2007年 | 679篇 |
2006年 | 599篇 |
2005年 | 527篇 |
2004年 | 492篇 |
2003年 | 432篇 |
2002年 | 397篇 |
2001年 | 359篇 |
2000年 | 303篇 |
1999年 | 262篇 |
1998年 | 215篇 |
1997年 | 225篇 |
1996年 | 182篇 |
1995年 | 146篇 |
1994年 | 96篇 |
1993年 | 97篇 |
1992年 | 98篇 |
1991年 | 86篇 |
1990年 | 59篇 |
1989年 | 50篇 |
1988年 | 42篇 |
1987年 | 39篇 |
1986年 | 17篇 |
1985年 | 11篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1973年 | 2篇 |
1955年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
181.
Miyasaka H Nezu T Sugimoto K Sugiura K Yamashita M Clérac R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1592-1602
Mn(III)-Ni(II)-Mn(III) linear-type trinuclear complexes bridged by oximate groups were selectively synthesized by the assembly reaction of [Mn2(5-Rsaltmen)2(H2O)2](ClO4)2 (5-Rsaltmen2-=N,N'-(1,1,2,2-tetramethylethylene) bis(5-R-salicylideneiminate); R=Cl, Br) with [Ni(pao)2(phen)] (pao-=pyridine-2-aldoximate; phen=1,10-phenanthroline) in methanol/water: [Mn2(5-Rsaltmen)2Ni(pao)2(phen)](ClO4)2 (R=Cl, 1; R=Br, 2). Structural analysis revealed that the [Mn(III)-ON-Ni(II)-NO-Mn(III)] skeleton of these trimers is in every respect similar to the repeating unit found in the previously reported series of 1D materials [Mn2(saltmen)2Ni(pao)2(L1)2](A)(2) (L(1)=pyridine, 4-picoline, 4-tert-butylpyridine, N-methylimidazole; A=ClO4-, BF4-, PF6-, ReO4-). Recently, these 1D compounds have attracted a great deal of attention for their magnetic properties, since they exhibit slow relaxation of the magnetization (also called single-chain magnet (SCM) behavior). This unique magnetic behavior was explained in the framework of Glauber's theory, generalized for chains of ferromagnetically coupled anisotropic spins. Thus, in these 1D compounds, the [Mn(III)-ON-Ni(II)-NO-Mn(III)] unit was considered as an S(T)=3 anisotropic spin. Direct-current magnetic measurements on 1 and 2 confirm their S(T)=3 ground state and strong uniaxial anisotropy (D/k(B) approximately -2.4 K), in excellent agreement with the magnetic characteristic deduced in the study on the SCM series. The ac magnetic susceptibility of these trimers is strongly frequency-dependent and characteristic of single-molecule magnet (SMM) behavior. The relaxation time tau shows a thermally activated (Arrhenius) behavior with tau0 approximately 1x10(-7) s and Delta(eff)/k(B) approximately 18 K. The effective energy barrier for reversal of the magnetization Delta(eff) is consistent with the theoretical value (21 K) estimated from |D| S2T. The present results reinforce consistently the interpretation of the SCM behavior observed in the [Mn2(saltmen)2Ni(pao)2(L1)2](A)2 series and opens new perspectives to design single-chain magnets. 相似文献
182.
Christian K. Riener Andreas Ebner Alex A. Gall Yuri L. Lyubchenko Hermann J. Gruber 《Analytica chimica acta》2003,479(1):59-75
We have established an easy-to-use test system for detecting receptor-ligand interactions on the single molecule level using atomic force microscopy (AFM). For this, avidin-biotin, probably the best characterized receptor-ligand pair, was chosen. AFM sensors were prepared containing tethered biotin molecules at sufficiently low surface concentrations appropriate for single molecule studies. A biotin tether, consisting of a 6 nm poly(ethylene glycol) (PEG) chain and a functional succinimide group at the other end, was newly synthesized and covalently coupled to amine-functionalized AFM tips. In particular, PEG800 diamine was glutarylated, the mono-adduct NH2-PEG-COOH was isolated by ion exchange chromatography and reacted with biotin succinimidylester to give biotin-PEG-COOH which was then activated as N-hydroxysuccinimide (NHS) ester to give the biotin-PEG-NHS conjugate which was coupled to the aminofunctionalized AFM tip. The motional freedom provided by PEG allows for free rotation of the biotin molecule on the AFM sensor and for specific binding to avidin which had been adsorbed to mica surfaces via electrostatic interactions. Specific avidin-biotin recognition events were discriminated from nonspecific tip-mica adhesion by their typical unbinding force (∼40 pN at 1.4 nN/s loading rate), unbinding length (<13 nm), the characteristic nonlinear force-distance relation of the PEG linker, and by specific block with excess of free d-biotin. The convenience of the test system allowed to evaluate, and compare, different methods and conditions of tip aminofunctionalization with respect to specific binding and nonspecific adhesion. It is concluded that this system is well suited as calibration or start-up kit for single molecule recognition force microscopy. 相似文献
183.
