全文获取类型
收费全文 | 219篇 |
免费 | 14篇 |
专业分类
化学 | 178篇 |
力学 | 3篇 |
数学 | 34篇 |
物理学 | 18篇 |
出版年
2022年 | 2篇 |
2021年 | 5篇 |
2020年 | 8篇 |
2019年 | 7篇 |
2018年 | 6篇 |
2017年 | 4篇 |
2016年 | 12篇 |
2015年 | 7篇 |
2014年 | 7篇 |
2013年 | 12篇 |
2012年 | 20篇 |
2011年 | 20篇 |
2010年 | 10篇 |
2009年 | 8篇 |
2008年 | 10篇 |
2007年 | 18篇 |
2006年 | 18篇 |
2005年 | 11篇 |
2004年 | 14篇 |
2003年 | 7篇 |
2002年 | 2篇 |
2001年 | 4篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1980年 | 1篇 |
1935年 | 1篇 |
排序方式: 共有233条查询结果,搜索用时 46 毫秒
101.
Frontispiece: Self‐Immolative Linkers as Caps for the Design of Gated Silica Mesoporous Supports 下载免费PDF全文
102.
103.
Fernando Giménez 《Journal of Geometry》1992,45(1-2):63-86
We give some estimates for the volume of a cone with vertex a submanifold P of a Riemannian or Kaehler manifold M. The estimates are functions of bounds of the mean curvature of P and the sectional curvature of M. They are sharp on cones having a basis which is contained in a tubular hypersurface about P in a space form or in a complex space form.Work partially supported by DGICYT Grant No. PB90-0014-C03-01. 相似文献
104.
Vargas-Berenguel A Ortega-Caballero F Santoyo-González F García-López JJ Giménez-Martínez JJ García-Fuentes L Ortiz-Salmerón E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):812-827
In order to evaluate the ability of multivalent glycosides based on a beta-cyclodextrin core as site-specific molecular carriers, a study on both the inclusion complexation behaviour and lectin binding affinity of branched and hyperbranched beta-cyclodextrins is presented. A series of cluster galactosides constructed on beta-cyclodextrin scaffolds containing seven 1-thio-beta-lactose or beta-lactosylamine bound to the macrocyclic core through different spacer arms were synthesised. In addition, the first synthesis of three first-order dendrimers based on a beta-cyclodextrin core containing fourteen 1-thio-beta-D-galactose, 1-thio-beta-lactose and 1-thio-beta-melibiose residues was performed. Calorimetric titrations performed at 25 degrees C in buffered aqueous solution (pH 7.4) gave the affinity constants and the thermodynamic parameters for the complex formation of these beta-cyclodextrin derivatives with guests sodium 8-anilino-1-naphthalenesulfonate (ANS) and 2-naphthalenesulfonate, and lectin from peanut (Arachis hypogaea) (PNA). The persubstitution of the primary face of the beta-cyclodextrin with saccharides led to a slight increase of the binding constant values for the inclusion complexation with ANS relative to the native beta-cyclodextrin. However, the increase of the steric congestion due to the presence of the saccharide residues on the narrow rim of the beta-cyclodextrin may cause a decrease of the binding ability as shown for sodium 2-naphthalenesulfonate. The spacer arms are not passive elements and influence the host binding ability according to their chemical nature. PNA forms soluble cross-linked complexes with cluster galactosides and lactosides scaffolded on beta-cyclodextrin but not with cluster galactopyranosylamines or melibiose. Both, perbranched and hyperbranched beta-cyclodextrins, form stronger complexes with PNA than the monomeric analogues. However, the use of hyperbranched CDs does not contribute to the improvement of the complex stability relative to heptakis-glycocyclodextrin derivatives. Finally, a titration experiment with PNA and a complex formed by a heptakis lactose beta-cyclodextrin derivative with sodium 2-naphthalenesulfonate showed the formation of a soluble cross-linked complex with stronger affinity constant and higher stoichiometry than those observed for the complex formation of PNA with the same heptakis-lactose beta-cyclodextrin derivative, suggesting the formation of a three component complex. 相似文献
105.
Joan Gregori José J. García-Jareño David Giménez-Romero Francisco Vicente 《Journal of Solid State Electrochemistry》2005,9(2):83-90
Anodic nickel dissolution in acid media has been analyzed by means of electrochemical quartz crystal microbalance and electrochemical impedance spectroscopy techniques. The experimental impedance spectra have been fitted to an equivalent circuit which is related to a mechanism of two consecutive electron transfers followed by a Ni2+ mass transfer step. That way, an estimation for values of rate constants and surface concentrations of the Ni(0), Ni(I) and Ni(II) species has been obtained. 相似文献
106.
