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571.
Jung C 《Analytical and bioanalytical chemistry》2008,392(6):1031-1058
Cytochrome P450 proteins (CYPs) are a big class of heme proteins which are involved in various metabolic processes of living
organisms. CYPs are the terminal catalytically active components of monooxygenase systems where the substrate binds and is
hydroxylated. In order to be functionally competent, the protein structures of CYPs possess specific properties that must
be explored in order to understand structure–function relationships and mechanistic aspects. Fourier transform infrared spectroscopy
(FTIR) is one tool that is used to study these structural properties. The application of FTIR spectroscopy to the secondary
structures of CYP proteins, protein unfolding, protein–protein interactions and the structure and dynamics of the CYP heme
pocket is reviewed. A comparison with other thiolate heme proteins (nitric oxide synthase and chloroperoxidase) is also included.
Figure The protein secondary structure, protein unfolding, redox-partner protein–protein interaction, structural changes induced
by the reduction of the heme iron, and the structure and dynamics of the active site of cytochromes P450 (CYP) can be studied
using Fourier transform infrared spectroscopy (FTIR). FTIR spectroscopy is a good approach for gaining a deeper insight into
structure–function relationships in CYPs.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
572.
[reaction: see text] Herein, we present a successful synthesis of the tricyclic core of vinigrol (1). Our approach takes advantage of a highly regioselective intramolecular Diels-Alder reaction of the diene 11 to construct two rings of the tricyclic vinigrol skeleton 12. 相似文献
573.
574.
Patricia Wollstadt Martina Hasenjger Christiane B. Wiebel-Herboth 《Entropy (Basel, Switzerland)》2021,23(2)
Entropy-based measures are an important tool for studying human gaze behavior under various conditions. In particular, gaze transition entropy (GTE) is a popular method to quantify the predictability of a visual scanpath as the entropy of transitions between fixations and has been shown to correlate with changes in task demand or changes in observer state. Measuring scanpath predictability is thus a promising approach to identifying viewers’ cognitive states in behavioral experiments or gaze-based applications. However, GTE does not account for temporal dependencies beyond two consecutive fixations and may thus underestimate the actual predictability of the current fixation given past gaze behavior. Instead, we propose to quantify scanpath predictability by estimating the active information storage (AIS), which can account for dependencies spanning multiple fixations. AIS is calculated as the mutual information between a processes’ multivariate past state and its next value. It is thus able to measure how much information a sequence of past fixations provides about the next fixation, hence covering a longer temporal horizon. Applying the proposed approach, we were able to distinguish between induced observer states based on estimated AIS, providing first evidence that AIS may be used in the inference of user states to improve human–machine interaction. 相似文献
575.
576.
Aquasols containing silica nanoparticles with diameters of 75 to 95 nm were obtained directly by hydrolysis of 2 wt.% tetraethoxysilane (TEOS) in water in the presence of a non-ionic surfactant. The reaction was catalyzed by hydrochloric acid, ammonia, or sodium hydroxide. The particle size, which mainly depends on the concentration of TEOS in water, was determined by dynamic light scattering (DLS). Whereas the catalysts have almost no influence on the particle size, they very strongly affect the morphology of the silica particles formed. The dried SiO(2) particles obtained via the HCl-catalyzed reaction have film-forming properties and show no measurable BET surface area. SiO(2) particles prepared with ammonia as catalyst form nanoporous films on glass, and the BET surface area of the freeze-dried particles is 540 m(2)/g. Using sodium hydroxide as catalyst results in some agglomeration of uniform spherical particles with a BET surface area of 237 m(2)/g. (29)Si MAS NMR investigations of the freeze-dried particles provide information about the degree of condensation and the ratio of "free" hydroxyl groups. The silica aquasols described have a surprisingly high hydrophilizing effect on hydrophobic fibers (PP, PET). Silica nanoparticles of comparable diameters, prepared by the "St?ber method", dispersed in alcohol do not show any hydrophilizing properties worth to mention. 相似文献
577.