The synthesis of liquid single crystal hydrogels (“LSCH”) in suitable molds offers an innovative concept to realize bifocal contact‐ or intraocular‐lenses. LSCH combine the properties required for applications as bifocal ophthalmic lenses: the soft and water‐containing hydrogel enables oxygen permeation and exhibits high birefringence due to the liquid crystalline phase structure built up by rigid rod‐like amphiphiles. Via a photo‐initiated crosslinking reaction of aqueous solutions of monomeric lyotropic liquid crystalline amphiphiles in the macroscopically ordered liquid crystalline state, we obtain optically uniaxially ordered and transparent LSCH. The orientation process and the phase structure of the anisotropic hydrogel is analyzed by deuterium NMR‐spectroscopy. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
184.
Masaru Kawakami Katherine Byrne Bhavin S Khatri Tom C B McLeish D Alastair Smith 《Chemphyschem》2006,7(8):1710-1716
The viscoelastic properties of single poly(ethylene glycol) (PEG) molecules were measured by analysis of thermally and magnetically driven oscillations of an atomic force microscope (AFM) cantilever/molecule system. The molecular and monomer stiffness and friction of the PEG polymer were derived using a simple harmonic oscillator (SHO) model. Excellent agreement between the values of these two parameters obtained by the two approaches indicates the validity of the SHO model under the experimental regimes and the excellent reproducibility of the techniques. A sharp minimum in the monomeric friction is seen at around 180 pN applied force which we propose is due to a force induced change in the shape of the energy landscape describing the conformational transition of PEG from a helical to a planar state, which in turn affects the timescale of the transition and therefore modifies the measured internal friction. A knowledge of the viscoelastic response of PEG monomers is particularly important since PEG is widely used as a linker molecule for tethering groups of interest to the AFM tip in force spectroscopy experiments, and we show here that care must be exercised because of the force-dependent viscoelastic properties of these linkers. 相似文献
185.
Synthesis and Structure of Silver(II) Tetrafluoroaurate(III) Ag[AuF4]2 Intensive green single crystals of Ag[AuF4]2 can be obtained by heating up micro crystalline Ag[AuF4]2 in autoclaves (p(F2) ~ 200 bar, T ~ 400°C, t ~ 14 d). It crystallizes monoclinic, space group P21/n ? C; (No. 14) with a = 522.3(1), b = 1101.3(3), c = 550.5(2) pm, β = 94.98(3), Z = 2 and is isotypic with Pd[AuF4]2. 相似文献
186.
Stochastic detection of motor protein-RNA complexes by single-channel current recording. 总被引:1,自引:0,他引:1
Yann Astier Denis E Kainov Hagan Bayley Roman Tuma Stefan Howorka 《Chemphyschem》2007,8(15):2189-2194
A label- and immobilization-free approach to detecting the reversible formation of complexes between nucleic acids and proteins at the single-molecule level is described. The voltage-driven translocation of individual oligoribonucleotides through a nanoscale protein pore is observed by single-channel current recordings. The oligoribonucleotide 5'-C25A(25)-3' gives rise to current blockades with an average duration of approximately 0.5 ms. In the presence of the RNA-binding ATPase P4, a viral packaging motor from bacteriophage phi8, longer events of tens to hundreds of milliseconds are observed. Upon addition of ATP the long events disappear, indicating the dissociation of the P4RNA complex. The frequency of events also depends on the concentration of P4 and the length of the oligoribonucleotide, thereby confirming the specificity of the P4RNA events. This study shows that single-channel current recordings can be used to monitor RNA-protein complex formation, thus opening up a new means to examine the motor activity of RNA- or DNA-processing enzymes. 相似文献
187.
