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   3155篇
  免费   449篇
  国内免费   654篇
化学   3520篇
晶体学   146篇
力学   21篇
综合类   32篇
数学   6篇
物理学   533篇
  2024年   6篇
  2023年   35篇
  2022年   79篇
  2021年   97篇
  2020年   143篇
  2019年   121篇
  2018年   83篇
  2017年   115篇
  2016年   150篇
  2015年   163篇
  2014年   200篇
  2013年   319篇
  2012年   269篇
  2011年   216篇
  2010年   166篇
  2009年   190篇
  2008年   217篇
  2007年   200篇
  2006年   204篇
  2005年   206篇
  2004年   164篇
  2003年   188篇
  2002年   127篇
  2001年   92篇
  2000年   104篇
  1999年   61篇
  1998年   47篇
  1997年   68篇
  1996年   50篇
  1995年   42篇
  1994年   34篇
  1993年   18篇
  1992年   19篇
  1991年   16篇
  1990年   9篇
  1989年   4篇
  1988年   4篇
  1987年   4篇
  1986年   5篇
  1985年   4篇
  1984年   4篇
  1983年   1篇
  1982年   2篇
  1981年   1篇
  1980年   2篇
  1979年   3篇
  1978年   2篇
  1976年   1篇
  1975年   1篇
  1972年   2篇
排序方式: 共有4258条查询结果,搜索用时 31 毫秒
111.
To achieve targeted distribution of anticancer drugs with sustained activity, ferromagnetic ethylcellulose microcapsules containing an anticancer drug, mitomycin C (FM-MMC-mc), were prepared by a method based on phase separation principles. Two prototypes of FM-MMC-mc were made: one with the drug as the core and zinc ferrite on its capsular surface (outer type); the other with both the drug and zinc ferrite as the core (inner type). Both preparations provided a sustained-release property and a sensitive response to conventional magnetic force, although certain differences in the release rate of drug, magnetic responsiveness, and particle size were found between the two dosage forms. Animal studies showed that the magnetic microcapsules could be magnetically controlled in the artery and urinary bladder. VX2 tumors in the rabbit hind limb and urinary bladder were successfully treated with magnetic control of FM-MMC-mc. Pharmacokinetic study revealed that the targeting of the microcapsules markedly enhanced the drug absorption into the surrounding tissues for a prolonged period of time. The results indicate the feasibility and effectiveness of the magnetic microcapsules as a targeted drug delivery system.  相似文献   
112.
The solid-liquid equilibria of the quasi-quaternary system H2O-Zn(NO3)2·6H2O-Cu(NO3)2·3H2O-NH4NO3 were studied at 25°C by using a synthetic method based on conductivity measurements. Three isoplethic sections has been established at 25°C and the stable solid phases which appear are: NH4NO3(IV), Zn(NO3)2·6H2O, anhydrous Cu(NO3)2, Cu(NO3)2·3H2O and metastable Cu(NO3)·2.5H2O. Neither double salts, nor mixed crystals are observed at these temperatures and composition range.  相似文献   
113.
张尊听  史娟  贺云 《化学学报》2006,64(9):930-934
以白杨素为先导化合物, 对其进行磺化, 磺化衍生物与锌络合, 在含水10%的二甲基亚砜(DMSO)溶液中重结晶, 得双核锌配位化合物[Zn(C15H8O7S)(DMSO)]2•H2O. 采用IR, 1H NMR, DSC-TGA, 元素分析和X射线单晶衍射法对标题化合物进行了表征和晶体结构测定. 标题化合物属正交晶系, 空间群Pbcn, Zn(II)的配位数为5, 配位原子均为氧原子, 每个五配位的锌都具有四方锥型的配位构型, 被2个配体5-羟基氧负离子-7-羟基黄酮-6-磺酸根的5-羟基氧负离子桥联, 形成了一个中心Zn2O2的菱形平面. 水溶性白杨素黄酮配体与Zn(II)通过氢键、π-π堆积和配位作用自组装形成了一个三维结构的超分子化合物. 差示扫描量热分析(DSC-TGA)结果表明,标题化合物配体骨架分解温度为518.26 ℃. 同时, 标题化合物固体具有较强的光致发光现象, 在λex=423 nm条件下可发出λem=488 nm的黄色荧光, 并对其发光机制进行了探讨.  相似文献   
114.
