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181.
Jean F. M. Oth 《Colloid and polymer science》1960,168(1):49-56
Résumé Nous avons mesuré, en fonction de la température, le degré de gonflement dans l'eau de fibres de collagène amorphes qui ont
été tannées différemment, ceci dans le but de pouvoir déterminer, pour chaque degré de tannage (pontage chimique) la chaleur
de mélange du collagène amorphe sec avec l'eau de gonflement.
En utilisant la théorie relative au gonflement des réseaux polymériques amorphes dans un excès de diluant, on a pu montrer
que le paramètre thermodynamiqueχ
1 caractéristique du système collagène-eau (paramètre deFlory-Huggins) varie avec la composition du réseau gonflé. Par contre, le paramètre ?enthalpique? correspondantϰ
1=−
=−0,34 est indépendant de cette composition.
La chaleur de mélangeΔH
mél/V
0 d'un cm3 de collagène amorphe sec avec l'eau de gonflement peut être calculée pour les différents degrées de tannage. Elle a le signe
deϰ
1, i. e. elle est négative et est donnée par:ΔH
mél/V
0=RT gK1(1−v2
éq).
Sa valeur absolue est donc d'autant moins importante que le degré de tannage des fibres est poussé; v2
éq augmente en effet avec la concentration en liens intermoléculaires introduits dans les échantillons.
La variation d'enthalpie accompagnant la transformation d'une fibre de collagène cristalline sèche en fibre amorphe gonflée
(enthalpie de rétraction dans l'eau) diminuée de la chaleur de mélange correspondant au gonflement de la fibre amorphe sèche
dans l'eau donne la chaleur de fusion du collagène sec. Cette quantité est égale à:ΔH/V
0=28±1,5 cal./cm3 et est indépendante du degré de tannage comme on doit s'y attendre.
Travail effectué au Laboratoire de Chimie-Physique de l'Université de Liège, Liège (Belgique). 相似文献
Summary We have measured the temperature dependence of the swelling of amorphous collagen fibres of different degrees of tanning in an excess of water. This was done for the purpose of determining the heat of mixing of amorphous dry collagen with the equilibrium swelling water for each degree of tanning (chemical crosslinking). Using the theory of swelling of polymeric networks in an excess of diluent we were able to show that the parameterχ 1 of the system collagen-water (Flory-Huggins parameter) is a function of the composition of the swollen network. On the other hand, the energy parameterϰ 1=− =−0,34 is found to be concentration independent. The heat of mixingΔH mél/V 0 of 1 cm3 of dry amorphous collagen with the equilibrium swelling water can be calculated for the different degrees of tanning. It has the same sign asϰ 1, i. e. is negative, and is given byΔH mél/V 0=RTϰ 1 (1−v2 éq). Its absolute value decreases therefore with increasing degrees of tanning, sincev 2 éq increases with the density of the cross-links in the sample. The change in heat content on transforming 1 cm3 of dry crystalline collagen fibre into amorphous swollen fibre (heat of shrinking in water), decreased by the heat of swelling of the dry amorphous fibre in water, gives the heat of fusion of dry collagen. This latter equalsΔH/V 0=28±1.5 cal/cm3 and is, as expected, independent of the degree of tanning.
Zusammenfassung Um die Mischungsw?rme des amorphen trockenen Kollagens mit dem Quellungswasser zu bestimmen, wurde die Temperaturabh?ngigkeit des Quellungsgrades von verschieden stark gegerbten amorphen Kollagenfasern gemessen. Auf Grund der Theorie der Quellung von amorphen polymeren Netzwerken in einem überschu? von Quellungsmittel konnte gezeigt werden, da? der thermodynamische (Flory- Huggins) Parameterχ 1 für das System Kollagen-Wasser vom Quellungsgrad des Netzwerkes abh?ngt. Hingegen ist der Enthalpieparameterϰ 1=− =−0,34 davon unabh?ngig. Die Mischungsw?rmeΔH mél/V0 eines cm3 trockenen amorphen Kollagens mit dem Quellungswasser kann für verschiedene Gerbungsgrade (Vernetzungsgrade) berechnet werden. Sie hat das gleiche Vorzeichen wieϰ 1 d. h. ist negativ, und gehorcht der Gleichung:ΔH mél/V 0=RTϰ 1 (1−v2 éq). Der Betrag der Mischungsw?rme ist um so kleiner, je h?her der Gerbungsgrad der Faser ist; in der Tat w?chstv 2 éq mit der Konzentration der Vernetzungspunkte an. Wenn von der Enthalpie?nderung, welche mit dem übergang von einer trockenen kristallinen Faser zu einer gequollenen amorphen verbunden ist, (Schrumfungsenthalpie im Wasser), die oben definierte QuellungsenthalpieΔH mél/V 0 abgezogen wird, so bleibt die Schmelzw?rme des trockenen Kollagens übrig. Diese Schmelzw?rme betr?gt:ΔH/V 0=28±1,5 cal./cm3 und ist, wie zu erwarten, vom Vernetzungsgrad (Gerbungsgrad) des Fadens unabh?ngig.