Fokin AA Tkachenko BA Gunchenko PA Gusev DV Schreiner PR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):7091-7101
The structures, strain energies, and enthalpies of formation of diamantane 1, triamantane 2, isomeric tetramantanes 3-5, T(d)-pentamantane 6, and D(3d)-hexamantane 7, and the structures of their respective radicals, cations, as well as radical cations, were computed at the B3LYP/6-31G* level of theory. For the most symmetrical hydrocarbons, the relative strain (per carbon atom) decreases from the lower to the higher diamondoids. The relative stabilities of isomeric diamondoidyl radicals vary only within small limits, while the stabilities of the diamondoidyl cations increase with cage size and depend strongly on the geometric position of the charge. Positive charge located close to the geometrical center of the molecule is stabilized by 2-5 kcal mol(-1). In contrast, diamondoid radical cations preferentially form highly delocalized structures with elongated peripheral C-H bonds. The effective spin/charge delocalization lowers the ionization potentials of diamondoids significantly (down to 176.9 kcal mol(-1) for 7). The reactivity of 1 was extensively studied experimentally. Whereas reactions with carbon-centered radicals (Hal)(3)C(*) (Hal=halogen) lead to mixtures of all possible tertiary and secondary halodiamantanes, uncharged electrophiles (dimethyldioxirane, m-chloroperbenzoic acid, and CrO(2)Cl(2)) give much higher tertiary versus secondary selectivities. Medial bridgehead substitution dominates in the reactions with strong electrophiles (Br(2), 100 % HNO(3)), whereas with strong single-electron transfer (SET) acceptors (photoexcited 1,2,4,5-tetracyanobenzene) apical C(4)-H bridgehead substitution is preferred. For diamondoids that form well-defined radical cations (such as 1 and 4-7), exceptionally high selectivities are expected upon oxidation with outer-sphere SET reagents. 相似文献
188.
采用物理涂附法将单链DNA固定到金表面得到ssDNA/Au修饰电极。研究表明,该电极在pH 5,0.2 mol/L NaAc-HAc缓冲底液中,可用于测定水中痕量Pb2 。Pb2 以Pb-DNA络合物的形式吸附在电极上,以示差脉冲伏安法测定Pb2 ,在0.15 V(vsSCE)处有灵敏的氧化峰,其峰电流与Pb2 浓度在5.0×10-8~1.0×10-6mol/L范围内呈良好的线性关系,此法的检测限为2.0×10-8mol/L,该修饰电极的稳定性和抗干扰性都较好。用该电极对饮用水中的Pb进行检测,得到了满意的结果。 相似文献
189.
Twenty-one R2R′2N+X− -type (R=methyl or ethyl, R′=alkyl, X=Br or I) quaternary ammonium (QA) halides have been prepared by using a novel one-pot synthetic route in which a formamide (dimethyl-, diethylformamide, etc.) is treated with alkyl halide in the presence of sodium or potassium carbonate. The formation of QA halides was verified with 1H-NMR, 13C-NMR, MS and elemental analysis. The crystal structures of four QA halides (two bromide and two iodide) were determined using X-ray single crystal diffraction, and the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. The thermal properties of all compounds were studied using TG/DTA and DSC methods. The smallest compounds decomposed during or before melting. The decreasing trend of melting points was observed when the alkyl chain length was increased. The liquid ranges of 120-180 °C were observed for compounds with 5-6 carbon atoms in the alkyl chain. The low melting points and wide liquid ranges suggest potential applicability of these compounds for example as ionic liquids precursors. 相似文献
190.
高硅沸石中二元物系表面扩散系数的预测 总被引:1,自引:0,他引:1
用动力学蒙特卡罗(Kinetic Monte Carlo,KMC)方法模拟客体分子单组分及双组分混合物在高硅沸石(Silicalite)分子筛中的扩散,与分子动力学(Molecular Dynamics,MD)方法的模拟结果及Maxwell-Stefan(M-S)方程计算对比说明KMC方法的合理性,而由真实的体系性质获得正确的跳跃频率值及合适的晶格模型是获得正确计算结果的关键,且一旦由单组分研究获得正确的跳跃频率值及晶格模型,便可直接移用至多组分体系的KMC模拟中。 相似文献