全文获取类型
收费全文 | 4652篇 |
免费 | 236篇 |
国内免费 | 39篇 |
专业分类
化学 | 3219篇 |
晶体学 | 24篇 |
力学 | 116篇 |
数学 | 547篇 |
物理学 | 606篇 |
无线电 | 415篇 |
出版年
2023年 | 51篇 |
2022年 | 49篇 |
2021年 | 91篇 |
2020年 | 115篇 |
2019年 | 111篇 |
2018年 | 85篇 |
2017年 | 65篇 |
2016年 | 150篇 |
2015年 | 132篇 |
2014年 | 172篇 |
2013年 | 252篇 |
2012年 | 323篇 |
2011年 | 382篇 |
2010年 | 179篇 |
2009年 | 152篇 |
2008年 | 352篇 |
2007年 | 335篇 |
2006年 | 334篇 |
2005年 | 285篇 |
2004年 | 232篇 |
2003年 | 201篇 |
2002年 | 169篇 |
2001年 | 39篇 |
2000年 | 36篇 |
1999年 | 44篇 |
1998年 | 39篇 |
1997年 | 46篇 |
1996年 | 63篇 |
1995年 | 37篇 |
1994年 | 31篇 |
1993年 | 28篇 |
1992年 | 25篇 |
1991年 | 27篇 |
1990年 | 28篇 |
1989年 | 16篇 |
1988年 | 13篇 |
1987年 | 15篇 |
1986年 | 18篇 |
1985年 | 25篇 |
1984年 | 28篇 |
1983年 | 14篇 |
1982年 | 15篇 |
1981年 | 15篇 |
1980年 | 19篇 |
1979年 | 10篇 |
1978年 | 22篇 |
1977年 | 12篇 |
1976年 | 16篇 |
1975年 | 9篇 |
1974年 | 10篇 |
排序方式: 共有4927条查询结果,搜索用时 93 毫秒
801.
Angell Y Chen D Brahimi F Saragovi HU Burgess K 《Journal of the American Chemical Society》2008,130(2):556-565
Piperidine-functionalized, 1,4-disubstituted-1,2,3-triazoles of generic structure 1 were conceived as "minimalist" mimics of peptidic beta-turn structures. Key features of these molecules include (i) the possibility of incorporating amino acid side chains corresponding to many of the protein amino acids; (ii) a close correspondence of separations of these side chains to i + 1 to i + 2 residues in turns; (iii) facile adjustment of the side-chain vectors on docking while only influencing two critical degrees of freedom; and (iv) some electrostatic polarity. Fifteen monomers of this type were made via copper-mediated cycloaddition reactions. Solution-phase methodologies were devised to assemble these monomers into bivalent compounds in high purity states (typically >85%) so that they could be used in first-pass biological assays without further purification. The skeleton for forming these bivalent compounds is triazine-based. There is a third site which allowed for introduction of a fluorescent label (library of compounds 2) or an alkyne-functionalized triethylene glycol chain (library of compounds 3) included to promote water-solubility and to allow incorporation of probes via copper-mediated cycloaddition reactions. In the event, two 135-membered libraries were prepared, one consisting of compounds 2 and the other of 3. No protecting groups or coupling agents were required; these attributes of the method were important to allow most of the products to be obtained in over 85% purities. The fluorescein-tagged library of compounds 2 was screened in a fluorescence-activated cell sorting (FACS) assay using cells transfected to overexpress one of the following neurotrophin receptors: TrkA, TrkC, and p75. Preliminary findings indicate four compounds 2gm, 2gn, 2gi, and 2gj bound the TrkA receptor selectively; all of these contain a threonine-lysine turn mimic. Thus, a pharmacological probe for the TrkA receptor has been developed. 相似文献
802.
Frankowski KJ Golden JE Zeng Y Lei Y Aubé J 《Journal of the American Chemical Society》2008,130(18):6018-6024
A tandem Diels-Alder/azido-Schmidt reaction sequence provides rapid access to the core skeleton shared by several Stemona alkaloids including stenine, neostenine, tuberostemonine, and neotuberostemonine. The discovery and evolution of inter- and intramolecular variations of this process and their applications to total syntheses of (+/-)-stenine and (+/-)-neostenine are described. The stereochemical outcome of the reaction depends on both substrate type and reaction conditions, enabling the preparation of both (+/-)-stenine and (+/-)-neostenine from the same diene/dienophile combination. 相似文献
803.
