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611.
The electrical conductivity of molten binary and ternary mixtures based on the NaF-AlF3-SiO2 system was investigated by means of a tube-cell (composed of pyrolytic boron nitride) with stationary electrodes. An impedance/gain-phase analyser (National Instruments; a high-performance modular chassis controlled by Labview? software) was used for the cell impedance measurement. The conductivity was found to vary linearly with temperature in all the mixtures investigated. The concentration dependence of electrical conductivity (isotherms) thus obtained was divided into two parts. The first represents the concentration region of up to 10 mole % of SiO2, the second the region with a higher concentration of SiO2 (from 10 mole % to 40 mole %). While the conductivity decreased considerably with the concentration of SiO2 in the second part, it increased surprisingly in the low concentration range. From these results, the influence of electrolyte composition and temperature on the electrical conductivity was examined. 相似文献
612.
Liquid chromatographic analysis of milk samples from 6 cows treated with tylosin in a veterinary practice indicated that tylosin persisted in milk for more than 3 days after the final treatment. The concentration of tylosin was not below the stated maximum residue limit (0.05 mg/kg). The milk from 3 cows being treated for mastitis catarrhalis chronica contained tylosin residues for 3.5 days after the last withdrawal time (72 h). No residue was detected in the milk of any animal 6 days after cessation of therapy. 相似文献
613.
Martin A. Bennett Tai-Nang Huang Jozef L. Latten 《Journal of organometallic chemistry》1984,272(2):189-205
The η-hexamethylbenzenehydridoruthenium(II) complexes RuHCl(η-C6Me6)L (L = PPh3 (11), AsPh3 (12), P(C6H4-p-F)3 (14), P(C6H4-p-Me)3 (15), P(C6H4-p-OMe)3 (16), P-t-BuPh2 (17), P-i-PrPh2 (18), P-i-Pr3 (19), PCy3 (20) and P-t-BuMe2 (21)) have been made by heating [RuCl2(η-C6Me6)]2, the ligand and sodium carbonate in propan-2-ol. The triarylphosphine complexes 11, 14 and 15 react with methyllithium to give aryl ortho-metallated hydridoruthenium(II) complexes such as Ph2)(η-C6Me6) (22) and 19 similarly gives the isopropyl cyclometallated complex -i-Pr2(η-C6Me6) (29) as a mixture of diastereomers. Reaction of 17 with methyllithium gives initially the t-butyl cyclometallated complex Ph2)(η-C6Me6) (25) which isomerizes by a first order process (k.2 h?1 in C6D6 or THF-d8 at 50°C) to the aryl ortho-metallated complex -t-BuPh)(η-C6Me6) (26). The similarly generated isopropyl cyclometallated complex Ph2)(η-C6Me6) (27) has not been isolated in a pure state owing to rapid isomerization to -i-PrPh)(η-C6Me6) (28); both 27 and 28 exist as a pair of diastereomers. The formation of the cyclometallated complexes and the isomerizations are thought to involve intermediate 16-electron ruthenium(O) complexes Ru(η-C6Me6)L. 相似文献
614.
Surfactants are frequently used in the preparation of background electrolytes (BGEs) in capillary zone elcetrophoresis (CZE) in order to affect and to optimize both the electroosmotic flow (EOF) and the separation process. Their effects are, however, always multiple, the resulting situation may be very complex and the separation process may even be destroyed. We use the surfactant cetyltrimethylammonium bromide (CTAB) as a model example and bring experimental results and related discussion which elucidate the multiple effect of surfactants in an integrated way. It is shown that even at concentration levels lower than 10(-4) M CTAB strongly reduces the cathodic EOF in bare fused-silica capillaries and converts it into anodic EOF. The magnitude and polarity of the EOF depends not only on the concentration of CTAB but also on the composition of BGEs used. The interactions of CTA cations with the bare capillary wall reduce sorption of cationic analytes and enables their analysis. CTA cations at levels below their critical micelles concentration (CMC) already interact with anionic analytes and reduce their mobilities. This association is strong with highly charged anions and by this, the reversal of the EOF, applying BGEs with highly charged anions is less effective. These interactions are competitive and also depend on the composition of the BGE used. At levels above its CMC, CTAB forms micelles and enables the application of the micellar electrokinetic capillary chromatography (MEKC) mode and the analysis of, e.g., neutral components. Simultaneously, it is shown that the presence of CTAB may increase the number of potentially formed system zones. 相似文献
615.
Abstract— Absorption and fluorescence polarization spectra, as well as absolute fluorescence quantum yields, and lifetimes of phycobiliproteins separated from intact phycobilisomes of Porphyridium cruentum, Nostoc sp. and Fremyella diplosiphon were measured. Two different types of phycoerythrin, in addition to phycocyanin and allophycocyanin, were separated from both Porphyridium cruentum and Nostoc sp. phycobilisomes. They were distinguishable by the shape of their absorption spectra, values of fluorescence quantum yields and their limiting polarization. Phycobilisomes of Fremyella diplosiphon had a type of phycoerythrin that was different from the above kinds. By the use of fluorescence quantum yields and lifetime data, the values of natural lifetimes, the decadic molar extinction coefficients, as well as Förster's critical distances R 0 for excitation energy transfer, between phycobiliproteins in phycobilisomes, were estimated. The values obtained of Förster's critical distances indicate that for most efficient energy transfer from phycoerythrin to allophycocyanin, the outer layers of Porphyridium cruentum and Nostoc sp. phycobilisomes should be composed of bangiophycean, phycoerythrin and cyanophytan phycoerythrin-II respectively. 相似文献
616.
