全文获取类型
收费全文 | 164篇 |
免费 | 4篇 |
专业分类
化学 | 151篇 |
晶体学 | 3篇 |
力学 | 4篇 |
数学 | 3篇 |
物理学 | 7篇 |
出版年
2023年 | 2篇 |
2022年 | 3篇 |
2021年 | 2篇 |
2020年 | 2篇 |
2018年 | 2篇 |
2017年 | 2篇 |
2016年 | 3篇 |
2015年 | 5篇 |
2014年 | 2篇 |
2013年 | 3篇 |
2012年 | 11篇 |
2011年 | 12篇 |
2010年 | 5篇 |
2009年 | 10篇 |
2008年 | 10篇 |
2007年 | 12篇 |
2006年 | 16篇 |
2005年 | 11篇 |
2004年 | 9篇 |
2003年 | 6篇 |
2002年 | 3篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1979年 | 1篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1969年 | 1篇 |
1931年 | 1篇 |
1916年 | 1篇 |
排序方式: 共有168条查询结果,搜索用时 15 毫秒
71.
Nativi C Francesconi O Gabrielli G De Simone I Turchetti B Mello T Di Cesare Mannelli L Ghelardini C Buzzini P Roelens S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(16):5064-5072
The biological activity of a set of structurally related aminopyrrolic synthetic receptors for monosaccharides has been tested versus yeast and yeast-like microorganisms and compared to their binding affinity toward mannosides. Antibiotic activity comparable to that of well-known polyene (amphotericin B) or azole (ketoconazole) drugs has been found for some members of the family, along with a general correlation with binding abilities. A systematic structure-activity-affinity investigation shed light on the structural and functional requirements necessary for antibiotic activity and identified the tripodal compound 1 as the most potent compound of the set. Together with toxicity tests and inhibitor localization experiments performed through fluorescence microscopy, these studies led to the characterization of a new class of carbohydrate binding agents possessing antibiotic activity, in which pyrrolic groups precisely structured on a tripodal architecture appear to be responsible for permeability through the cell wall of pathogens, as well as for antibiotic activity inside the cytoplasm. 相似文献
72.
I Radivojevic G Bazzan BP Burton-Pye K Ithisuphalap R Saleh MF Durstock LC Francesconi CM Drain 《The journal of physical chemistry. C, Nanomaterials and interfaces》2012,116(30):15867-15877
Metalloporphyrin and metallophthalocyanine dyes ligating Hf(IV) and Zr(IV) ions bind to semiconductor oxide surfaces such as TiO(2) via the protruding group IV metal ions. The use of oxophylic metal ions with large ionic radii that protrude from the macrocycle is a unique mode of attaching chromophores to oxide surfaces in the design of dye-sensitized solar cells (DSSCs). Our previous report on the structure and physical properties of ternary complexes wherein the Hf(IV) and Zr(IV) ions are ligated to both a porphyrinoid and to a defect site on a polyoxometalate (POM) represents a model for this new way of binding dyes to oxide surfaces. The Zr(IV) and Hf(IV) complexes of 5,10,15,20-tetraphenylporphyrin (TPP) with two ligated acetates, (TPP)Hf(OAc)(2) and (TPP)Zr(OAc)(2), and the corresponding metallophthalocyanine (Pc) diacetate complexes, (Pc)Hf(OAc)(2) and (Pc)Zr(OAc)(2), were evaluated as novel dyes for the fabrication of dye-sensitized solar cells. Similarly to the ternary complexes with the POM, the oxide surface replaces the acetates to affect binding. In DSSCs the Zr(IV) phthalocyanine dye performs better than the Zr(IV) porphyrin dye, and reaches an overall efficiency of ~ 1.0%. The Hf(IV) dyes are less efficient. The photophysical properties of these complexes in solution suggested energetically favorable injection of electrons into the conduction band of TiO(2) semiconductor nanoparticles, as well as a good band gap match with I(3) (-)/I(-) pair in liquid 1-butyl-3-methyl imidazolium iodide. The combination of blue absorbing TPP with the red absorbing Pc complexes can increase the absorbance of solar light in the device; however, the overall conversion efficiency of DSSCs using TiO(2) nanoparticles treated with a mixture of both Zr(IV) complexes is comparable, but not greater than, the single (Pc)Zr. Thus, surface bound (TPP)Zr increases the absorbance in blue region of the spectra, but at the cost of diminished absorbance in the red in this DSSC architecture. 相似文献
73.
