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   245篇
  免费   6篇
  国内免费   1篇
化学   152篇
晶体学   1篇
力学   24篇
数学   27篇
物理学   48篇
  2024年   1篇
  2023年   5篇
  2022年   6篇
  2021年   10篇
  2020年   7篇
  2019年   11篇
  2018年   13篇
  2017年   13篇
  2016年   11篇
  2015年   7篇
  2014年   16篇
  2013年   24篇
  2012年   20篇
  2011年   21篇
  2010年   8篇
  2009年   12篇
  2008年   14篇
  2007年   12篇
  2006年   7篇
  2005年   3篇
  2004年   4篇
  2003年   1篇
  2002年   9篇
  2001年   1篇
  1999年   3篇
  1998年   1篇
  1997年   1篇
  1996年   2篇
  1994年   1篇
  1993年   2篇
  1992年   1篇
  1991年   1篇
  1990年   2篇
  1988年   1篇
  1985年   1篇
排序方式: 共有252条查询结果,搜索用时 0 毫秒
71.
    
The McMurry coupling of a bis-salisaldehyde 3a with methyl linker as the smallest member of its alkyl series is known to give the remarkably lower yield of the corresponding stilbenophanes. The half part of this molecule, unlike bigger analogues, is a good leaving group which affordsthreo isomer of 4H, 4′H–4,4′-bibenzo[d][1,3]dioxine 4 in high diastereoisomeric ratio (99>). A further study showed that the formation of this key by-product is the reason for formation of other by-products, namely, 5a,10b-dihydrobenzofuro[2,3-b]benzofuran 9 and 2-(2,3-dihydrobenzofuran-2-yl)phenol 10. Two reaction pathways for the formation of by-products have been proposed which are responsible for the unusual activity of dialdehyde 3a.  相似文献   
72.
    
The present study describes a novel and very sensitive electrochemical assay for determination of hydrogen peroxide (H2O2) based on synergistic effects of reduced graphene oxide‐ magnetic iron oxide nanocomposite (rGO‐Fe3O4) and celestine blue (CB) for electrochemical reduction of H2O2. rGO‐Fe3O4 nanocomposite was synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X‐ray diffraction (XRD), electrochemical impedance spectroscopy and cyclic voltammetry. Chitosan (Chit) was used for immobilization of amino‐terminated single‐stranded DNA (ss‐DNA) molecules via a glutaraldehyde (GA) to the surface of rGO‐Fe3O4. The MTT (3‐(4,5‐Dim ethylt hiazol‐2‐yl)‐2,5‐diphenylt etrazolium bromide) results confirmed the biocompatibility of nanocomposite. Experimental parameters affecting the ss‐DNA molecules immobilization were optimized. Finally, by accumulation of the CB on the surface of the rGO‐Fe3O4‐Chit/ssDNA, very sensitive amperometric H2O2 sensor was fabricated. The electrocatalytic activity of the rGO‐Fe3O4‐Chit/DNA‐CB electrode toward H2O2 reduction was found to be very efficient, yielding very low detection limit (DL) of 42 nM and a sensitivity of 8.51 μA/μM. Result shows that complex matrices of the human serum samples did not interfere with the fabricated sensor. The developed sensor provided significant advantages in terms of low detection limit, high stability and good reproducibility for detection of H2O2 in comparison with recently reported electrochemical H2O2 sensors.  相似文献   
73.
Cell encapsulation represents an alternative nonviral technique to treat multiple diseases, leading to a reduction or even absence of administration of immunosuppressants. Hydrogels have been introduced as novel materials suitable for cell encapsulation. This study involves agarose–gelatin blend hydrogels with four different weight percentage ratios (100:0, 75:25, 50:50, 25:75) of agarose to gelatin. Prepared blend hydrogels were assessed in terms of rheological behavior (gel point by using complex viscosity), cell attachment (hemocytometer), cell viability and cytotoxicity (3-(3,4-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliium bromide, MTT assay), and mechanical and integral stability (Bradford test and shear force rupture assay, respectively). Based on the obtained rheological experimental results, the sol-gel transition point for 50:50 was in the physiological condition range (35°C–37°C). The percent of nonattached cells on the surface of the hydrogel decreased from 92% for the 100:0 sample to 46.3% for the 50:50 sample, and the cell viability was more than 95%. A good structural integrity was achieved for samples with weight ratio of 50:50; 20.195% gelatin was released during the 24 h in phosphate buffer solution at 25°C and the mechanical stability of agarose–gelatin microcapsules under shear force were improved about 14% rather than pure agarose microcapsule.  相似文献   
74.
