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   2316篇
  免费   205篇
  国内免费   177篇
化学   1458篇
晶体学   23篇
力学   95篇
综合类   9篇
数学   283篇
物理学   830篇
  2024年   24篇
  2023年   50篇
  2022年   52篇
  2021年   63篇
  2020年   91篇
  2019年   70篇
  2018年   70篇
  2017年   63篇
  2016年   90篇
  2015年   73篇
  2014年   91篇
  2013年   132篇
  2012年   157篇
  2011年   168篇
  2010年   99篇
  2009年   129篇
  2008年   128篇
  2007年   124篇
  2006年   119篇
  2005年   103篇
  2004年   75篇
  2003年   60篇
  2002年   57篇
  2001年   63篇
  2000年   55篇
  1999年   65篇
  1998年   35篇
  1997年   46篇
  1996年   49篇
  1995年   34篇
  1994年   19篇
  1993年   33篇
  1992年   31篇
  1991年   31篇
  1990年   22篇
  1989年   10篇
  1988年   9篇
  1987年   10篇
  1986年   9篇
  1985年   9篇
  1984年   10篇
  1983年   6篇
  1982年   10篇
  1981年   6篇
  1980年   4篇
  1979年   5篇
  1978年   3篇
  1976年   4篇
  1974年   3篇
  1973年   6篇
排序方式: 共有2698条查询结果,搜索用时 15 毫秒
71.
The persistence length and the overlap concentration(c~*) of poly(ethylene oxide)(PEO) and hydroxyethylcellulose(HEC) with similar molecular weight in 1×TBE buffer were studied by laser light scattering and viscometry.Their effect on DNA separation was investigated by capillary electrophoresis.It was determined that the persistence length of HEC was at least 5 times higher than that of PEO.Therefore,the c~* of HEC was smaller than that of PEO by a factor of ca.2.5.It was also found that the c~* values de...  相似文献   
72.
DTA was used to study thermal properties and thermal stability of (50-x)Li2O-xTiO2-50P2O5 (x=0–10 mol%) and 45Li2Ot-yTiO2-(55-y)P2O5 (y=5–20 mol%) glasses. The addition of TiO2 to lithium phosphate glasses results in a non-linear increase of glass transition temperature. All prepared glasses crystallize under heating within the temperature range of 400–540°C. The lowest tendency towards crystallization have the glasses with x=7.5 and y=10 mol% TiO2. X-ray diffraction analysis showed that major compounds formed by annealing of the glasses were LiPO3, Li4 P2O7, TiP2O7 and NASICON-type LiTi2(PO4)3. DTA results also indicated that the maximum of nucleation rate for 45Li2O-5TiO2-50P2O5 glass is close to the glass transition temperature.  相似文献   
73.
Bulk glasses of the series (1 ? x)[0.5K2O–0.1B2O3–0.4P2O5]–xNb2O5 with x = 0–45.7 mol% Nb2O5 were prepared by slow cooling in air and investigated by Raman, 31P, and 11B MAS NMR spectroscopy. The incorporation of Nb2O5 into the parent borophosphate glass results in a substantial increase in the glass transition temperature and chemical durability of glasses. Raman spectra showed that Nb atoms form distorted NbO6 octahedra, which are isolated at low Nb2O5 content, whereas at higher Nb2O5 content they form clusters. 11B NMR spectra of the glasses revealed the interaction between Nb2O5 and BO4 tetrahedral units, which results in a partial transformation of tetrahedral BO4 units to trigonal BO3 units and the formation of mixed B(OP)4?n(ONb)n units.  相似文献   
74.
Amorphous and polycrystalline (Pb0.76Ca0.24)TiO3 (PCT) thin films deposited on an Si(1 0 0) substrate have been prepared by a simple sol-gel process. The microstructure and surface morphologies of the thin films have been studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). The polycrystalline PCT film on the Si(1 0 0) substrate has a tetragonal perovskite structure with grain size from 60 to 110 nm. AFM reveals smooth surfaces and root mean square (rms) roughness of 0.17 and 4.4 nm for amorphous and polycrystalline films, respectively. The refractive index n and extinction coefficient k of the amorphous and polycrystalline thin films was obtained by spectroscopic ellipsometry as a function of the photon energy in the range from 2.0 to 5.4 eV. The maximum n and direct bandgap energies of amorphous and polycrystalline thin films were 2.66 and 4.11 eV, 2.64 and 3.84 eV, respectively.  相似文献   
75.
本文对在玻璃碳电极上不可逆溶出催化的理论进行了研究,推导了溶出催化过程的电流方程,峰电流和峰电势方程,并用微计算机模拟出各种关系曲线,从理论方程得知溶出催化伏安法所得的峰电流比溶出伏安法的峰电流提高了二个数量级。本文还用钯的溶出催化实验验证理论方程,所得的实验结果均与理论方程相吻合。  相似文献   
76.
