首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   329篇
  免费   8篇
  国内免费   3篇
化学   231篇
晶体学   2篇
力学   9篇
数学   46篇
物理学   52篇
  2024年   1篇
  2023年   5篇
  2022年   6篇
  2021年   14篇
  2020年   2篇
  2019年   9篇
  2018年   2篇
  2017年   5篇
  2016年   9篇
  2015年   11篇
  2014年   13篇
  2013年   25篇
  2012年   20篇
  2011年   22篇
  2010年   9篇
  2009年   19篇
  2008年   22篇
  2007年   24篇
  2006年   20篇
  2005年   17篇
  2004年   14篇
  2003年   6篇
  2002年   8篇
  2001年   7篇
  2000年   6篇
  1999年   3篇
  1998年   4篇
  1997年   3篇
  1996年   3篇
  1995年   1篇
  1994年   3篇
  1993年   1篇
  1991年   3篇
  1990年   4篇
  1988年   3篇
  1987年   1篇
  1985年   3篇
  1983年   1篇
  1982年   1篇
  1981年   3篇
  1980年   1篇
  1979年   1篇
  1978年   1篇
  1975年   1篇
  1962年   2篇
  1956年   1篇
排序方式: 共有340条查询结果,搜索用时 15 毫秒
61.
Three sets of new and related chiral phospholane and phosphepine ligands have been prepared for Rh-catalyzed enantioselective hydrogenation. The size and substitution pattern of the cyclic monophosphanes were varied. More importantly, the ligands differ in the nature of the heterocyclic group linked to the trivalent phosphorus atom: 2-pyridone or 2-alkoxypyridine. In the corresponding Rh complexes, the pyridone units of two monodentate P ligands can assemble by hydrogen bonding and form chelates. In contrast, synthetic precursors bearing alkoxypyridine appendages are not able to aggregate via intramolecular hydrogen bonds. The nature of self-assembly is dependent on the nature of the P ligand and the solvent used for the hydrogenation (CH2Cl2 vs. MeOH). These features affect the rate of the reaction as well as the enantioselectivity, which varied in the range of 0-99 % ee Complexation studies and DFT calculations were performed to explain these differences.  相似文献   
62.
The stability and bioavailability of anticancer agents, such as gemcitabine, can be increased by forming prodrugs. Gemcitabine is rapidly deaminated to the inactive metabolite (2('),2(')-difluorodeoxyuridine), thus to improve its stability a series of increasingly lipophilic gemcitabine prodrugs linked through the 4-amino group to valeroyl, lauroyl, and stearoyl acyl chains were synthesized. Studies of monolayer properties are important to improve understanding of biological phenomena involving lipid/gemcitabine or lipid/gemcitabine derivative interactions. The interfacial behavior of monolayers constituted by DMPC plus gemcitabine or lipophilic gemcitabine prodrugs at increasing molar fractions was studied at the air/water interface at temperatures below (10 degrees C) and above (37 degrees C) the lipid phase transition. The effect of the hydrophobic chain length of gemcitabine derivatives on the isotherm of pure DMPC was investigated by surface tension measurement, and the results are reported as molar fractions as a function of mean molecular area per molecule. The results show that the compounds interact with DMPC producing mixed monolayers that are subject to an expansion effect, depending on the prodrug chain length. The results give useful hints of the interaction of these prodrugs with biological membranes and increase knowledge on the incorporation site of such compounds, as a function of their lipophilicity, in a lipid carrier; they may lead to improved liposomal formulation design.  相似文献   
63.
The results obtained for the r63 electro‐optic coefficient of B‐doped and undoped KDP (KH2PO4) crystals irradiated with neutrons (including thermalized neutrons) produced by scattering of 30 Mev cyclotron protons on a target of Ta201, are presented and compared to those obtained for non‐irradiated doped and undoped crystals. The B‐doped (H3BO3, Na2B4O7 and Li2B4O7) crystals were obtained by the conventional growth method by temperature decrease with 1 wt % dopant concentration in solution. The thermal neutron flux was around ϕ = 1. 1010 n/cm2 s. Pulses of ∼15 μs long, in damped oscillatory mode (V= 8 kV, τ=1.95 μs) were used for the electro‐optic measurements. A Pockels cell, a photomultiplier, a He‐Ne laser (λ=632.8 nm, 5 mW, linearly polarized) and a Tk 720 A oscilloscope complete the experimental setup. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)  相似文献   
64.