Graber S Doyle K Neuburger M Housecroft CE Constable EC Costa RD Ortí E Repetto D Bolink HJ 《Journal of the American Chemical Society》2008,130(45):14944-14945
A new iridium(III) complex showing intramolecular interligand pi-stacking has been synthesized and used to improve the stability of single-component, solid-state light-emitting electrochemical cell (LEC) devices. The pi-stacking results in the formation of a very stable supramolecularly caged complex. LECs using this complex show extraordinary stabilities (estimated lifetime of 600 h) and luminance values (average luminance of 230 cd m-2) indicating the path toward stable ionic complexes for use in LECs reaching stabilities required for practical applications. 相似文献
804.
We summarized both advantages and disadvantages of different light modulators used in cw-CRDS experiments. For the first time, we introduce the use of a semiconductor optical amplifier (SOA) as light modulator in cw-CRDS. A direct comparison of the sensitivity realized on the same instrument using an SOA as modulator with use of an acousto-optic modulator (AOM) has been made. It is found that the SOA has larger extinction ratio (81 dB) than the AOM. For our instrument, with single-shot initial signal-to-noise ratio of 1400:1, these two modulators are found giving equivalent sensitivity. 相似文献
805.
Application of MELC and MEEKC for the Analysis of Paracetamol and Related Impurities in Suppositories 总被引:1,自引:0,他引:1
Rapid MELC and MEEKC methods were developed for paracetamol suppository assay. MELC methods for paracetamol analysis and for separation of paracetamol and its impurities were previously reported. In this study, further development of MEEKC methods and a MELC method using anionic and cationic microemulsions gave excellent validation results for paracetamol content in suppositories. SDS Microemulsion instability resulted in poor reproducibility for impurity separations using gradient elution. A novel isocratic CTAB MELC method achieved reproducible separation of paracetamol and its impurities at 0.1% levels. MEEKC methods using SDS and CTAB microemulsions resolved all of the impurities however detection at 0.1% levels was not possible. These methods gave significant benefits in terms of reduced sample pre-treatment requirements. CTAB microemulsions had greater solubilising power than their SDS equivalent and were more stable due to their longer alkyl chain length. 相似文献
806.
Daiguebonne C Kerbellec N Guillou O Bünzli JC Gumy F Catala L Mallah T Audebrand N Gérault Y Bernot K Calvez G 《Inorganic chemistry》2008,47(9):3700-3708
Reaction in water between rare earth ions (Ln = Y, La-Tm, except Pm) and the sodium salt of terephthalic acid leads to a family of lanthanide-based coordination polymers of general formula [Ln2(C8H4O4)3(H2O)4] n with Ln = La-Tm or Y. The isostructurality of the compounds with the previously reported Tb-containing polymer is ascertained on the basis of their X-ray powder diffraction diagrams. The coordination water molecules can be reversibly removed without destroying the crystal structure for compounds involving one of the lighter lanthanide ions (La-Eu). For compounds involving one of the heavier lanthanide ions (Tb-Tm) or yttrium, a structural change occurs during the drying process. X-ray diffraction data show this new anhydrous phase corresponding to the linking of pairs of Er(III) ions through mu-carboxylate bridges. Porosity profiles calculated for the anhydrous phases of Tb(III) and Er(III) show the presence of channels with very small sections. The luminescent properties of all the compounds have been recorded and the two most luminescent polymers, namely, the europium- and the terbium-containing ones, have been studied in more detail. Tb(III)-containing compounds display large quantum yields, up to 43%. Polyvinylpyrrolidone nanoparticles doped with [Ln2(C8H4O4)3(H2O)4] n (Ln = Eu, Tb, Er) have also been synthesized and characterized. The encapsulation of the coordination polymers results in somewhat reduced luminescence intensities and lifetime, but the nanoparticles can be dispersed in water and remain unchanged in this medium for more than 20 h. 相似文献
807.
The molecular structure of sodium ethylmercury thiosalicylate (also known as thimerosal and Merthiolate) and related arylthiolate mercury alkyl compounds, namely PhSHgMe and PhSHgEt, have been determined by single crystal X-ray diffraction. (1)H NMR spectroscopic studies indicate that the appearance of the (199)Hg mercury satellites of the ethyl group of thimerosal is highly dependent on the magnetic field and the viscosity of the solvent as a consequence of relaxation due to chemical shift anisotropy. 相似文献
808.
