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81.
Kundu SK Matsunaga T Yoshida M Shibayama M 《The journal of physical chemistry. B》2008,112(37):11537-11541
The hydrogel consisting of an oligomeric electrolyte, poly[pyridinium-1,4-diyl-iminocarbonyl-1,4-phenylenemethylene chloride] ( 1-Cl) underwent self-healing at temperatures lower than its gelation temperature after destruction of the gel network in a shear flow. The self-healing mechanism was investigated by rheological measurements on three different kinds of gels including a low-molecular weight organogelator and a polymeric hydrogelator. Although all of the three gels exhibited thermo-reversible hysteresis loops in the shear moduli, only 1-Cl hydrogel recovered its mechanical properties after vigorous agitation. It is conjectured that the self-healing is due to formation of network structure via a chlorine ion mediated hydrogen bond for which the activation energy is on the order of 10 kJ/mol. 相似文献
82.
Wada M Yokota C Ogata Y Kuroda N Yamada H Nakashima K 《Analytical and bioanalytical chemistry》2008,391(3):1057-1062
A sensitive high-performance liquid chromatography (HPLC)–fluorescence method for determination of morphine (Mor) in rat brain
and blood microdialysates was developed using 4-(4,5-diphenyl-1H-imidazol-2-yl)benzoyl chloride (DIB-Cl) as a label. Mor was labeled with DIB-Cl under mild reaction conditions (at room temperature
for 10 min). The separation of DIB-Mor was carried out on an octadecylsilica (ODS) column with CH3CN/0.1 M acetate buffer (pH 5.4) within 14 min. The detection limits of Mor in brain and blood microdialysates at a signal-to-noise
ratio of 3 were 0.4 and 0.6 ng mL−1, respectively. The proposed method was successfully applied to the preliminarily study of potential pharmacokinetic interaction
between Mor and diclofenac. 相似文献
83.
Trehalose is a non-reducing disaccharide that is found in many organisms but not in mammals. This sugar plays important roles in cryptobiosis of selaginella mosses, tardigrades (water bears), and other animals which revive with water from a state of suspended animation induced by desiccation. The interesting properties of trehalose are due to its unique symmetrical low-energy structure, wherein two glucose units are bonded face-to-face by 1-->1-glucoside links. The Hayashibara Co. Ltd., is credited for developing an inexpensive, environmentally benign and industrial-scale process for the enzymatic conversion of alpha-1,4-linked polyhexoses to alpha,alpha-D-trehalose, which made it easy to explore novel food, industrial, and medicinal uses for trehalose and its derivatives. Trehalosechemistry is a relatively new and emerging field, and polymers of trehalose derivatives appear environmentally benign, biocompatible, and biodegradable. The discriminating properties of trehalose are attributed to its structure, symmetry, solubility, kinetic and thermodynamic stability and versatility. While syntheses of trehalose-based polymer networks can be straightforward, syntheses and characterization of well defined linear polymers with tailored properties using trehalose-based monomers is challenging, and typically involves protection and deprotection of hydroxyl groups to attain desired structural, morphological, biological, and physical and chemical properties in the resulting products. In this review, we will overview known literature on trehalose's fascinating involvement in cryptobiology; highlight its applications in many fields; and then discuss methods we used to prepare new trehalose-based monomers and polymers and explain their properties. 相似文献
84.
Ohyama K Oyamada K Kishikawa N Ohba Y Wada M Maki T Nakashima K Kuroda N 《Journal of chromatography. A》2008,1208(1-2):242-245
Three new chiral stationary phases with different lengths of l-phenylalanine peptide were prepared by solid-phase synthesis with tert-butoxycarbonyl (Boc)-l-phenylalanine on silica. The effect of phenylalanine peptide length on enantioselectivity was studied. The best separation of R/S-warfarin was achieved by the chiral stationary phase with intermediate peptide length. These stationary phases were found to exist mainly in alpha-helical conformation by using FT-IR spectra. The end-capping reagents for the N-terminus of the peptide were also evaluated. 相似文献
85.
Nakamura S Yonehara M Uchiyama M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(4):1068-1078
Silylmetalation of alkenes is challenging due to the low reactivity of the substrates. In contrast, carbometalation of alkenes has been realized through several innovative methods, including activation of the reagent and the substrate. A similar approach could be applicable to silylmetalation of alkenes, and we have recently developed a bimetal activation method using zincate complexes for this purpose. Here, we describe how the silylzincation of alkenes was achieved. First, the strategies for carbometalation of alkenes will be summarized. Secondly, the history and development of silylzincation chemistry are briefly described. Then the details of our findings related to two types of silylzincation of alkenes, as well as recent progress in mechanistic studies, are discussed. The key point in the silylzincation of alkenes proved to be the bimetal activation of the substrate. One metal (copper or titanium) strongly coordinates and activates the alkene moiety, and the other metal (zinc) acts as the electron acceptor from the silyl group by way of the alkene moiety. This dual activation concept is expected to be applicable to other combinations of metals, as well as to new types of reactions. 相似文献
86.
