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661.
On-site verification of the chemical weapon convention (CWC) requires provision for the detection and identification of alkyl phosphonic acids as well as some organic acids that are amenable to GC-MS only after derivatisation. Various derivatisation methods have been used for the identification of these acids and for many cases the methyl derivatives are less prone to artifacts possibly leading to false positive identification. Methylation with diazomethane is widely used but, especially for on-site analysis it has limitation due to the potential explosive and health hazards. Other methylation procedures like trimethylsilyldiazomethane (TMSD), thermally assisted methylation (TAM) by trimethylphenylammonium hydroxide (TMPAH) and trimethylsulfonium hydroxide (TMSH) are evaluated. Data for methylation for the alkyl alkylphosphonic acids, alkylphosphonic acids and benzilic acid are reported. In addition, TAM followed by the silylation in the same sample without any additional sample preparation is also reported. Several parameters such as solvent, temperature, amount of reagents, time, etc. were studied. The two commercially available reagents namely, TMPAH and TMSH for TAM and subsequent silylation were evaluated. The LOD with TMPAH was below 0.5 ng per injection since all of the acids were detected by GC-MS with the S/N of >3 in full scan mode by AMDIS and their inter day relative standard deviation was from 4.7% to 10.8%. 相似文献
662.
Tothadi S Mukherjee A Desiraju GR 《Chemical communications (Cambridge, England)》2011,47(44):12080-12082
2- and 5-methylresorcinol form co-crystals with 4,4'-bipyridine in which some of the bipyridine molecules are loosely bound. These molecules can be replaced with other molecules of a similar shape and size to give a general method for the engineering of a ternary co-crystal. 相似文献
663.
Gautam C. Patil Pallavi Raote M.B. Sai Prasad J.P. Nilaya D.J. Biswas 《Optics Communications》2011,284(8):2189-2191
The possibility of triggering a switch-less TE gas laser has been experimentally explored. To this end, the parallel spark preioniser array that functions as a switch of the switch-less laser has been optically triggered by transporting UV photons from the triggering discharge by means of an optical fiber. The maximum triggerable range was studied as a function of the number of spark channels in the triggering discharge and the gas composition in the triggered parallel spark preioniser. 相似文献
664.
In this paper, we studied the optical and physical properties of electrochemically prepared porous silicon layers. The atomic force microscopy analysis showed that the etching depth, pore diameter and surface roughness increase as the etching time increased from 30 to 50 mA/cm2. By tuning two current densities J1 = 50 mA/cm2 and J2 = 30 mA/cm2, two samples of 1D porous silicon photonic crystals were fabricated. The layered structure of 1D photonic crystals has been confirmed by scanning electron microscopy measurement which showed white and black strips of two distinct refractive index layers. Finally, the measured reflectance spectra of 1D porous silicon photonic crystals were compared with simulated results. 相似文献
665.
Biswajit Das Kinshuk Banerjee Gautam Gangopadhyay 《Journal of mathematical chemistry》2013,51(2):588-602
In this work we have shown how an applied mechanical force affects an oligomeric enzyme kinetics in a chemiostatic condition where the statistical characteristics of random walk of the substrate molecules over a finite number of active sites of the enzyme plays important contributing factors in governing the overall rate and nonequilibrium thermodynamic properties. The analytical results are supported by the simulation of single trajectory based approach of entropy production using Gillespie’s stochastic algorithm. This microscopic numerical approach not only gives the macroscopic entropy production from the mean of the distribution of entropy production which depends on the force but also a broadening of the distribution by the applied mechanical force, a kind of power broadening. In the nonequilibrium steady state (NESS), both the mean and the variance of the distribution increases and then saturates with the rise in applied force corresponding to the situation when the net rate of product formation reaches a limiting value with an activationless transition. The effect of the system-size and force on the entropy production distribution is shown to be constrained by the detailed fluctuation theorem. 相似文献
666.
Naveen Gautam Yogesh Dixit Rahul Dixit Sudesh Kumar Gupta Dinesh Chand Gautam 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1127-1136
Abstract 4H-1,4-benzothiazines were prepared by condensation followed by oxidative cyclization of substituted 2-aminobenzenethiols with β-diketones in dimethylsulfoxide. On refluxing with 30% hydrogen peroxide in glacial acetic acid, 4H-1,4-benzothiazines yielded 4H-1,4-benzothiazine-1,1-dioxides. Structural evaluation has been done by spectral and elemental analysis. All the synthesized compounds were evaluated for their antibacterial and antifungal activity and all these have shown moderate to high activity against the test microbes. Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional text, figures and tables. 相似文献
667.