Recently, a new macro-mechanical model for ductile damage was presented by Wierzbicki, Xue et al., trying to address the role assumed by Lode angle and pressure sensitivity. The new model requires several experimental tests to identify all its parameters, but should outperform the “standard” formulations at high triaxiality levels. In this work a comparison between the Lemaitre’s Continuous Damage Mechanics model and the Wierzbicki’s one is proposed. After calibration of both models, the displacement field measured using the Digital Image Correlation technique in a large shear test case is compared with results of Finite Element simulations obtained using the two damage models considered. Results are not conclusive but show that the new damage model is quite accurateas rupture criterion, but damage evolution history deviates to some extent from the experimentally observed behavior. 相似文献
74.
This study presents an evaluation of the static and dynamic mechanical behavior of low porosity, ductile two-dimensional auxetic metamaterials. The full in-plane displacement fields and the eigenmodes of different geometric structures were investigated and compared with finite element simulations using speckle interferometry and digital image correlation. The results showed strong agreement, validating the theoretical approach used and establishing a method for testing and quantitatively assessing the performance of negative Poisson ratio structures, and metamaterials in general, for different purposes and fields. The findings of this study also increase our knowledge of elastic instabilities in metallic auxetic structures, with further applications in several engineering fields that can benefit from combining the qualities of ductile materials with additional features typical of these smart structures. 相似文献
75.
Excess molar volumes
for binary mixtures of acetonitrile + dichloromethane, acetonitrile + trichloromethane, and acetonitrile + tetracloromethane at 25°C have been used to calculate partial molar volumes
, excess partial molar volumes
, and apparent molar volumes
of each component as a function of composition. The V
m
Evalues are negative over the entire composition range for the systems studied. The applicability of the Prigogine–Flory–Patterson theory was explored. The agreement between theoretical and experimental results is satisfactory for the systems with dichloromethane and tetrachloromethane. For the unsymmetrical behavior of the system with trichloromethane, however, the agreement is poor. 相似文献
76.
Direct measurement of lipid-soluble arsenic species in biological samples with HPLC-ICPMS 总被引:2,自引:0,他引:2
Lipid-soluble arsenicals (arsenolipids) occur in a wide range of biological samples where they may play a key role in the biosynthesis of organoarsenic compounds from inorganic arsenic. The study of these compounds has been hindered, however, by the lack of a suitable analytical technique able to separate and measure the various lipid species. As a source of arsenolipids, we used 10 crude fish oils from various regions of the world. Total arsenic analyses on the fish oils, performed with ICPMS following acid digestion with microwave-assisted heating, gave concentrations from 4.3 to 10.5 mg As kg(-1). All of the arsenic was soluble in non-polar solvents such as hexane. Analysis of the fish oils for arsenolipids was performed by normal phase HPLC-ICPMS with various mixtures of organic solvents as mobile phases. Inherent problems of instability associated with the introduction of organic solvents to the plasma were overcome by the use of reduced column flow, a chilled spray chamber, and the addition of oxygen directly to the plasma. All ten fish oils appeared to contain the same 4-6 major arsenolipids, but in varying amounts depending on the origin of the fish. Further chromatography with both normal phase and reversed-phase conditions on some of the oils indicated the presence of many more minor arsenolipids. Quantification was achieved by external calibration against triphenylarsine oxide or triphenylarsine sulfide, and the sum of species following HPLC of the oils matched well the total arsenic results (92-107%). The method was applied to samples of food supplements (fish oil capsules) and a packaged food product (cod liver) whereby arsenolipids were measured and found to be significant arsenic constituents. This study represents the first attempt to directly measure intact arsenolipids and, with appropriate sample preparation, may be suitable for quantitative measurement of these arsenicals in a range of biological samples, including foodstuffs. 相似文献
77.
