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71.
Localized Mixed‐Valence and Redox Activity within a Triazole‐Bridged Dinucleating Ligand upon Coordination to Palladium 下载免费PDF全文
Daniël L. J. Broere Raoul Plessius Dr. Joanne Tory Dr. Serhiy Demeshko Prof. Dr. Bas de Bruin Dr. Maxime A. Siegler Prof. Dr. Frantisek Hartl Dr. Jarl Ivar van der Vlugt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(39):13965-13975
The new dinucleating redox‐active ligand ( LH4 ), bearing two redox‐active NNO‐binding pockets linked by a 1,2,3‐triazole unit, is synthetically readily accessible. Coordination to two equivalents of PdII resulted in the formation of paramagnetic (S= ) dinuclear Pd complexes with a κ2‐N,N′‐bridging triazole and a single bridging chlorido or azido ligand. A combined spectroscopic, spectroelectrochemical, and computational study confirmed Robin–Day Class II mixed‐valence within the redox‐active ligand, with little influence of the secondary bridging anionic ligand. Intervalence charge transfer was observed between the two ligand binding pockets. Selective one‐electron oxidation allowed for isolation of the corresponding cationic ligand‐based diradical species. SQUID (super‐conducting quantum interference device) measurements of these compounds revealed weak anti‐ferromagnetic spin coupling between the two ligand‐centered radicals and an overall singlet ground state in the solid state, which is supported by DFT calculations. The rigid and conjugated dinucleating redox‐active ligand framework thus allows for efficient electronic communication between the two binding pockets. 相似文献
72.
Hongxiang Teng Liang Yang Frantisek Mikes Yasuhiro Koike Yoshiyuki Okamoto 《先进技术聚合物》2007,18(6):453-457
Copolymers of methyl methacrylate (MMA) with 2,3,5,6‐tetrafluorophenyl methacrylate (TFPMA), pentafluorophenyl methacrylate (PFPMA), and 4‐trifluoromethyl‐2,3,5,6‐tetrafluorophenyl methacrylate (TFMPMA) were investigated. All the three systems showed a random copolymerization character. The composition, glass transition temperature (Tg), and refractive index of the copolymers obtained were studied. Tgs of TFPMA/MMA and PFPMA/MMA copolymers were found to deviate positively from the Gordon–Taylor equation. However, Tgs of TFMPMA/MMA copolymers were well fit with the Gordon–Taylor equation. These results indicated the existence of interaction between MMA and either TFPMA or PFPMA units in copolymers. This interaction resulted in the enhancement of the Tg of MMA polymers through the copolymerization with TFPMA and PFPMA. The refractive index and the light transmittance of copolymers were close to those of PMMA. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
73.
Ivo Nischang Oliver Brueggemann Frantisek Svec 《Analytical and bioanalytical chemistry》2010,397(3):953-960
Porous polymer monoliths have emerged as unique materials for many applications, including liquid-chromatographic analyses
at an unrivaled speed, solid-phase extraction, and enzyme immobilization in capillary and microfluidic chip format. This article
reviews the state of the art in the preparation of monoliths in narrow-bore capillaries and microfluidic chips and their miniaturization
under conditions of spatial confinement. New developments in their preparation mainly using free radical polymerization techniques
with a focus on morphological aspects in view of homogeneous porous materials are described. The suitability of monoliths
for analysis of both large and small molecules is also discussed. 相似文献
74.
Otevrel J Mandelova Z Pesko M Guo J Kralova K Sersen F Vejsova M Kalinowski DS Kovacevic Z Coffey A Csollei J Richardson DR Jampilek J 《Molecules (Basel, Switzerland)》2010,15(11):8122-8142
In this study, a series of twelve ring-substituted salicylanilides and carbamoylphenylcarbamates were prepared and characterized. The compounds were analyzed using RP-HPLC to determine lipophilicity. They were tested for their activity related to the inhibition of photosynthetic electron transport (PET) in spinach (Spinacia oleracea L.) chloroplasts. Moreover, their site of action in the photosynthetic apparatus was determined. Primary in vitro screening of the synthesized compounds was also performed against mycobacterial, bacterial and fungal strains. Several compounds showed biological activity comparable with or higher than the standards 3-(3,4-dichlorophenyl)-1,1-dimethylurea, isoniazid, penicillin G, ciprofloxacin or fluconazole. The most active compounds showed minimal anti-proliferative activity against human cells in culture, indicating they would have low cytotoxicity. For all compounds, the relationships between lipophilicity and the chemical structure are discussed. 相似文献
75.