In this work we make an experimental and theoretical investigation of transition probabilities (A) and lifetimes of Xe II. Eighteen Aij's corresponding to the 6p-6d array were measured using a Laser Produced Plasma (LPP) as the spectroscopic source. The ab initio (AI) and Least Square Fitting (LSF) approaches were used to calculate the atomic parameters. Relativistic corrections and Configuration Interaction (CI) effects have been taken into account using the HFR approach described by Cowan. Whereas the AI parameters corresponding to 6p levels are not very affected by CI effects, several of the 6d levels with J=1/2, 3/2and 5/2 making transitions to the fundamental levels 5p5 are affected by CI effects due to both, discrete nd and continuum states, modifying their lifetimes values. An extensive comparison with other measurements and calculations are made. In particular, concerned with branching ratio and forbidden transitions. Received 15 July 1999  相似文献   
65.
66.
67.
In the field of FTIR spectroscopy, the far infrared (FIR) spectral region has been so far less investigated than the mid-infrared (MIR), even though it presents great advantages in the characterization of those inorganic compounds, which are inactive in the MIR, such as some art pigments, corrosion products, etc. Furthermore, FIR spectroscopy is complementary to Raman spectroscopy if the fluorescence effects caused by the latter analytical technique are considered. In this paper, ATR in the FIR region is proposed as an alternative method to transmission for the analyses of pigments. This methodology was selected in order to reduce the sample amount needed for analysis, which is a must when examining cultural heritage materials. A selection of pigments have been analyzed in both ATR and transmission mode, and the resulting spectra were compared with each other. To better perform this comparison, an evaluation of the possible effect induced by the thermal treatment needed for the preparation of the polyethylene pellets on the transmission spectra of the samples has been carried out. Therefore, pigments have been analyzed in ATR mode before and after heating them at the same temperature employed for the polyethylene pellet preparation. The results showed that while the heating treatment causes only small changes in the intensity of some bands, the ATR spectra were characterized by differences in both intensity and band shifts towards lower frequencies if compared with those recorded in transmission mode. All pigments' transmission and ATR spectra are presented and discussed, and the ATR method was validated on a real case study. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   
68.
Collision induced (CI) processes involving hydrogen atoms on a graphite surface are studied quantum mechanically within the rigid, flat surface approximation, using a time-dependent wave packet method. The Eley-Rideal (ER) reaction and collision induced desorption (CID) cross sections are obtained with the help of two propagations which use different sets of coordinates, a "product" and a "reagent" set. Several adsorbate-substrate initial states of the target H atom in the chemisorption well are considered, and CI processes are studied over a wide range of projectile energy. Results show that (i) the Eley-Rideal reaction is the major reactive outcome and (ii) CID cross sections do not exceed 4 A2 and present dynamic thresholds for low values of the target vibrational quantum number. ER cross sections show oscillations at high energies which cannot be reproduced by classical and quasiclassical trajectory calculations. They are related to the vibrational excitation of the reaction products, which is a rather steep decreasing function of the collision energy. This behavior causes a selective population of the low-lying vibrational states and allows the quantization of the product molecular states to manifest itself in a collisional observable. A peak structure in the CID cross section is also observed and is assigned to the selective population of metastable states of the transient molecular hydrogen.  相似文献   
69.
Ethyl- and propyl-prism[6]arenes are obtained in high yields and in short reaction times, independent of the nature and size of the solvent, in the cyclization of 2,6-dialkoxynaphthalene with paraformaldehyde. PrS[6]Et or PrS[6]nPr adopt, both in solution and in the solid state, a folded cuboid-shaped conformation, in which four inward oriented alkyl chains fill the cavity of the macrocycle. On these bases, we proposed that the cyclization of PrS[6]Et or PrS[6]nPr occurs through an intramolecular thermodynamic self-templating effect. In other words, the self-filling of the internal cavity of PrS[6]Et or PrS[6]nPr stabilizes their cuboid structure, driving the equilibrium toward their formation. Molecular recognition studies, both in solution and in the solid state, show that the introduction of guests into the macrocycle cavity forces the cuboid scaffold to open, through an induced-fit mechanism. An analogous conformational change from a closed to an open state occurs during the endo-cavity complexation process of the pentamer, PrS[5]. These results represent a rare example of a thermodynamically controlled cyclization process driven through an intramolecular self-template effect, which could be exploited in the synthesis of novel macrocycles.

Ethyl- and propyl-prism[6]arenes are obtained by an intramolecular thermodynamic self-template effect: the self-filling of the internal cavity stabilizes their cuboid structure, driving the equilibrium toward their formation.  相似文献   
70.
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号