柳萍  周定 《分析试验室》1996,15(4):73-75
本文建立了流动注射二甲酚橙光度法测定镀锌纯化液中Zn ̄2+的自动分析方法。利用区域采样技术和调整管路参数自动完成对样品的上千倍稀释,确定了最佳分析条件并研究了干扰离子的影响及消除办法。所建方法仪器简单,分析速度为84次/小时,变异系数(Zn ̄2+16.0g/L,n=20)为1.O%,用于实际钝化液分析,相对误差小于±10%。  相似文献   
115.
Raman spectra of aqueous Zn(II)–perchlorate solutions were measured over broad concentration (0.50–3.54 mol-L–1) and temperature (25–120°C) ranges. The weak polarized band at 390 cm–1 and two depolarized modes at 270 and 214 cm–1 have been assigned to 1(a 1g), 2(e g), and 5(f 2g) of the zinc–hexaaqua ion. The infrared-active mode at 365 cm–1 has been assigned to 3(f 1u). The vibrational analysis of the species [Zn(OH2) 2 + ] was done on the basis of O h symmetry (OH2 as point mass). The polarized mode 1(a 1g)-ZnO6 has been followed over the full temperature range and band parameters (band maximum, full width at half height, and intensity) have been examined. The position of the 1(a 1g)-ZnO6 mode shifts only about 4 cm–1 to lower frequencies and broadens by about 32 cm–1 for a 95°C temperature increase. The Raman spectroscopic data suggest that the hexaaqua–Zn(II) ion is thermodynamically stable in perchlorate solution over the temperature and concentration range measured. These findings are in contrast to ZnSO4 solutions, recently measured by one of us, where sulfate replaces a water molecule of the first hydration sphere. Ab initio geometry optimizations and frequency calculations of [Zn(OH2) 2 + ] were carried out at the Hartree–Fock and second-order Møller–Plesset levels of theory, using various basis sets up to 6-31 + G*. The global minimum structure of the hexaaqua–Zn(II) species corresponds with symmetry T h. The unscaled vibrational frequencies of the [Zn(OH2) 2 + ] are reported. The unscaled vibrational frequencies of the ZnO6, unit are lower than the experimental frequencies (ca. 15%), but scaling the frequencies reproduces the measured frequencies. The theoretical binding enthalpy for [Zn(OH2) 2 + ] was calculated and accounts for ca. 66% of the experimental single-ion hydration enthalpy for Zn(II).Ab initio geometry optimizations and frequency calculations are also reported for a [Zn(OH2) 2 18 ] (Zn[6 + 12]) cluster with 6 water molecules in the first sphere and 12 in the second sphere. The global minimum corresponds with T symmetry. Calculated frequencies of the zinc [6 + 12] cluster correspond well with the observed frequencies in solution. The 1-ZnO6 (unscaled) mode occurs at 388 cm–1 almost in perfect correspondence to the experimental value. The theoretical binding enthalpy for [Zn(OH2) 2 18 ] was calculated and is very close to the experimental single ion-hydration enthalpy for Zn(II). The water molecules of the first sphere form strong hydrogen bonds with water molecules in the second hydration shell because of the strong polarizing effect of the Zn(II) ion. The importance of the second hydration sphere is discussed.  相似文献   
116.
