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41.
In this work, kinetic data of crystallization processes have been determined by measurement of the intensities of reflection of X-ray diffraction spectra and modeled using the Avrami-Eroféev and Jander expressions. We have created a simple Microsoft Excel spreadsheet that allows students to calculate the kinetic data. Students will be able to calculate the kinetic parameters of any crystallization process, for example, hydrothermal crystallization of catalytic materials like zeolites. The possibility of using the spreadsheet with different models or expressions and discriminating among them is also validated by comparing the model results with experimental data (differential thermal analyses, DTA) from papers available in the recent literature. 相似文献
42.
Photoprotection of Mammalian Acid-Soluble Collagen by Cuttlefish Sepia Melanin In Vitro 总被引:1,自引:0,他引:1
Julian M. Menter Abrienne M. Patta Thomas D. Hollins Cyril L. Moore Isaac Willis 《Photochemistry and photobiology》1998,68(4):532-537
Several important clinical conditions can result in close association between the pigment melanin and dermal collagen. Because melanin and its precursors can be chemically reactive in ground and excited states, it is important to know whether the resulting melanin-collagen interaction results in photoprotection or photoaggression. Acidic and neutral air-saturated collagen suspensions (0.033%) were irradiated with0–2.6 times 104 J/m2 UVC or with0–83 times 104 J/m2 solar-simulating UV radiation (SSR). Photochemical destruction of a photolabile collagen fluorophore (δem 360 nm) and collagen chain degradation were monitored as functions of irradiation time in the presence and absence of added (0–100μg) sepia eumelanin. Melanin retarded collagen photodamage but did not qualitatively alter the fluorescence fading kinetics. Both H202 and 02 can be produced by UV irradiation of eumelanin. Added H202 and K02 destroyed collagen fluorescence and caused 50% chain degradation at ca10–20-fold molar excess. Previous studies have demonstrated that eumelanins efficiently scavenge 02 . We demonstrated that eumelanin also efficiently scavenges H202 as evidenced by its ability to (a) compete with scopoletin for peroxide uptake and (b) directly take up H202 through a dialysis bag. The latter observation suggests that peroxide scavenging could occur in vivo by melanin sequestered in melanophages. Thus, neither UV-generated 02 nor H202 are likely to be present in concentrations high enough to cause measurable collagen damage. Absorption and/or scattering of excitation radiation away from the target chromophore appears to be the primary photoprotection mechanism, although scavenging of active 02 intermediates may play an important, if subtle role. 相似文献
43.
Emilio Bustelo Isaac de los Ríos Manuel J. Tenorio M. Carmen Puerta Pedro Valerga 《Monatshefte für Chemie / Chemical Monthly》2000,131(12):1311-1320
Summary. The solid-state tautomerization of the hydrido-alkynyl derivatives [Cp
*RuH(C&*CR)-(dippe)][BPh4] (Cp* = C5Me5; R = SiMe3, Ph, H; dippe = 1,2-bis-(diisopropylphosphino)-ethane) to their vinylidene isomers [Cp
*Ru*C*CHR(dippe)][BPh4] was studied by IR spectroscopy. Characteristic isothermic αvs. t curves for each individual rearrangement process were recorded. Their shape, and hence the isomerization mechanism, depends
strongly on the nature of the substituent R. The kinetic analysis of the above curves using the Avrami-Erofeev provided some mechanistic information about the isomerization process in the solid.
Received July 7, 2000. Accepted August 29, 2000 相似文献
44.
Gita Dvorakova Robert Haschick Khalid Chiad Markus Klapper Klaus Müllen Andrea Biffis 《Macromolecular rapid communications》2010,31(23):2035-2040
The preparation of nanosized, molecularly imprinted polymer particles by nonaqueous emulsion polymerization is presented. Monodisperse cross‐linked polymer nanospheres with a diameter of around 100 nm were synthesized using a standard monomer mixture of methacrylic acid and ethylene dimethacrylate, containing (±)‐propranolol as a template. The rebinding efficiency of the resulting particles was determined by batch rebinding tests and isothermal titration calorimetry (ITC). The results indicate that the proposed imprinting process under nonaqueous conditions lead to particles with an enhanced capacity of template rebinding compared to both nonimprinted ones and to particles obtained by more conventional emulsion polymerization in water.
45.
Gómez L Garcia-Bosch I Company A Sala X Fontrodona X Ribas X Costas M 《Dalton transactions (Cambridge, England : 2003)》2007,(47):5539-5545
A novel family of chiral manganese complexes Lambda-1(CF(3)SO(3)) and Delta-2(CF(3)SO(3)), have been stereoselectively prepared, characterized and studied as epoxidation catalysts. The complexes are structurally related to [Mn(II)(CF(3)SO(3))(2)(alpha-MCP)] (MCP=N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)cyclohexane-trans-1,2-diamine), recently reported as a very efficient epoxidation catalyst in combination with peracetic acid. Pinene rings have been fused to the 4 and 5 positions of the two pyridine groups of the ligand, giving rise to complexes where the two labile binding sites of the manganese ion are confined in a better-defined chiral pocket than in the parent [Mn(II)(CF(3)SO(3))(2)(alpha-MCP)]. Chirality in these complexes arises from the stereochemistry of the trans-diaminocyclohexane ring, from the pinene ring and also from the topological chirality adopted by the ligand upon binding to the manganese ion. While previous studies have demonstrated that small modifications in the structure of the MCP ligand result in a dramatic loss of efficiency, Lambda-1(CF(3)SO(3)) and Delta-2(CF(3)SO(3)) exhibit comparable catalytic activity to [Mn(II)(CF(3)SO(3))(2)(alpha-MCP)]. In addition, the complexes exhibit a remarkable stereoselectivity (up to 46% ee) in the epoxidation of selected substrates. The results reported in this work point towards modification of the 4 and 5 positions of the pyridine groups as a new strategy towards the design of stereoselective versions of this family of highly active and environmentally benign epoxidation catalysts. 相似文献
46.
