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   187篇
  免费   5篇
化学   104篇
力学   10篇
数学   23篇
物理学   55篇
  2022年   2篇
  2016年   2篇
  2015年   3篇
  2014年   4篇
  2013年   5篇
  2012年   7篇
  2011年   7篇
  2010年   4篇
  2009年   5篇
  2008年   10篇
  2007年   8篇
  2006年   4篇
  2005年   8篇
  2004年   11篇
  2003年   6篇
  2002年   7篇
  2001年   9篇
  2000年   5篇
  1999年   4篇
  1996年   2篇
  1993年   3篇
  1992年   3篇
  1991年   1篇
  1990年   5篇
  1989年   9篇
  1988年   3篇
  1987年   5篇
  1986年   6篇
  1984年   4篇
  1983年   1篇
  1982年   3篇
  1981年   3篇
  1980年   3篇
  1979年   2篇
  1977年   1篇
  1975年   2篇
  1974年   3篇
  1973年   4篇
  1972年   1篇
  1941年   1篇
  1940年   1篇
  1939年   2篇
  1936年   1篇
  1930年   1篇
  1925年   1篇
  1924年   1篇
  1923年   2篇
  1913年   1篇
  1908年   1篇
  1905年   1篇
排序方式: 共有192条查询结果,搜索用时 15 毫秒
1.
2.
3.
Paramagnetic enhancement of nuclear spin-lattice relaxation rates (PREs) was measured in aqueous solution of the trisaccharide raffinose in the presence of a gadolinium(III) complex, GdDTPA-BMA, used as a magnetic resonance imaging contrast agent. The relaxation enhancement of aqueous protons was measured over a broad range of magnetic fields, using field-cycling apparatus in addition to conventional spectrometers. The nuclear magnetic relaxation dispersion profile thus obtained was interpreted with a recently developed model, allowing for both inner- and outer-sphere relaxation. The relaxation enhancement for the carbon-13 nuclei in raffinose was studied under high-resolution conditions at three magnetic fields, whereas the sugar proton PRE was measured at two fields. The PRE of the sugar nuclei could be interpreted in a consistent way, assuming that it was caused by the outer-sphere mechanism. The electron spin relaxation was found to be a less important source of modulation of the electron-nuclear dipole-dipole interaction than the mutual translational diffusion.  相似文献   
4.
Large configuration interaction calculations of the proton—proton coupling constant for several geometrical configurations of the ammonia molecules are reported. The analytical expressions for the energy surface and the coupling constant as functions of two cartesian displacement coordinates are fitted to the calculated values. The potential is used for the calculation of the vibrational wavefunctions for 15NH3 and 15ND3 species and the vibrational averaging of the coupling constant is carried out using these functions. Though the value of the coupling constants shows a very strong geometry dependence, the vibrational corrections are found to be small. A possible correlation of the proton—proton coupling constant with an angular parameter in the NH2 group in RNH2 compounds is indicated.  相似文献   
5.
Mesoporous carbons were synthesized from polyacrylonitrile (PAN) using ordered and disordered mesoporous silica templates and were characterized using transmission electron microscopy (TEM), powder X-ray diffraction, nitrogen adsorption, and thermogravimetry. The pores of the silica templates were infiltrated with carbon precursor (PAN) via polymerization of acrylonitrile from initiation sites chemically bonded to the silica surface. This polymerization method is expected to allow for a uniform filling of the template with PAN and to minimize the introduction of nontemplated PAN, thus mitigating the formation of nontemplated carbon. PAN was stabilized by heating to 573 K under air and carbonized under N2 at 1073 K. The resulting carbons exhibited high total pore volumes (1.5-1.8 cm3 g(-1)), with a primary contribution of the mesopore volume and with relatively low microporosity. The carbons synthesized using mesoporous templates with a 2-dimensional hexagonal structure (SBA-15 silica) and a face-centered cubic structure (FDU-1 silica) exhibited narrow pore size distributions (PSDs), whereas the carbon synthesized using disordered silica gel template had broader PSD. TEM showed that the SBA-15-templated carbon was composed of arrays of long, straight, or curved nanorods aligned in 2-D hexagonal arrays. The carbon replica of FDU-1 silica appeared to be composed of ordered arrays of spheres. XRD provided evidence of some degree of ordering of graphene sheets in the carbon frameworks. Elemental analysis showed that the carbons contain an appreciable amount of nitrogen. The use of our novel infiltration method and PAN as a carbon precursor allowed us to obtain ordered mesoporous carbons (OMCs) with (i) very high mesopore volume, (ii) low microporosity, (iii) low secondary mesoporosity, (iv) large pore diameter (8-12 nm), and (v) semi-graphitic framework, which represent a desirable combination of features that has not been realized before for OMCs.  相似文献   
6.
The protonated form of 1,8-bis(dimethylamino)naphthalene (DMANH(+)) consists of a rigid, aromatic framework, substituted by two amino groups that are connected by a strong, symmetric (on the NMR time-scale) hydrogen bond bridge. The reorientational motion of the molecule in dimethylformamide-d7 solution was characterized by T(1) and NOE measurements for aromatic (13)C nuclei. Treating the reorientation of DMANH(+) as anisotropic rotational diffusion of a rigid body, the diffusion tensor was determined with good accuracy. Measurements and interpretation of (15)N T(1) and NOE indicate that the proton transfer between potential minima in the hydrogen bond bridge is faster than the molecular reorientation.  相似文献   
7.
Arrays of graphitic carbon nanoclusters were obtained by pyrolysis of nanoscale phase-separated block copolymers of polyacrylonitrile and poly(n-butyl acrylate). Upon heating in an inert atmosphere to temperatures ranging from approximately 400 to 1200 degrees C, polyacrylonitrile domains were converted into carbon nanoclusters, maintaining the overall shape and spacing, whereas the poly(n-butyl acrylate) phase was sacrificed. Preservation of the original nanoscale morphology of a block copolymer was possible only if pyrolysis was preceded by oxidation at temperatures of approximately 230 degrees C, in analogy with thermal stabilization of polyacrylonitrile precursor in the process used in the manufacturing of carbon fibers. Preorganization of the carbon precursor through self-assembly in block copolymers of polyacrylonitrile appears to be an attractive and robust strategy for templated synthesis of well-defined nanostructured carbon materials.  相似文献   
8.
9.
We demonstrate a simple bioconjugate polymer system that undergoes reversible self‐assembling into extended fibrous structures, reminiscent of those observed in living systems. It is comprised of green fluorescent protein (GFP) molecules linked into linear oligomeric strands through click step growth polymerization with dialkyne poly(ethylene oxide) (PEO). Confocal microscopy, atomic force microscopy, and dynamic light scattering revealed that such strands form high persistence length fibers, with lengths reaching tens of micrometers, and uniform, sub‐100 nm widths. We ascribe this remarkable and robust form of self‐assembly to the cooperativity arising from the known tendency of GFP molecules to dimerize through localized hydrophobic patches and from their covalent pre‐linking with flexible PEO. Dissipative particle dynamics simulations of a coarse‐grained model of the system revealed its tendency to form elongated fibrous aggregates, suggesting the general nature of this mode of self‐assembly.  相似文献   
10.
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