Johansson FB Bond AD Nielsen UG Moubaraki B Murray KS Berry KJ Larrabee JA McKenzie CJ 《Inorganic chemistry》2008,47(12):5079-5092
A matched set of dinuclear cobalt complexes with II-II, II-III, and III-III oxidation states have been prepared and structurally characterized. In [(bpbp)Co2(O2P(OPh)2)2]n+ ( n = 1, 2, or 3; bpbp(-) = 2,6-bis(( N,N'-bis-(2-picolyl)amino)-methyl)-4-tertbutylphenolato), the nonbonded Co...Co separations are within the range 3.5906(17) to 3.7081(11) angstroms, and the metal ions are triply bridged by the phenolate oxygen atom of the heptadentate dinucleating ligand and by two diphenylphosphate groups. The overall structures and geometries of the complexes are very similar, with minor variations in metal-ligand bond distances consistent with oxidation state assignments. The CoIICoIII compound is a valence-trapped Robin-Day class II complex. Solid state 31P NMR spectra of the diamagnetic CoIIICoIII (3) and paramagnetic CoIICoIII (2) and CoIICoII (1) complexes show that 31P isotropic shifts broaden and move downfield by about 3000 ppm for each increment in oxidation state. Cyclic voltammetry corroborates the existence of the CoIICoII, CoIICoIII, and CoIIICoIII species in solution. The redox changes are not reversible in the applied scanning timescales, indicating that chemical changes are associated with oxidation and reduction of the cobalt centers. An investigation of the spectroscopic properties of this series has been carried out for its potential usefulness in analyses of the related spectroscopic properties of the dicobalt metallohydrolases. Principally, magnetic circular dichroism (MCD) has been used to determine the strength of the magnetic exchange coupling in the CoIICoII complex by analysis of the variable-temperature variable-field (VTVH) intensity behavior of the MCD signal. The series is ideal for the spectroscopic determination of magnetic coupling since it can occur only in the CoIICoII complex. The CoIICoIII complex contains a nearly isostructural CoII ion, but since CoIII is diamagnetic, the magnetic coupling is switched off, while the spectral features of the CoII ion remain. Analysis of the MCD data from the CoIICoIII complex has been undertaken in the theoretical context of a 4T1g ground-state of the CoII ion, initially in an octahedral ligand field that is split by both geometric distortion and zero-field splitting to form an isolated doublet ground state. The MCD data for the CoIICoII pair in the [(bpbp)Co2(O2P(OPh)2)2]+ complex were fitted to a model based on weak antiferromagnetic coupling with J = -1.6 cm (-1). The interpretation is confirmed by solid state magnetic susceptibility measurements. 相似文献
809.
Blanchet V Raffael K Turri G Chatel B Girard B Garcia IA Wilkinson I Whitaker BJ 《The Journal of chemical physics》2008,128(16):164318
Pump-probe photoionization has been used to map the relaxation processes taking place from highly vibrationally excited levels of the S(2) state of azulene, populated directly or via internal conversion from the S(4) state. Photoelectron spectra obtained by 1+2(') two-color time-resolved photoelectron imaging are invariant (apart from in intensity) to the pump-probe time delay and to the pump wavelength. This reveals a photoionization process which is driven by an unstable electronic state (e.g., doubly excited state) lying below the ionization potential. This state is postulated to be populated by a probe transition from S(2) and to rapidly relax via an Auger-like process onto highly vibrationally excited Rydberg states. This accounts for the time invariance of the photoelectron spectrum. The intensity of the photoelectron spectrum is proportional to the population in S(2). An exponential energy gap law is used to describe the internal conversion rate from S(2) to S(0). The vibronic coupling strength is found to be larger than 60+/-5 microeV. 相似文献
810.
Scroll waves are three-dimensional excitation patterns that rotate around one-dimensional space curves. Typically these filaments are closed loops or end at the system boundary. However, in excitable media with anomalous dispersion, filaments can be pinned to the wake of traveling wave pulses. This pinning is studied in experiments with the 1,4-cyclohexanedione Belousov-Zhabotinsky reaction and a three-variable reaction-diffusion model. We show that wave-pinned filaments are related to the coexistence of rotating and translating wave defects in two dimensions. Filament pinning causes a continuous expansion of the total filament length. It can be ended by annihilating the pinning pulse in a frontal wave collision. Following such an annihilation, the filament connects itself to the system boundary. Its postannihilation shape that is initially the exposed rim of the scroll wave unwinds continuously over numerous rotation periods. 相似文献