Isaac Zigelboim Daniel Offen Eldad Melamed Hana Panet Moshe Rehavi Yoram Cohen 《Journal of inclusion phenomena and macrocyclic chemistry》2007,59(3-4):323-329
Although magnetic resonance imaging (MRI) is one of the most important imaging modalities of the central nervous system (CNS),
one of the main drawbacks of MRI is its limited specificity. This can potentially be partially alleviated by target-specific
contrast agents. In the present paper we describe a simple high yield synthesis of two such gadolinium-based spiperone targeted
MRI contrast agents, 1a and 1b. The R1 relaxivities of 1a and 1b were evaluated and found to be 5.94 and 8.31 mM−1 s−1, respectively at 9.4T, while their R2 relaxivities at the same magnetic field were found to be 18.05 and 22.60 mM−1 s−1, respectively. In addition and very importantly compound 1a, which is a gadolinium-based, spiperone-targeted MRI contrast agent, was found to preserve some of the spiperone affinity
toward the dopamine D2 receptor. Compounds 1a and 1b thus represent potential agents for in vitro dopamine receptor imaging using MRI in experimental models.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
47.
A versatile nonaqueous emulsion polyaddition process for the one-step fabrication of spherical polyurethane nanoparticles
is presented. Three different emulsion systems were used consisting of N,N′-dimethylformamide (DMF) dispersed in n-hexane, acetonitrile dispersed in cyclohexane, and acetonitrile dispersed in tetradecane. After successful stabilization
of the emulsion systems by using a poly(isoprene)-poly(methylmethacrylate) block copolymer, the fabrication of the polyurethanes
was carried out within the dispersed polar phase. The polyurethane particles showed average diameters as small as 35 nm. Additionally,
infrared (IR) characterization revealed that the formation of any urea, which decreases the mechanical properties of the polyurethanes,
was prevented during the polyaddition. This was attributed to the anhydrous reaction conditions. Gel permeation chromatography
(GPC) analysis demonstrated the average molecular weights (M
n) of the polyurethanes to be as high as 16,500 g/mol, corresponding to conversions of 0.98. Comparable molecular weights and
conversions have not previously been achieved without the formation of urea. 相似文献
48.
Biomolecules such as serum proteins can interact with drugs in the body and influence their pharmaceutical effects. Specific and precise methods that analyze these interactions are critical for drug development or monitoring and for diagnostic purposes. Affinity capillary electrophoresis (ACE) is one technique that can be used to examine the binding between drugs and serum proteins, or other agents found in serum or blood. This article will review the basic principles of ACE, along with related affinity-based capillary electrophoresis (CE) methods, and examine recent developments that have occurred in this field as related to the characterization of drug–protein interactions. An overview will be given of the various formats that can be used in ACE and CE for such work, including the relative advantages or weaknesses of each approach. Various applications of ACE and affinity-based CE methods for the analysis of drug interactions with serum proteins and other binding agents will also be presented. Applications of ACE and related techniques that will be discussed include drug interaction studies with serum agents, chiral drug separations employing serum proteins, and the use of CE in hybrid methods to characterize drug binding with serum proteins. 相似文献
49.
50.
Julian M. Menter Patricia P. Acin Robert M. Sayre † Isaac Willis 《Photochemistry and photobiology》1992,55(5):705-712
This work provides a dose-response model of UV-induced epidermal-stratum corneum thickening induced by irradiation at wavelength lambda. This model assumes that photobiochemical reaction(s) can give rise to hyperplasia in a manner which is predictable from a simple photochemical kinetic scheme. In this work, we derive an equation which predicts an approximately linear relationship between the logarithm of the increase in optical skin thickening measured at 320 nm (delta OD320) and total cumulative dose (DT) seen by the target cells in or near the basal layer. For each excitation wavelength lambda, the slope R(lambda) of the log delta OD320 vs DT plot is proportional to epsilon(lambda) phi rx, where epsilon(lambda) is the extinction coefficient for the target chromophore at excitation wavelength, and phi rx is the quantum yield for the photochemical reaction(s) leading to hyperplasia. Our data previously obtained from irradiation of SK-1 hairless mice with "monochromatic" UV wavebands at 280, 290, 300, 307 and 313 nm (Menter et al., 1988, Photochem. Photobiol. 47, 225-260.) and data from Sterenborg and van der Leun at 254 and 313 nm (1988, Photodermatology 5, 71-82) are in good agreement with this model, except for 254 and 280 nm excitation, which are greatly attenuated by epidermis-stratum corneum. For excitation at the latter wavelengths, "dark" regressive processes successfully compete with the "light" reaction(s) which lead to (pre)cancerous lesion. This difficulty notwithstanding, the "intrinsic" action spectrum for hyperplasia derived from these measurements indicates that the target chromophore preferentially absorbs in the UV-C region.(ABSTRACT TRUNCATED AT 250 WORDS) 相似文献