Giménez R Manrique AB Uriel S Barberá J Serrano JL 《Chemical communications (Cambridge, England)》2004,(18):2064-2065
Thermotropic smectic phases have been observed for the first time in a zinc coordination complex with tetrahedral geometry; this complex, which contains the pyrazole dimer bis[3,5-bis(p-decyloxyphenyl)pyrazolyl]ethane as the ligand, exhibits fluorescence. 相似文献
107.
In this work an excitation emission molecular fluorescence technique with PARAFAC calibration is proposed for enrofloxacine determination in feeding water from poultry farms. In accordance with the working criteria of the 2002/657/EC European Decision, the proposed method has a capability of detection, CCbeta, of 6.8 microg l(-1), for both probabilities of false positive and false negative of 5%. The accuracy of the method is demonstrated and its precision is 1.7 microg l(-1), expressed as standard deviation. This method allows one to identify and determine the quantity of enrofloxacine present in water samples from poultry farms without it being necessary to determine the possible interferents, nor separate them in a step previous to calibration. 相似文献
108.
Francisco Vicente Joan Gregori Jose Juan García-Jareño David Giménez-Romero 《Journal of Solid State Electrochemistry》2005,9(10):684-690
The electrochemical quartz crystal microbalance results show that nickel electrodissolution and nickel passivation occur simultaneously. Besides, the anodic transferred charge decreases and the passive layer thickness increases with the number of successive voltammetric cycles. Mass balances across the metal/passive layer/solution have been done from the instantaneous F(dm/dQ) function. A dynamic process for generation of an inner NiO and a Ni(OH)2 outer passive layers is suggested. 相似文献
109.
Esther?Campos GiménezEmail author Thierry?Bénet Lionel?Spack 《Accreditation and quality assurance》2004,9(10):605-614
The measurement uncertainty in the calculation of the amount of blocked and reactive lysine (as determined by the furosine method) was evaluated according to the procedure described in the Eurachem/CITAC guide. The analytical method involves the chromatographic determination of lysine and furosine after acid hydrolysis. The calculation of blocked and reactive lysine in the initial protein is based on known conversion factors. The estimation of the uncertainty was performed in two steps: (1) determination of the uncertainty in the chromatographic determination of lysine and furosine, and (2) determination of the uncertainty in the calculation of blocked and reactive lysine. The individual contributions to the final uncertainty were identified, quantified, and combined in uncertainty budgets. The largest contribution to the calculation of blocked lysine came from estimating the conversion factor of blocked lysine into furosine during acid hydrolysis. For the calculation of reactive lysine, the main contribution came from the chromatographic determination of lysine. The uncertainty estimates were compared to available validation data (in-house and collaborative standard deviations of reproducibility). 相似文献
110.
Clemente-Juan JM Coronado E Gaita-Ariño A Giménez-Saiz C Güdel HU Sieber A Bircher R Mutka H 《Inorganic chemistry》2005,44(10):3389-3395
The magnetic exchange interactions in a C0(3)(11) moiety encapsulated in Na(17) [(NaOH(2))Co(3)(H(2)O)(P(2)W(15)O(56))(2)] (NaCo(3)) were studied by a combination of magnetic measurements (magnetic susceptibility and low-temperature magnetization), with a detailed Inelastic Neutron Scattering (INS) investigation. The novel structure of the salt was determined by X-ray crystallography. The ferromagnetic Co(3)O(14) triangular cluster core consists of three octahedrally oxo-coordinated Co(II) ions sharing edges. According to the single-ion anisotropy and spin-orbit coupling usually assumed for octahedral Co(II) ions, the appropiate exchange Hamiltonian to describe the ground-state properties of the isosceles triangular Co(3) spin cluster is anisotropic and is expressed as H = - 2sigma(alpha)(=)(x,y,z)(J(alpha)(12)S(1alpha)S(2alpha) + J(alpha)(23)S(2alpha)S(3alpha) + J(alpha)(13)S(1alpha)S(3alpha)), where J(alpha) are the components of the exchange interactions between the Co(II) ions. To reproduce the INS data, nonparallel anisotropic exchange tensors needed to be introduced, which were directly connected to the molecular symmetry of the complex. The following range of parameters (value +/- 0.5 cm(-1)) was found to reproduce all experimental information while taking magnetostructural relations into account: J(x)(12) = J(y)(13) = 8.6 cm(-1); J(y)(12) = J(x)(13) = 1.4 cm(-1); J(z)(12) = J(z)(13) = 10.0 cm(-1); J(x)(23) = J(y)(23) = 6.5 cm(-1) and = 3.4 cm(-1). 相似文献