Travail effectué au Laboratoire de Chimie-Physique de l'Université de Liège, Liège (Belgique). 相似文献
182.
Furuta P Brooks J Thompson ME Fréchet JM 《Journal of the American Chemical Society》2003,125(43):13165-13172
The site isolation of two dyes capable of electronic interaction via Forster energy transfer has been studied with the two dyes coumarin 343 and pentathiophene encapsulated by dendrons containing both solubilizing and electroactive moieties. Photoluminescence studies of mixtures of the dendritic dyes show that at high dendron generation, significant site isolation is achieved with relative emission characteristics influenced by both the degree of site isolation and the emission quantum yield of the dyes. Electroluminescence studies carried out in organic light emitting diode devices confirm that color tuning may be achieved by mixing the two encapsulated dyes in a single layer. However, selective carrier trapping by one of the core component dyes can dramatically influence the effectiveness of other components in the device. 相似文献
183.
The reversible folding of deca-alanine is chosen as a test case for characterizing a method that uses an adaptive biasing force (ABF) to escape from the minima and overcome the barriers of the free-energy landscape. This approach relies on the continuous estimation of a biasing force that yields a Hamiltonian in which no average force is exerted along the ordering parameter xi. Optimizing the parameters that control how the ABF is applied, the method is shown to be extremely effective when a nonequivocal ordering parameter can be defined to explore the folding pathway of the peptide. Starting from a beta-turn motif and restraining xi to a region of the conformational space that extends from the alpha-helical state to an ensemble of extended structures, the ABF scheme is successful in folding the peptide chain into a compact alpha helix. Sampling of this conformation is, however, marginal when the range of xi values embraces arrangements of greater compactness, hence demonstrating the inherent limitations of free-energy methods when ambiguous ordering parameters are utilized. 相似文献
184.
Chemical investigation of the dichloromethane extract of the Red Sea marine sponge Lamellodysidea herbacea led to the isolation of seven new polychlorinated derivatives 3-6 and 8-10 in addition to the known dysidamide 1, dysidamide B 2 and dysidamide C 7. Their structures were established by extensive NMR spectroscopic data. The absolute configuration of compound 9 was determined by X-ray crystallographic diffraction analysis. Dysidamide 1 exhibited neurotoxic effects towards both mesencephalic and cortical murine neurones at 0.8 μg/ml. 相似文献
185.
Shen R Lin CT Bowman EJ Bowman BJ Porco JA 《Journal of the American Chemical Society》2003,125(26):7889-7901
The total synthesis and stereochemical assignment of the potent antitumor macrolide lobatamide C, as well as synthesis of simplified lobatamide analogues, is reported. Cu(I)-mediated enamide formation methodology has been developed to prepare the highly unsaturated enamide side chain of the natural product and analogues. A key fragment coupling employs base-mediated esterification of a beta-hydroxy acid and a salicylate cyanomethyl ester. Three additional stereoisomers of lobatamide C have been prepared using related synthetic routes. The stereochemistry at C8, C11, and C15 of lobatamide C was assigned by comparison of stereoisomers and X-ray analysis of a crystalline derivative. Synthetic lobatamide C, stereoisomers, and simplified analogues have been evaluated for inhibition of bovine chromaffin granule membrane V-ATPase. The salicylate phenol, enamide NH, and ortho-substitution of the salicylate ester have been shown to be important for V-ATPase inhibitory activity. 相似文献
186.