Marco Pradella Romolo Dorizzi Davide Giavarina Franco Rigolin Stefano Biasioli 《Analytica chimica acta》1989
An expert system is described to assist physicians in the management of patients suffering from electrolyte and acid/base disorders. The knowledge base includes rules about these disorders and is designed around the MicroExpert system. The inference engine is a modified PASCAL program. The rule base (FLUID) comprises information on 3 items (sodium and water, potassium, and acid/base disorders), selected by interpretation of screening tests. If necessary, further tests may be required by the program. The system is evaluated with cases taken from the literature and from recent problems in this laboratory. The overall success rate of the system was about 90% in terms of agreement between predicted and actual diagnoses. 相似文献
78.
Summary As a continuation of our studies on excess functions of binary systems containing acetonitrile-amines mixtures, in this work excess molar enthalpy (HmE) of acetonitrile+diethylamine or s-butylamine mixtures have been determined as a function of composition at 288.15, 293.15, 298.15 and 303.15 K at atmospheric pressure using a modified 1455 Parr adiabatic calorimeter. The excess enthalpy data are positive for both systems over the whole composition range. ERAS-Model calculations allowing for self-association and cross-association of the components were performed. The results of the calculations and the influence of temperature and isomers chains on the excess enthalpy behavior are discussed. 相似文献
79.
Zhang X Zhang C Guo H Huang W Polenova T Francesconi LC Akins DL 《The journal of physical chemistry. B》2005,109(41):19156-19160
The novel polyoxometalate ([(Eu2PW10O38)4(W3O8(H2O)2(OH)4)]22-), also referred to herein as Eu8P4W43, has been immobilized inside the channels of MCM-41 mesoporous molecular sieve material by means of the incipient wetness method. For proper host-guest interaction, amine groups were introduced into the system as a result of an aminosilylation procedure. A stable and integrated Eu8P4W43 polyoxometalate was shown to be formed inside the channels of the modified MCM-41. The products were characterized by XRD, UV-vis absorption, emission, Raman excitation, Raman, and 31P solid-state NMR measurements. Infrared and Raman spectra of the polyoxometalate/MCM-41 composite systems are interpreted as showing spectral shifts due to site induced electrostatic interactions. The photoluminescent behavior of the composite at room temperature indicates a characteristic Eu3+ emission pattern corresponding to 5D0- 7F(J) transitions. A strong photoluminescence suggests the potential utility of the polyoxometalate as a luminescent material. 相似文献
80.
The preparation of the alpha-1 and alpha-2 isomers of the Wells-Dawson 17 tungsto derivatives by standard methods is accompanied by a significant proportion of the other isomer present as an impurity. In this study, the alpha-1 and alpha-2 isomers of [Zn(H(2)O)P(2)W(17)O(61)](8)(-) have been prepared in >98% purity by reacting isomerically pure K(9)Li[alpha-1-P(2)W(17)O(61)] and K(10)[alpha-2-P(2)W(17)O(61)], respectively, with ZnCl(2), while rigorously controlling the pH at 4.7. The molecules were isolated as potassium salts. For (183)W NMR and (31)P NMR characterization, both molecules were ion exchanged by cation-exchange chromatography, maintaining the pH at 4.7, to obtain the lithium salts. Removal of water and isolation of a solid sample of [alpha-1-Zn(H(2)O)P(2)W(17)O(61)](8)(-) was achieved by lyophilization at -40 degrees C. The chemical shift data from (31)P and (183)W NMR spectroscopy of the isolated [alpha-1-Zn(H(2)O)P(2)W(17)O(61)](8)(-) and [alpha-2-Zn(H(2)O)P(2)W(17)O(61)](8)(-) isomers are consistent with a mixture of the alpha-1 and alpha-2 isomers reported previously;(1) the molecules have the expected C(1) and C(s)() symmetry, respectively. The [alpha-1-Zn(H(2)O)P(2)W(17)O(61)](8)(-) isomer is stable in the pH range of 4.6-6 at temperatures <35 degrees C. Using the same ion exchange and lyophilization techniques, the lacunary [alpha-1-P(2)W(17)O(61)](10)(-) isomer was isolated as the lithium salt; characterization by (183)W NMR spectroscopy confirms the C(1) symmetry. 相似文献