Aurora, commonly seen in the polar sky, is a ubiquitous phenomenon occurring on Earth and other solar system planets. The colorful emissions are caused by electron beams hitting the upper atmosphere, after being accelerated by quasistatic electric fields at 1-2 R(E) altitudes, or by wave electric fields. Although aurora was studied by many past satellite missions, Cluster is the first to explore the auroral acceleration region with multiprobes. Here, Cluster data are used to determine the acceleration potential above the aurora and to address its stability in space and time. The derived potential comprises two upper, broad U-shaped potentials and a narrower S-shaped potential below, and is stable on a 5 min time scale. The scale size of the electric field relative to that of the current is shown to depend strongly on altitude within the acceleration region. To reveal these features was possible only by combining data from the two satellites.  相似文献   
75.
In this paper the meshless Local Multi Quadrics-based Differential Quadrature (MQ-DQ) method is applied to obtain the electric field distribution for different applicable irregular geometries. This method is the combination of Differential Quadrature approximation of derivatives and function approximation of MQ-Radial Basis Function (RBF). Three different geometries with irregular boundaries are considered and the obtained results are compared with those gained by Finite Element (FE) solutions achieved by COMSOL commercial code. Outcomes prove that current technique is in very good agreement with FEM and this fact that MQ-DQ method is an accurate and flexible method in solution of electrostatic equations.  相似文献   
76.
Summary. The oxidation of arenes and sulfides by potassium permanganate was accomplished in good yields under solvent free and heterogeneous conditions when manganese(II) sulfate is used as a solid support. After extraction of the organic products, the inorganic products can be reoxidized to permanganate. This result is important because it provides an approach to oxidation reactions that is, in theory, infinitely sustainable.  相似文献   
77.
Summary. A variety of 1,3-diyne compounds are prepared in a solvent-free reaction on KF/alumina in the presence of catalytic amounts of Cu(OAc)2·H2O with up to 96% yields at room temperature.  相似文献   
78.
Cytidine triphosphate synthetase (CTPS) catalyzes the formation of cytidine triphosphate from glutamine, uridine-5'-triphosphate (UTP), and adenosine-5'-triphosphate. Inhibitors of CTPS are of interest because of their potential as therapeutic agents. One approach to potent enzyme inhibitors is to use analogues of high energy intermediates formed during the reaction. The CTPS reaction proceeds via the high energy intermediate UTP-4-phosphate (UTP-4-P). Four novel analogues of uridine-4-phosphate (U-4-P) and 3-deazauridine-4-phosphate (3-deazaU-4-P) were synthesized in which the labile phosphate ester oxygen was replaced with a methylene and difluoromethylene group. The methylene analogue of U-4-P, compound 1, was prepared by a reaction of the sodium salt of tert-butyl diethylphosphonoacetate with protected, 4-O-activated uridine followed by acetate deprotection and decarboxylation. It was found that this compound undergoes relatively facile dephosphonylation presumably via a metaphosphate intermediate. The difluoromethylene derivative, compound 2, was prepared by electrophilic fluorination of protected 1. This compound was stable and did not undergo dephosphonylation. Synthesis of the methylene analogue of 3-deazaU-4-P, compound 3, was achieved by ribosylation of protected 4-(phosphonomethyl)-2-hydroxypyridine. Electrophilic fluorination was also employed in the preparation of protected 4-(phosphonodifluoromethyl)-2-hydroxypyridine which was used as the key building block in the synthesis of difluoro derivative 4. These compounds represent the first examples of a nucleoside in which the base has been chemically modified with a methylene or difluormethylenephosphonate group.  相似文献   
79.
This room-temperature Darzens condensation of α-chloroacetophenone with various aromatic aldehydes mediated by [bmim][BF4] ionic liquid in the presence of sodium tert-butoxide resulted in the sole formation of good to excellent yields of trans-α,β-epoxy ketones in short time periods. In contrast, tert-butyl 2-chloroacetate underwent Darzens reactions with aldehydes giving mixtures of both cis and trans products with low selectivity. In all reactions, the ionic liquid was recovered and reused in the subsequent reactions without significant loss of activity.  相似文献   
80.
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