Electrochromatography (EC) in microfluidic chips is emerging as an attractive alternative to capillary electrophoresis (CE) for on-chip separations. This review summarizes recent developments in the rapidly growing area of chip electrochromatography with a focus on "column" technologies. Relevant achievements are summarized according to the types of stationary phase used for the separations including open channels, microfabricated structures, and channels packed with beads or containing a porous monolith. The advantages and disadvantages of each, as well as practical aspects of their application, are discussed. The analytical performance of these devices is demonstrated with separations involving various families of compounds mostly in the reversed-phase chromatographic mode. 相似文献
187.
Graziano Bonetti Patrick Pibarot Alain Chaintreau Jean Paul Marion 《Journal of separation science》1992,15(5):305-306
The use of diethylene glycol monoethyl ether as a flavor solvent is restricted. Since existing methods of quantitation are tedious or require sophisticated multi-dimensional GC instrumentation, a simple method has been developed using low cost GC-MS. Monitoring of ions 31 and 45 enables quantitation of DEGEE in essential oils at levels down to 1 μg/g with accuracy equal to or better than 15%. 相似文献
188.
Poly(ethylene glycol) (PEG 3400) was used as a soluble polymeric support for the synthesis of a series of novel benzazepines. The key step for the preparation of these heterocycles was a phosphine-free palladium-catalyzed Heck reaction. Palladium nanoparticles formed during the course of the reaction were characterized. The presence of PEG 3400 influenced the outcome of the reaction in terms of selectivity. 相似文献
189.
Weeber JC Finot E Legay G Cathelat A Lacroute Y Dereux A 《Langmuir : the ACS journal of surfaces and colloids》2004,20(23):10179-10185
We report on the near-field imaging of microstructured polymer layers deposited on an homogeneous metal thin film on which a surface plasmon mode is excited. The microstructures in the polymer layers are designed by electron beam lithography, and the near-field imaging is performed with a photon scanning tunneling microscope (PSTM). We show that, despite their very small height, the microstructures can be conveniently imaged with a PSTM thanks to the field enhancement at the surface of the metal thin film supporting the surface plasmon. The influence of the illumination conditions on the contrast of the PSTM images is discussed. In particular, we show that both the field enhancement and the near-field intensity distribution around the microstructures depend dramatically upon the illumination conditions, leading to the conclusion that the PSTM is well suited for spatially resolved near-field surface plasmon sensing purposes. 相似文献
190.
Frère P Allain M Elandaloussi el H Levillain E Sauvage FX Riou A Roncali J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):784-792
The electrochemical and chemical oxidation of extended TTF 4 and 5 are analysed by cyclic voltammetry, Visible/NIR and ESR spectroscopies, and the X-ray structures of the new salts 5 x BF(4)(CH(2)Cl(2)) and 4 x ClO(4)(THF)(1/2) are presented. The effects of structural factors on the pi-dimerization or the disproportionation reaction of the cation radical are shown. The oxidation of compound 4 presents the successive formation of stable cation radical and dication species both in dichloromethane (DCM) and in a CH(3)CN/THF mixture. In contrast, for compound 5, the stability of the oxidation states strongly depends on the nature of the solvent. In DCM, the oxidation of 5 proceeds by two close one-electron transfers while in CH(3)CN/THF the dication is directly formed via a two-electron process. The X-ray structures of the two salts reveal the formation of pi-dimers of cation radical. While the dimer (5(2))(2+) is due mainly to pi-pi interactions between the conjugating spacer, the multiplication of the sulfur atoms in compound 4 contributes to stabilize the dimer by the combined effects of S-S and pi-pi interactions. Visible/NIR and ESR experiments confirm the higher tendency of 4(+)(.) to dimerize with the occurrence of dimer and monomer in solution, while for 5(+)(.) only the monomer is detected in DCM. On the other hand, by dissolution of 5 x BF(4)(CH(2)Cl(2)) in CH(3)CN, only the neutral and the dicationic states of compounds 5 are observed owing to the disproportionation reaction. 相似文献