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51.
Cathodic reduction of phenacyl bromides N-acyl hydrazones lead to dimeric 1,4-diaryl-1,4-butanedione di-N-acylhydrazones, which give the corresponding 1-N-acylamino-2,5-diarylpyrroles in good yields. 相似文献
52.
The research on aggregation-induced emission (AIE) has drawn increasing interests in the past decade. With the efforts scientists paid, a variety of AIE systems have been developed, among which the tetraphenylethelene and silole derivatives are the most studied. Development of new AIE systems could further enrich the AIE molecules and promote the development of AIE area. In this communication, we prepared a new AIE system based on 1,2,4,6-tetraphenylpyridinium ions according to the restriction of intramolecular rotation mechanism. These molecules could be facilely synthesized via one-step and one-pot reaction. The ionic AIE-active molecules could find wide application in sensing and optoelectronic areas. 相似文献
53.
S. Ö. Akdemir S. D. Eryilmaz E. Öztekin 《International journal of quantum chemistry》2012,112(6):1585-1591
In this article, extremely simple analytical formulas are obtained for rotational overlap integrals which occur in integrals over two reduced rotation matrix elements. The analytical derivations are based on the properties of the Jacobi polynomials and beta functions. Numerical results and special values for rotational overlap integrals are obtained by using symmetry properties and recurrence relationships for reduced rotation matrix elements. The final results are of surprisingly simple structures and very useful for practical applications. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012 相似文献
54.
55.
János B. Czirok Ákos Tarcsay Pál D. Mezei András Simon László Balázs 《Supramolecular chemistry》2013,25(10-12):722-728
The size limit of substituents allowing O-through-the-annulus rotation of substituted calix[4]arenes was further extended to the propargyloxy group in 24-propargyloxy-25,26,27-tris(N,N-dimethylcarbamoylmethoxy)-p-tert-butylcalix[4]arene by demonstrating its free but slow motion affording equilibrium between the partial cone and 1,2-alternate conformers. The effect of solvent and upper rim substituents R1 on the conformational inversion was investigated by means of 1H NMR. The rotational isomerisation of the parent (R1 = H) analogue could not unambiguously be detected. The experimental results were supported by comprehensive density functional theory studies. 相似文献
56.
Lisa Roeder Philipp Bender Andreas Tschöpe Rainer Birringer Annette M. Schmidt 《Journal of polymer science. Part A, Polymer chemistry》2012,50(24):1772-1781
The mechanical characterization of complex soft matter by quasi-static magnetometry using nanoscopic magnetic probes is demonstrated for model hydrogels doped with two types of elongated magnetic nanoparticles. Chemically crosslinked poly(acrylamide) (PAAm) hydrogels serve as the matrix in which nickel nanorods or weakly magnetized hematite (α-Fe2O3) ellipsoids are embedded as local probes. We investigated the swelling behavior of the ferrogels in order to verify that their equilibrium swelling degree in water is not influenced by the probes, shows a good correlation with the Frenkel–Flory–Rehner model. The proposed magnetomechanical method relies on a correlation between the shear modulus of the PAAm hydrogel matrix and the coercive fields of the corresponding isotropic ferrogels. By extending the Stoner–Wohlfarth model for single-domain blocked magnetic particles by a term for particle rotation in an elastic matrix, information on the shear modulus of the matrix can be obtained. Comparison of the results with the expected relation from rubber elasticity theory illustrates both the general potential as well as the limits of the approach. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 相似文献
57.
Structures of Highly Twisted Amides Relevant to Amide N−C Cross‐Coupling: Evidence for Ground‐State Amide Destabilization
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Dr. Vittorio Pace Prof. Dr. Wolfgang Holzer Guangrong Meng Shicheng Shi Prof. Dr. Roger Lalancette D.Sc. Roman Szostak Prof. Dr. Michal Szostak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14494-14498
Herein, we show that acyclic amides that have recently enabled a series of elusive transition‐metal‐catalyzed N?C activation/cross‐coupling reactions are highly twisted around the N?C(O) axis by a new destabilization mechanism of the amide bond. A unique effect of the N‐glutarimide substituent, leading to uniformly high twist (ca. 90°) irrespective of the steric effect at the carbon side of the amide bond has been found. This represents the first example of a twisted amide that does not bear significant steric hindrance at the α‐carbon atom. The 15N NMR data show linear correlations between electron density at nitrogen and amide bond twist. This study strongly supports the concept of amide bond ground‐state twist as a blueprint for activation of amides toward N?C bond cleavage. The new mechanism offers considerable opportunities for organic synthesis and biological processes involving non‐planar amide bonds. 相似文献
58.
Malek Taher Maghsoodlou Nourollah Hazeri Sayyed Mostafa Habibi Khorasani Aqil Ghulame Shahzadeh Mahmoud Nassiri 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):913-919
Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylenedicarboxylates in the presence of strong NH acids, such as indole and 2-methyl indole, 3-methyl indole, and 5-boromo indole. These stable ylides exist in a solution as a mixture of two geometrical isomers as a result of the restricted rotation around the carbon–carbon partial double bond resulting from the conjugation of the ylide moiety with the adjacent carbonyl group. 相似文献
59.
Effects of Salt on the Orientational Order in Decylammonium Chloride/Ammonium Chloride/Water Systems
The effect of NH4Cl on the temperature dependence of deuterium oxide splitting (water order) and proton line width (surfactant order) in decylammonium chloride (DACl), D2O systems is reported. The molar ratio of DACl to D2O was held constant at .085 and the molar ratio of NH4Cl to D2O was varied from .012 to .029. We find for the above concentration ranges that in the nematic range the relative temperature dependence of the D2O splitting is little affected by changes on salt concentration. The slopes of the proton line widths as a function of temperature decrease with increasing salt concentration. The results are compared with earlier data on salt effects on order obtained with the disodium cromoglycate system. 相似文献
60.
Beam structures undergoing finite deflections and rotations in space have extensive application in the subsea industry particularly for the analysis of holistic systems with larger numbers of mooring and riser components. In using the finite element analysis approach, there is an increasing requirement for large element sizes which preserve accuracy with regard to the coupling of axial, bending and torsion response.The authors outline a method for improving the current state of practice for the analysis of riser systems. The approach draws on the convected coordinates method, Euler–Bernoulli beam theory, the principle of virtual work and the finite element method. Two quasi-rotation measures are developed including a quasi-material rotation definition for rotational deformation relative to the convected axis of a beam and a quasi-space rotation definition to deal with the path dependent nature of rotations in three dimensions.The novel aspect of this work is to relate the rate of change of the quasi-material rotation vector along the beam axis to a linear transformation of the beam axis rate-of-rotation vector through utilising the convected coordinates axes system. In this way, incremental values of quasi-material rotation are directly linked to incremental values of nodal quasi-space rotation and a global Newton–Raphson solution technique for interconnecting beam elements is straightforward to assemble.Furthermore, this leads to accurate definitions of coupled axial, bending and torque response for beams with significant deflection. The approach has particular advantages in the analysis of subsea riser sections. Also, the accuracy of the solution is preserved for a fewer number of elements compared to alternative solutions for computationally sensitive load cases with highly non-linear loading regimes. 相似文献