A special class of engineered copolymers, called ionomers, comprising both electrically neutral repeating units and a fraction of ionized units was melt blended to weather resistant acrylonitrile/styrene/acrylate (ASA) terpolymer for improved electrical conductivity, heat sealing ability, direct adhesion to several polymers, glass and metals without affecting the aesthetics and colorability of ASA. The similar chemical nature of one of the components of each blended materials viz. acrylate rubber in ASA and acrylic acid of Na‐ionomer in addition to the presence of ionic crosslinking within Na‐ionomer, polar acrylonitrile group in ASA affects chain dynamics as compared to neat polymers. In this context, dynamic rheological properties, DMA properties, creep behavior and DSC of the newly developed ASA/Na‐ionomer blends were analyzed. Based on Na‐ionomer content, the blend system either forms “mushroom” or “brush” type conformation and formation of ionic crosslinking in “brush regime” leads to three tiers Caylay tree conformation. The different chain topology resulted into characteristic loss modulous (G″) curve during stress relaxation process. The chain conformation as well as ionic crosslinking and ion–dipole interaction between the blend components also affected DSC endotherm peak and glass transition temperature. The tan δ peak temperature from DMA also revealed the similar observation. The creep compliance of the blends was dependent on Na‐ionomer content and with temperature. The Findley model analysis of creep compliance suggested that the creep compliance was depended on Na‐ionomer content and ionic crosslinking controlled the creep. The findings can be utilized to design weather resistant smart polymer using suitable filler system. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
668.
Moumita Rana R. Bharathanatha Reddy Bibhuti Bhusan Rath Dr. Ujjal K. Gautam 《Angewandte Chemie (International ed. in English)》2014,53(49):13523-13527
A supramolecular crystallization‐based approach has been developed for the shape‐dependent separation of geometrical isomers under near‐ambient conditions. Difficulties to separate such isomers arise because of their very similar physical properties. The present approach relies on the ability of C60 to preferentially form solvate crystals with molecules of a specific geometry. Subsequently, these molecules are released upon mild heating to regenerate pure C60. By taking isomers of xylene and trimethylbenzene (TMB) as examples, we show that one of the isomers can be extracted from the rest with very high purity. To separate TMB isomers, a new C60–1,3,5‐TMB solvate was developed, which led to the isolation of isomer purities greater than 99.6 %. Versatility, a low operating temperature of approximately 100 °C, a separation efficiency of more than 10 weight % of C60 per cycle, and reagent recyclability makes this a promising molecular shape‐sorting approach. 相似文献
669.
Thai Son Dang Sanjay Kumar Palit Sayan Mukherjee Thang Manh Hoang Santo Banerjee 《The European physical journal. Special topics》2016,225(1):159-170
We investigate the complexity of a hyperchaotic dynamical system perturbed by noise and various nonlinear speech and music signals. The complexity is measured by the weighted recurrence entropy of the hyperchaotic and stochastic systems. The synchronization phenomenon between two stochastic systems with complex coupling is also investigated. These criteria are tested on chaotic and perturbed systems by mean conditional recurrence and normalized synchronization error. Numerical results including surface plots, normalized synchronization errors, complexity variations etc show the effectiveness of the proposed analysis. 相似文献
670.
Chandra S Gautam A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,70(5):1001-1005
Nickel(II) and copper(II) complexes are synthesized with a novel tetradentate macrocyclic ligand, i.e. 2,6,12,16,21,22-hexaaza;3,5,13,15-tetraphenyltricyclo[15,3,1,1(7-11)] docosa;1(21),2,5,7,9,11(22),12,15,17,19-decaene (L) and characterized by the elemental analysis, magnetic susceptibility measurements, mass, (1)H NMR, IR, electronic and EPR spectral studies. All the complexes are non-electrolytic in nature. Thus, these may be formulated as [M(L)X(2)] [M=Ni(II), Cu(II) and X=Cl(-), NO(3)(-) and (1/2)SO(4)(2-)]. Ni(II) and Cu(II) complexes show magnetic moments corresponding to two and one unpaired electron, respectively. On the basis of IR, electronic and EPR spectral studies an octahedral geometry has been assigned for Ni(II) and tetragonal geometry for Cu(II) complexes. 相似文献