It is proved that if a Schur superalgebra is not semisimple,then it is neither cellular nor quasi-hereditary (Theorem 2),and it has infinite global dimension (Corollary 18). The algebraS(m|n, r) with m, n 1 is semisimple if and only if p, the characteristicof the ground field, is zero or greater than r, or when m =n = 1 and p does not divide r. 2000 Mathematics Subject Classification17A70 (primary), 20C30 (secondary). 相似文献
76.
Monolithic columns for capillary electrochromatography are receiving quite remarkable attention. This review summarizes results excerpted from numerous papers concerning this rapidly growing area with a focus on monoliths prepared from synthetic polymers. Both the simplicity of the in situ preparation and the large number of readily available chemistries make the monolithic separation media a vital alternative to capillary columns packed with particulate materials. Therefore, they are now a well-established stationary phase format in the field of capillary electrochromatography. A wide variety of synthetic approaches as well as materials used for the preparation of the monolithic stationary phases are presented in detail. The analytical potential of these columns is demonstrated with separations involving various families of compounds and different chromatographic modes. 相似文献
77.
Determination of 1-methylhistidine and 3-methylhistidine by capillary and chip electrophoresis with contactless conductivity detection 总被引:1,自引:0,他引:1
CE with capacitively coupled contactless detection (C4D) was used to determine 3-methylhistidine (3-MH) and 1-methylhistidine (1-MH). The C4D response to 3-MH was studied in a BGE consisting of 500 mM acetic acid and ammonia at varying concentration and the results were compared with the theory. Complete separation of a model mixture of 3-MH, 1-MH, and histidine (His) was attained in two optimized BGEs, one containing 500 mM HAc, 20 mM NH4OH, and 0.1 % m/v hydroxyethylcellulose (HEC), pH 3.4 (I) and the other consisting of 100 mM morpholinoethanesulfonic acid (MES), 25 mM LiOH, and 0.1 % m/v HEC, pH 5.5 (II). These optimized BGEs were tested in CE/C4D analyses of urine. Promising results were obtained for separation and determination of 3-MH, 1-MH, and His on a silicon microchip, using aluminum strips as the C4D electrodes; the three analytes were baseline-separated within less than 30 s with a separation channel effective length of 38 mm. The LOD were satisfactory and amounted to 26.4 microM for 3-MH and 18.3 microM for 1-MH. 相似文献
78.
A simple and cost-effective laboratory-made liquid junction interface was used for coupling of CE with MS. In this device the capillary column and the spray tip were positioned in the electrode vessel containing appropriate spray liquid. The electrospray potential was applied on the electrode inside the liquid junction. A stable electrospray was produced at nanoliter per minute flow rates generated in the emitter tip without using an external pump. This arrangement provided high durability of the spray tip and independent optimization of the CE separation (use of coated capillaries) and ESI conditions. CE-MS analysis of mixtures of drugs, peptides, tryptic digests of proteins and biological fluids was optimized with respect to the effects of the distance between the separation capillary and electrospray tip and pressure applied on the liquid junction. The sensitivity of the system, in terms of the LOD (base peak monitoring) was below 10 ng/mL for the beta-blocker drugs and below 200 ng/mL for peptide analysis. 相似文献
79.
Jagesar DC Hartl F Buma WJ Brouwer AM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(6):1935-1946
The macrocycle in rotaxane 1 is preferentially hydrogen bonded to the succinamide station in the neutral form, but can be moved to the naphthalimide station by one-electron reduction of the latter. The hydrogen bonding between the amide NH groups of the macrocycle and the C double bond O groups in the binding stations in the thread was studied with IR spectroscopy in different solvents in both states. In addition, the solvent effect on the vibrational frequencies was analyzed; a correlation with the solvent acceptor number (AN) was observed. The conformational switching upon reduction could be detected by monitoring the hydrogen-bond-induced shifts of the nu(CO) frequencies of the C double bond O groups of the succinamide and the reduced naphthalimide stations. The macrocycle was found to shield the encapsulated station from the solvent: wavenumbers of nu(CO) bands of the C double bond O groups residing inside the macrocycle cavity remain unaffected by the solvent polarity. 相似文献
80.
The strength of capillary bridges in randomly packed granular media was analyzed by means of computer simulations. A novel simulation method, based on the tracking of moving interfaces, has been implemented and used for determining the equilibrium shape of capillary bridges in a granular medium under a range of liquid saturations and solid-phase geometry. The net force acting on each grain due to the capillary bridges was evaluated, as well as the aggregate force acting between two wet granular media during their separation in the normal directions. The simulation results are consistent with previous experimental observations and reveal interesting phenomena such as the existence of a maximum in the tensile strength of a wet granular medium as function of liquid saturation. 相似文献