Mo HJ  Shen Y  Ye BH 《Inorganic chemistry》2012,51(13):7174-7184
Five imidazole-based anion receptors A-E are designed for cyanide anion recognition via hydrogen bonding interaction in water. Only receptors A [Ru(bpy)(2)(mpipH)](ClO(4))(2) (bpy is bipyridine and mpipH is 2-(4-methylphenyl)-imidazo[4,5-f]-1,10-phenanthroline) and E [Ru(2)(bpy)(4)(mbpibH(2))](ClO(4))(4) (mbpibH(2) is 1,3-bis([1,10]-phenanthroline-[5,6-d]imidazol-2-yl)benzene) selectively recognize CN(-) from OAc(-), F(-), Cl(-), Br(-), I(-), NO(3)(-), HSO(4)(-), ClO(4)(-), H(2)PO(4)(-), HCO(3)(-), N(3)(-), and SCN(-) anions in water (without organic solvent) at physiological conditions via formation of multiple hydrogen bonding interaction with binding constants of K(A(H2O)) = 345 ± 21 and K(E(H2O)) = 878 ± 41, respectively. The detection limits of A and E toward CN(-) in water are 100 and 5 μM, respectively. Receptor E has an appropriate pK(a2)* value (8.75) of N-H proton and a C-shape cavity structure with three-point hydrogen bonding, consisting of two NH and one cooperative phenyl CH hydrogen bonds. Appropriate acidity of N-H proton and multipoint hydrogen bonding are both important in enhancing the selectivity and sensitivity toward CN(-) in water. The phenyl CH···CN(-) hydrogen bonding interaction is observed by the HMBC NMR technique for the first time, which provides an efficient approach to directly probe the binding site of the receptor toward CN(-). Moreover, CN(-) induced emission lifetime change of the receptor has been exploited in water for the first time. The energy-optimized structure of E-CN adduct is also proposed on the basis of theoretical calculations.  相似文献   
77.
We report on the construction of a label-free electrochemical immunosensor for detecting the core antigen of the hepatitis C virus (HCV core antigen). A glassy carbon electrode (GCE) was modified with a nanocomposite made from gold nanoparticles, zirconia nanoparticles and chitosan, and prepared by in situ reduction. The zirconia nanoparticles were first dispersed in chitosan solution, and then AuNPs were prepared in situ on the ZrO2-chitosan composite. In parallel, a nanocomposite was synthesized from AuNPs, silica nanoparticles and chitosan, and conjugated to a secondary antibody. The properties of the resulting nanocomposites were investigated by UV-visible photometry and transmission electron microscopy, and the stepwise assembly process was characterized by means of cyclic voltammetry and electrochemical impedance spectroscopy. An sandwich type of immunosensor was developed which displays high sensitivity to the HCV core antigen in the concentration range between 2 and 512?ng?mL?1, with a detection limit of 0.17?ng?mL?1 (at S/N?=?3). This immunosensor provides an alternative approach towards the diagnosis of HCV.
Fig
A sandwich-type immunosensor was constructed for the detection of HCV core Ag. AuNPs/ZrO2-Chits nanocomposites were prepared by in situ reduction method. AuNPs/SiO2-Chits nanocomposite integrated with secondary antibody (Ab2) without labeled HRP. The immunosensor displayed high sensitivity to HCV core antigen with a detection limit of 0.17?ng?mL?1 (S/N?=?3).  相似文献   
78.
We have previously examined the binding patterns of various substrates to human cytochrome P450 2D6 (CYP2D6) using a series of molecular modeling methods. In this study, we further explored the binding modes of various types of inhibitors to CYP2D6 using a combination of ligand- and protein-based modeling approaches. Firstly, we developed and validated a pharmacophore model for CYP2D6 inhibitors, which consisted of two hydrophobic features and one hydrogen bond acceptor feature. Secondly, we constructed and validated a quantitative structure-activity relationship (QSAR) model for CYP2D6 inhibitors which gave a poor to moderate prediction accuracy. Thirdly, a panel of CYP2D6 inhibitors were subject to molecular docking into the active site of wild-type and mutated CYP2D6 enzyme. We demonstrated that 8 residues in the active site (Leu213, Glu216, Ser217, Gln244, Asp301, Ser304, Ala305, and Phe483) played an important role in the binding to the inhibitors via hydrogen bond formation and/or π-π stacking interaction. Apparent changes in the binding modes of the inhibitors have been observed with Phe120Ile, Glu216Asp, Asp301Glu mutations in CYP2D6. Finally, we screened for potential binders/inhibitors from the Chinese herbal medicine Scutellaria baicalensis (Huangqin, Baikal Skullcap) using the established pharmacophore model for CYP2D6 inhibitors and molecular docking approach. Overall, 18 out of 40 compounds from S. baicalensis were mapped to the pharmacophore model of CYP2D6 inhibitors and most herbal compounds from S. baicalensis could be docked into the active site of CYP2D6. Our study has provided insights into the molecular mechanisms of interaction of synthetic and herbal compounds with human CYP2D6 and further benchmarking studies are needed to validate our modeling and virtual screening results.  相似文献   
79.
微波消解ICP-MS法测定广西北部湾海鸭蛋中硒和锗的含量   总被引:3,自引:0,他引:3  
以硝酸-过氧化氢(体积比为5:3)混合溶液为消解剂,微波消解法处理海鸭蛋样品,采用电感耦合等离子体质谱法测定样品溶液中的硒和锗的含量。选择适合的同位素元素,运用碰撞室技术(CCT)降低多原子离子对元素硒、锗的干扰,用钇作为在线内标。硒、锗工作曲线的线性范围均为0.0-100.0ng/mL,相关系数r=0.9996;硒、锗的检出限分别为1.1,0.15ng/mL,测定结果的相对标准偏差分别为4.78%,5.70%(n=6),加标回收率为92.2%-104.0%。用该法测定国家标准物质黄鱼(GBW08573)中硒的含量,测定值在标称值范围内。  相似文献   
80.
本文用WAXD、PLM、DSC方法研究了聚氧化乙烯(PEO)/聚乙烯基吡咯烷酮(PVP)共混体系的结晶行为,探索了两组分聚合物间相互作用及体系结晶度与非晶组分含量的关系。DSC研究表明PEO/PVP共混体系具有两个玻璃化转变温度,分别是纯组分的T_g,无相容性。应用Avrami和LH方程对其动力学参数进行了研究。偏光显微镜观察了共混物结构形态。  相似文献   
[首页] « 上一页 [3] [4] [5] [6] [7] 8 [9] [10] [11] [12] [13] 下一页 » 末  页»
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