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   1553篇
  免费   64篇
  国内免费   5篇
化学   1151篇
晶体学   15篇
力学   54篇
数学   83篇
物理学   319篇
  2024年   7篇
  2023年   10篇
  2022年   44篇
  2021年   33篇
  2020年   47篇
  2019年   58篇
  2018年   51篇
  2017年   78篇
  2016年   62篇
  2015年   58篇
  2014年   56篇
  2013年   142篇
  2012年   112篇
  2011年   129篇
  2010年   58篇
  2009年   59篇
  2008年   63篇
  2007年   67篇
  2006年   58篇
  2005年   40篇
  2004年   41篇
  2003年   24篇
  2002年   27篇
  2001年   7篇
  2000年   13篇
  1999年   9篇
  1998年   6篇
  1997年   9篇
  1996年   6篇
  1995年   8篇
  1994年   12篇
  1993年   14篇
  1992年   14篇
  1991年   17篇
  1990年   11篇
  1989年   12篇
  1988年   7篇
  1987年   14篇
  1986年   8篇
  1985年   16篇
  1984年   14篇
  1983年   14篇
  1981年   15篇
  1980年   11篇
  1979年   15篇
  1978年   10篇
  1977年   10篇
  1976年   4篇
  1974年   5篇
  1973年   4篇
排序方式: 共有1622条查询结果,搜索用时 15 毫秒
61.
62.
Well-defined four-arm star poly(?-caprolactone)-block-poly(cyclic carbonate methacrylate) (PCL-b-PCCMA) copolymers were synthesized by combining ring-opening polymerization (ROP) with atom transfer radical polymerization (ATRP). First, a four-arm poly(?-caprolactone) (PCL) macroinitiator [(PCL-Br)4] was prepared by the ROP of ?-CL catalyzed by stannous octoate at 110°C in the presence of pentaerythritol as the tetrafunctional initiator followed by esterification with 2-bromoisobutyryl bromide. The sequential ATRP of CCMA monomer was carried out by using the (PCL-Br)4 tetrafunctional macroinitiator (MI) and in the presence of CuBr/2, 2′-bipyridyl system in DMF at 80°C with [(MI)]:[CuBr]:[bipyridyl] = 1:1:3 to yield block polymers with controlled molecular weights (Mn (NMR) = 10700 to 27300 g/mol) by varying block lengths and with moderately narrow polydispersities (Mw/Mn = 1.2–1.4). Block copolymers with different PCL: PCCMA copolymer composition such as 50:50, 70:30 and 74:26 were prepared with good yields (48-74%). All these block copolymers were well characterized by NMR, FTIR and GPC and tested their thermal properties by DSC and TGA.  相似文献   
63.

A series of terbutaline sulphate drug incorporated polyvinyl alcohol (PVA) matrix films were produced by the solvent evaporation method. The effect of xanthan gum and plasticizers (propylene glycol and dibutyl phthalate) on the rate and amount of drug diffusion from PVA membrane across the hydrated cellophane membrane has been evaluated, using an open glass diffusion‐tube. The obtained films were clear, smooth and flexible having sufficient mechanical strength. The mechanical performance of the dry PVA films with xanthan gum and plasticizers were also ascertained. Polyvinyl alcohol‐xanthan gum blends showed a high rate of drug release compared to that of polyvinyl alcohol film alone. Among the two plasticizers employed, propylene glycol showed better permeability. Among different formulations studied, the formulation PVA/xanthan gum/propylene glycol (F7) was found to be an optimized composition for efficient transdermal delivery of the model drug, terbutaline sulphate. The mechanism of drug diffusion has been evaluated using the Peppas model. Stability studies carried out on polymer‐drug formulations revealed that the drug is stable at 40°C and 75% RH for a period of 6 weeks.  相似文献   
64.