We demonstrate that system zones (SZs) can be expected in background electrolytes (BGEs) with a low buffer capacity. The mobilities of this type of SZ (m(SZ)) could be determined by calculations both based on a mathematical model and by a simulation program. The values of m(SZ) are increasing for decreasing buffer capacities and lower concentrations of the BGEs. For completely unbuffered BGEs with a pH below 7, the m(SZ) reached values up to 350x10(-9) m(2)V(-1)s(-1). This value indicates that the existence of this type of SZ originates from migrating hydrogen ions. Although both the mathematical model and simulation program do not consider the influence of the pH of the sample solution, experiments have shown that the pH of the sample solution is also very important. The lower the pH of the sample solution, the larger the m(SZ) in a specific BGE for cationic SZs. Using completely unbuffered BGEs the hydrogen ions present in the original sample start to migrate freely through the capillary tube with the mobility of a single hydrogen ion and cause stepwise disturbances in the base line of the detector trace. It is remarkable that this type of SZ appears not to affect the electromigration dispersion (EMD) in a strong way and so far only dips could be obtained experimentally. 相似文献
617.
Ladislav Petruš Mária Petrušová Duy-Phong Pham-Huu Erika Lattová Božena Pribulová Jozef Turjan 《Monatshefte für Chemie / Chemical Monthly》2002,133(4):383-392
Summary. Since the development of the Sowden methodology in the middle of the twentieth century, several other efficient and complementary methods for the transformation
of sugar nitromethyl groups to aldehyde functionalities in their free, hemiacetal, or otherwise derivatized forms have been
developed. Hydrogen peroxide oxidation as well as ozonolysis of 1-deoxyalditol-1-nitronates in aqueous solution provide free
aldoses, thus presenting alternatives to the well-known Nef reaction. When applied to 2,5- or 2,6-anhydro-1-deoxy-1-nitroalditols, also known also as glycosylnitromethanes, the Nef reaction fails, and the hydrogen peroxide oxidation overoxidizes the expected products to 2,5- or 2,6-anhydroaldonic acids.
On the other hand, the ozonolysis of such compounds under pH-controlled conditions results in up to 85% of the interesting glycosylformaldehydes. The Nef reaction carried out in anhydrous low alcohols, however, has revealed a new conversion of glycosylnitromethanes to glycosylmethanal
dialkyl acetals, even more interesting C-glycoside synthons. A similar acid-catalyzed methanolysis of 1-deoxyalditol-1-nitronates
leads to methyl furanosides. Finally, a treatment of per-O-substituted glycosylnitromethanes with tributyltin hydride in boiling
benzene causes their radical reduction under a nearly quantitative formation of glycosylmethanal oximes.
Received November 12, 2001. Accepted November 20, 2001 相似文献
618.
Jozef??imaEmail author Lucia?Horváthová Mário?Izakovi? 《Monatshefte für Chemie / Chemical Monthly》2004,135(1):5-12
Summary. Photoredox reactions occurring in irradiated methanolic solutions of trans-[Fe(N
2
O
2
) (CH3OH)N3], where N
2
O
2
2– are tetradentate open-chain N
2
O
2
-Schiff base N,N-ethylenebis(R-salicylaldiminato) or N,N-1-methylethylenebis(R-salicylaldiminato) ligands denoted as R-salen and R-sal(Me)en, respectively (R=H, 5-Cl, 5-Br, 4-OCH3), have been investigated and their mechanism has been proposed. The complexes are redox stable in the dark. Ultraviolet and/or visible irradiation of methanolic solutions of the complexes induces photoreduction of Fe(III) to Fe(II). As an intermediate, CH2OH radicals were identified by EPR spin trapping technique. The final product of the photooxidation coupled with the photoreduction of Fe(III) is formaldehyde. The efficiency of the photoredox processes is strongly wavelength dependent and influenced by the peripheral groups R of the tetradentate ligands. Differences between the course of photochemical changes induced by 254nm radiation and the other wavelengths of incident radiation is rationalized by involving azide anions photoreactivity in observed redox changes. 相似文献
619.
[chemical reaction: see text]. We report here the synthesis of the 5'-[benzhydryloxybis(trimethylsilyloxy)]silyl-2'-methylseleno-2'-deoxyuridine phosphoramidite and its incorporation into oligonucleotides by solid-phase synthesis. The coupling yield of this phosphoramidite into oligonucleotides is higher than 99%. We also demonstrate that this 2'-methylselenophosphoramidite is compatible with the 5'-silyl-2'-ACE chemistry, for longer Se-RNA solid-phase synthesis. Our preliminary NMR study on the synthesized 2'-Se-DNA has revealed a U(Se)-A base pair and a duplex structure formation when its complementary strand was present. 相似文献
620.
Electromigration dispersion (EMD) properties of background electrolytes (BGEs) used in capillary zone electrophoresis (CZE) are of key importance for the success of an analysis. The knowledge of these properties may serve well for the prediction of the asymmetry of peaks of analytes, for the prediction of unsafe regions where a strong interference of system zones may be expected, and for the selection of optimum conditions where the analytes of interest may give sharp and practically symmetric peaks. Present theories enable one to calculate and predict EMD properties of many BGEs but there is also a lot of BGEs that are beyond the present theoretical models as far as their composition and equilibria involved are considered. This contribution brings a method for assessment of EMD properties of any BGE from easily accessible experimental data. The method proposed is illustrated by model examples both for cationic and anionic separations. Imidazole acetate, histamine acetate, and histidine acetate served as model BGEs for cationic separations; as the model BGE for anionic separations, Tris-borate and sodium-borate BGEs have been selected since these buffers are frequently used and borate is well-known for its complexing equilibria in aqueous solutions. 相似文献