Sharpless四唑合成中捕获双四唑锌配合物   总被引:5,自引:0,他引:5  
The reaction of malononitrile with ZnCl2 and NaN3 in the presence of 2,2′-bipyridine and water affords the first bis(tetrazole) Zn-complex intermediate, mono(2,2′-bipyridine)bis(tetrazolyl)methane aqua zinc(Ⅱ), [Zn(2,2′-bpy)(BTZ)(H2O)]·(H2O)2 (1) which gives a clue for Demko-Sharpless′ tetrazole synthesis. Crystal data for 1: C13H18N10O4Zn, Mr=443.74, monoclinic, space group P21/c, a=12.5705(18), b=16.078(2), c=9.1921(13)?, β=95.010(3)°, V=1850.7(5)?3, Z=4. CCDC: 197788.  相似文献   
117.
Introduction Molecular recognition and molecular self-assemblycarried out by cooperation of the weak interactions(electrostatic reaction, hydrogen bonds, van der Waalsforce, short-range repulsive force, etc) are the commonphenomena in nature. In recent years, the research onsupramolecular complex has been a crossing focus ofseveral subjects such as chemistry, physics, biology,material and information.1 Supramolecular complex hasa wide application foreground in material, catalysis,conductor,…  相似文献   
118.
吴玉霜  赵新那 《分析化学》1998,26(8):977-980
选择水杨基荧光酮-乳化剂OP-盐酸为显色体系,应用双波长分光光度法扣除硫酸锌的基体干扰,不分离直接测定了湿法炼锌过程中硫酸锌净化液中的痕量锗。测定范围在0-40mg/L。本法应用于株洲冶炼厂锌净化液中锗的测定,结果与该厂长期的萃取-比色法结果相吻合,而测定速度较萃取-比色法至少提高了一倍。  相似文献   
119.
反胶束法合成氧化锌微晶及其荧光特性   总被引:1,自引:0,他引:1  
0引言材料的结构(微结构)、尺寸和形貌等因素对其特性及其实际应用具有重要的影响。对无机材料特别是氧化物半导体进行结构控制的研究近年来引起了人们极大的关注。氧化锌作为一种宽带隙(3.2eV)半导体材料,可广泛应用于压电材料、气体传感器、橡胶添加剂和光学器件等领域,而且还因其在室温下可产生激射现象使其成为纳米光学材料研究领域中的一大热点[1 ̄6]。目前,除了传统的固相-气相(V S)反应外,用于氧化锌微晶的制备方法主要有共沉淀法[7]、多羟基化合物水解法[8]、有机金属气相沉积法[9 ̄12]和水热法[13]等。通过选择不同的制备方法和…  相似文献   
120.
Herein we describe the importance of side chains in C3-symmetric ligands in supramolecular chemistry. The reaction of the new ligand tris(5-bromo-2-methoxybenzylidene)triaminoguanidinium chloride [H3Me3Br3L]Cl (1) with ZnCl2 results in the formation of the monomeric complex (Et3NH)2[(ZnCl2)3Me3Br3L] (2), in which the ligand remains in a conformation less favourable for the coordination of metal centres. The use of the related tris(5-bromo-2-hydroxybenzylidene)triaminoguanidinium chloride, [H6Br3L]Cl, under similar conditions, results in the formation of two different dimeric compounds (NH4)[{[Zn(NH3)]3Br3L}2{mu-(OH)}3]1/4MeOH (3) and [Zn{Zn2(OH2)3(NH3)Br3L}2] (4), depending on the solvent mixture used. The comparable reaction of the ligand tris(5-bromo-2-hydroxy-3-methoxybenzylidene)triaminoguanidinium chloride [H6(OMe)3Br3L]Cl (5), leads to the formation of a doughnut-shaped, protein-sized coordination oligomer (Et3NH)18[{Zn[Zn2Cl{(OMe)3Br3L}]2}6(mu-Cl)6(OH2)6]x CH3CN (6), which comprises six dimeric [Zn5{(OMe)3Br3L}2] units. Whereas 3 and 4 decompose in DMSO solution, 6 is surprisingly stable in the same solvent.  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