von Eckstaedt CV Grice K Ioppolo-Armanios M Chidlow G Jones M 《Journal of chromatography. A》2011,1218(37):6511-6517
This paper describes the establishment of a robust method to determine compound specific δD and δ(13)C values of volatile organic compounds (VOCs) in a standard mixture ranging between C(6) and C(10) and was applied to various complex emission samples, e.g. from biomass combustion and car exhaust. A thermal desorption (TD) unit was linked to a gas chromatography isotope ratio mass spectrometer (GC-irMS) to enable compound specific isotope analysis (CSIA) of gaseous samples. TenaxTA was used as an adsorbent material in stainless steel TD tubes. We determined instrument settings to achieve a minimal water background level for reliable δD analysis and investigated the impact of storage time on δD and δ(13)C values of collected VOCs (176 days and 40 days of storage, respectively). Most of the standard compounds investigated showed standard deviations (SD)<6‰ (δD) when stored for 148 days at 4 °C. However, benzene revealed occasionally D depleted values (21‰ SD) for unknown reasons. δ(13)C analysis demonstrated that storage of 40 days had no effect on VOCs investigated. We also showed that breakthrough (benzene and toluene, 37% and 7%, respectively) had only a negligible effect (0.7‰ and 0.4‰, respectively) on δ(13)C values of VOCs on the sample tube. We established that the sample portion collected at the split flow effluent of the TD unit can be used as a replicate sample for isotope analysis saving valuable sampling time and resources. We also applied TD-GC-irMS to different emission samples (biomass combustion, petrol and diesel car engines exhaust) and for the first time δD values of atmospheric VOCs in the above range are reported. Significant differences in δD of up to 130‰ were observed between VOCs in emissions from petrol car engine exhaust and biomass combustion (Karri tree). However, diesel car emissions showed a high content of highly complex unresolved mixtures thus a baseline separation of VOCs was not achieved for stable hydrogen isotope analysis. The ability to analyse δD by TD-GC-irMS complements the characterisation of atmospheric VOCs and is maybe used for establishing further source(s). 相似文献
578.
Martine Croisy-Delcey Emile Bisagni Christiane Huel 《Journal of heterocyclic chemistry》1993,30(1):55-60
4-Chloroquinoline-5,8-dione ( 8a ) and 6-bromo-4-chloroquinoline-5,8-dione ( 8b ) were reacted with homophthalic anhydride to give tetracyclic compounds 10 and 11 respectively. The 6,11-dihydroxy derivative 12 was prepared in low yield by photochemical addition of benzocyclobutenedione to 4-chloroquinoline-5,8-dione ( 8a ) and in better yield through a Friedel-Crafts reaction of phthalic anhydride with 4-chloro-5,8-dimethoxyquinoline ( 7a ). Whereas 4-chloro-6-hydroxynaphtho[2,3-g]quinoline-5,12-dione ( 11 ) was substituted by amines in the usual way to the corresponding 4-amino-substituted derivatives, 4-chloro-11-hydroxynaph-tho[2,3-g]quinoline-5,12-dione ( 10 ) led to a mixture of 4-amino derivatives and the unexpected 2,6-disubstituted-imidazo[4,5,l-I-j]naphtho[2,3-g]quinolin-7-ones, 13a-b . 相似文献
579.
Frank Schwanke Oliver Safarowsky Christiane Heim Gabriele Silva Fritz Vgtle 《Helvetica chimica acta》2000,83(12):3279-3290
A new pathway for the supramolecular synthesis of oligocatenanes is developed. It is based on a combination of most suitable macrocyclic structural units, obtained from tert‐butyl‐substituted isophthalic acid and terephthalic acid building blocks. These structural parts guarantee, on the one hand, the solubility of the catenanes and their intermediates, and, on the other hand, the preferred formation of larger ring sizes of the macrocycles to be intertwined. Acting as monotopic and ditopic concave templates, the tetra‐ and octalactam macrocycles were submitted to threading procedures to yield higher‐order catenanes of the amide type. By repetition of the threading steps, it was possible to isolate multiply mechanically connected [n]catenanes up to n=4 composed of various macrocyclic units. 相似文献
580.
Roseli M. de Souza Andr L. Saraceno Christiane Duyck Carmem Lúcia P. da Silveira Ricardo Q. Auclio 《Microchemical Journal》2007,87(2):99-103
A simple procedure for the extraction of Fe, Ni and V from asphaltene into acid solutions prior to the ICP OES determination is proposed. Either sonication or vortex agitation was used to disperse the organic sample into concentrated nitric acid, achieving efficient analyte extraction into the aqueous acid solution. Both procedures were compared and the advantage of the ultrasound-assisted procedure was evaluated. In both cases, pre-heating of sample–acid mixtures was necessary to enable quantitative extractions. Optimized conditions for the ultrasonic bath were established: 1 L of water at room-temperature, 20 min of sonication and tubes (maximum of eight) in vertical position. By using the vortex, 50 min of vigorous mechanical agitation was needed for each one of the tubes containing samples. The acid solution obtained after extraction was directly aspirated into the ICP in order to perform quantification by optical emission. Calibration was made with aqueous analyte standards containing Sc as internal standard. The procedures were tested using certified fuel oil (SRM NIST 1634c) and the method was applied for the determination of Fe, V and Ni in one asphaltene sample obtained by the fractionation of the SRM NIST 1634c. Recoveries above 90% were achieved and limits of quantification in the asphaltene sample were 1.5, 15 and 1.0 μg g− 1 estimated for Fe, Ni and V, respectively. 相似文献