Choshi T Uchida Y Kubota Y Nobuhiro J Takeshita M Hatano T Hibino S 《Chemical & pharmaceutical bulletin》2007,55(7):1060-1064
An asymmetric synthesis of the core carbazole structure, 6-desprenyl-carquinostatin 3 and 6-descycloavandulyl-lavanduquinocin 3, toward a total synthesis of carquinostatin A (1) and lavanduquinocin (2), has been established. Lipase QLM (Meito) catalyzed enantioselective acetylation of the racemic alcohol 6 gave the (-)-acetate 7 and the (+)-alcohol 6 with high enantioselectivity. The absolute stereochemistry of the (-)- and (+)-alcohol 6 have been determined to be R- and S-configurations, respectively, by the advanced Mosher method. In the same manner, the (-)-acetate 13 and the (+)-alcohol 12 have been obtained from the racemic alcohol 12. The (R)-(-)-acetate 13, derived from the (R)-(-)-acetate 7, was the same as the (-)-acetate 13, which has been determined to be (R)-configuration. Oxidation of the (R)-(-)-acetate 13 followed by hydrolysis afforded (R)-(-)-6-desprenyl-carquinostatin [and (R)-(-)-6-descycloavandulyl-lavanduquinocin] 3. In addition, oxidation of the (S)-(+)-alcohol 12 provided (S)-(+)-3, which is the enantiomer of 6-desprenyl-carquinostatin A (R)-(-)-3. 相似文献
87.
Pressure-induced reentrant micellization of amphiphilic block copolymers in dilute aqueous solutions
Osaka N Miyazaki S Okabe S Endo H Sasai A Seno K Aoshima S Shibayama M 《The Journal of chemical physics》2007,127(9):094905
The pressure-induced structural changes of a block copolymer, poly(2-ethoxyethoxyethyl vinyl ether)-block-poly(2-hydroxyethyl vinyl ether) (pEOEOVE-b-pHOVE) in aqueous solutions, were studied by means of small-angle neutron scattering (SANS) and dynamic light scattering (DLS) from atmospheric pressure up to 400 MPa. pEOEOVE-b-pHOVE formed a spherical micellar structure above 40 degrees C due to poor solubility of pEOEOVE. Micellization phase diagram was determined by DLS, and a covex-upward pressure-temperature (P-T) phase diagram was obtained having a peak around (P,T)=(150 MPa,48 degrees C). The SANS curves at 50 degrees C were analyzed as a function of P. The micellar core size decreased by pressurizing at low P's (P相似文献
88.
A novel method for determining mode power distribution in a two-mode fiber illuminated by an offset beam by measuring the near field pattern on the test fiber endface is developed. This method utilizes the different field symmetries of the fundamental and the second order modes. Coupling efficiencies from a quasi Gaussian beam to the fundamental and the second order modes in a two mode fiber were measured by the new technique for various offset launching conditions, and were in good agreement with the theoretical ones. 相似文献
89.
A group of B-site partially substituted strontium cobaltites Sr0.9Ca0.1Co0.9B'0.1O2.5+δ (B'=Mn, Co, Ni, In, Fe and Al) were examined for phase transformation and oxygen permeation properties. As revealed by XRD
analysis, these oxides had 2H-BaNiO3-type structure (B'=Mn, Co, Ni and In) or brownmillerite-type structure (B'=Fe and Al) and transformed into perovskite-type
structure at elevated temperatures (750 °C or above). The transformation temperature was dependent on the B-site substituent
and agreed well with the switching-on temperature of oxygen permeation for the same oxide. Due to a lowering in transformation
temperature, the Fe- or Al-doped oxide was made oxygen permeable in the lower temperature range 750–850 °C where the undoped
oxide remained non-permeable. It was also found that for a series of Fe-partially substituted samples Sr0.9Ca0.1Co1−xFexO2.5+δ the transformation temperature lowered with increasing x up to 0.1, while, for x≥0.2, perovskite-type structure tended to
be stabilized at room temperature. TGDTA analysis revealed that phase transformation was accompanied by absorption or desorption
of oxygen. Based on the correlation between the oxygen permeability and the membrane thickness, the rate-determining step
of oxygen permeation in the present system was assumed to be of the bulk diffusion of oxide ion vacancies. 相似文献
90.
Mitsuhiro Ebara Takao Aoyagi Kiyotaka Sakai Teruo Okano 《Journal of polymer science. Part A, Polymer chemistry》2001,39(3):335-342
Aqueous gel deswelling rates for copolymer hydrogels comprising N‐isopropylacrylamide (IPAAm) and 2‐carboxyisopropylacrylamide (CIPAAm) in response to increasing temperatures were investigated. Compared with pure IPAAm‐based gels, IPAAm–CIPAAm gels shrink very rapidly in response to small temperature increases across their lower critical solution temperature (their volume is reduced by five‐sixths within 60 s). Shrinking rates for these hydrogels increase with increasing CIPAAm content. In contrast, structurally analogous IPAAm–acrylic acid (AAc) copolymer gels lose their temperature sensitivity with the introduction of only a few mole percent of AAc. Additionally, deswelling rates of IPAAm–AAc gels decrease with increasing AAc content. These results indicate that IPAAm–CIPAAm copolymer gels behave distinctly from IPAAm–AAc systems even if both comonomers, CIPAAm and AAc, possess carboxylic acid groups. Thus, we propose that the sensitive deswelling behavior for IPAAm–CIPAAm gels results from strong hydrophobic chain aggregation maintained between network polymer chains due to the similar chemical structures of CIPAAm and IPAAm. This structural homology facilitates aggregation of chain isopropylamide groups for both IPAAm and CIPAAm sequences with increasing temperature. The incorporation of AAc, however, shows no structural homology to IPAAm, inhibiting chain aggregation and limiting collapse. A functionalized temperature‐sensitive poly(N‐isopropylacrylamide) hydrogel containing carboxylic acid groups is possible with CIPAAm, producing rapid and large volume changes in response to smaller temperature changes. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 335–342, 2001 相似文献