Crystalline films (thickness ~1 μm) of Prussian blue-based molecular magnets, synthesized using electrochemical method at two different reduction potentials ?0.5 and ?0.9 V, result into K0.1CrII 1.45[CrIII(CN)6]?·?mH2O (film 1) and K0.8CrII 1.1[CrIII(CN)6]?·?mH2O (film 2), respectively. The structural and magnetic properties of such films are investigated using atomic force microscopy (AFM), X-ray diffraction (XRD), infrared (IR) spectroscopy, and dc magnetization measurements. The film morphology, examined using AFM, shows uniformly distributed triangular crystallites over the substrate surface. The presence of CrIII–C≡N–CrII sequence, in the range of 1,900 to 2,300 cm?1 in IR spectra, confirms formation of Prussian blue analogues. The XRD results reveal information about the crystalline nature of the films and the relative intensities of the Bragg peaks change with the K+ ions. The exchange interaction between Cr ions through C≡N ligand confirms that the electron transfer from C≡N molecule to Cr ions is ferrimagnetic in nature. The high Curie temperatures (T C) are found to be ~195 and ~215 K for film 1 and film 2, respectively. The higher value of T C is attributed to the inclusion of more K+ ions for film 2, resulting decreases in the CrIII(C≡N)6 vacancies and increases in the number of nearest neighbors of CrII ions. The branching in the zero field-cooled and field-cooled magnetization data below Curie temperature is explained in terms of kinetic behavior of magnetic domains with different cooling conditions and the presence of water molecule vacancies in the lattice.  相似文献   
65.
66.
The Biginelli-type compounds 4,5,8a-triarylhexahydropyrimido[4,5-d]pyrimidine-2,7(1H,3H)-diones were synthesized by a one-pot three-component reaction using sulfated tin oxide as a reusable catalyst. This method has the advantages of high yields, short reaction time, simple starting materials and reusability of catalyst for several times.  相似文献   
67.
3′O-silylated derivatives of 5′-O-DMT-2′deoxynucleoside (2) were synthesized in high yield by reaction of 5′-O-DMT-2′-deoxynucleosides (1) with tert-butyl dimethylsilylchloride using sodium hydride, benzyltriethylammonlum chloride [TEBA] and a catalytic amount of dibenzo-[18]-crown-6 [DB-18-C-6] or 15-crown-5 [15-C-51 under mild reaction conditions.  相似文献   
68.
2-Substituted benzoxazole and benzothiazole were synthesized from condensation of aldehyde and 2-aminophenol or 2-aminothiophenol via a one-pot process using diethyl bromo phoshonate and tert-butyl hypochlorite.  相似文献   
69.
The title compounds 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h and 6a , 6b , 6c , 6d , 6e , 6f , 6g , 6h have been synthesized from β‐diketones and chromones, respectively, having 5‐methyl‐3‐phenylisoxazole moiety. Substituted 2‐acetylphenyl 5‐methyl‐3‐phenylisoxazole‐4‐carboxylate 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h were converted into 1‐(2‐hydroxyphenyl)‐3‐(5‐methyl‐3‐phenylisoxazole‐4‐yl)propane‐1,3‐dione 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h by Baker–Venketaraman transformation. Further, the cyclodehydration of diketone 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h with glacial acetic acid in conc. HCl at reflux gave corresponding substituted 2‐(5‐methyl‐3‐phenylisoxazole‐4‐yl)‐4H‐chromen‐4‐one 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h . The corresponding 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h react with hydrazine hydrate in presence of glacial acetic acid in ethanol at reflux to furnish 2‐(5‐5(5‐methyl‐3‐phenylisoxazole‐4‐yl)‐1H‐pyrazole‐3‐yl)phenol 6a , 6b , 6c , 6d , 6e , 6f , 6g , 6h . The structures of all newly synthesized compounds have been confirmed by IR, 1H NMR, mass spectral data, as well as elemental analysis. The synthesized compounds have been screened for their antimicrobial activity. Some of the compounds show better antimicrobial activity as compared with the reference drugs Streptomycin, Ampicillin, Gentamycin, Cefixime, and Ketoconazole.  相似文献   
70.
A mild and efficient method has been developed for the chemoselective preparation of 1,1-diacetates (acylals) from aldehydes catalyzed in the presence of a catalytic amount (0.1 mmol) of anhydrous cobalt(II) bromide under solvent-free conditions. The remarkable selectivity under mild and neutral conditions, excellent yields, short reaction time, and easily available and inexpensive catalyst are important features of this method.  相似文献   
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