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211.
Watson RM Skorik YA Patra GK Achim C 《Journal of the American Chemical Society》2005,127(42):14628-14639
Recent studies on metal incorporation in ligand-modified nucleic acids have focused on the effect of metal coordination on the stability of metal-containing duplexes or triplexes and on the metal binding selectivity but did not address the effect of the sequence of the nucleic acid in which the ligands are incorporated. We have introduced 8-hydroxyquinoline Q in 10-mer PNA strands with various sequences and have investigated the properties of the duplexes formed from these strands upon binding of Cu(2+). Variable-temperature UV-vis spectroscopy shows that, in the presence of Cu(2+), duplexes are formed even from ligand-modified Q-PNA strands that have a large number of mismatches. Spectrophotometric titrations demonstrate that at any temperature, one Cu(2+) ion binds a pair of Q-PNA strands that each contain one 8-hydroxyquinoline, but below the melting temperature, the PNA duplex exerts a supramolecular chelate effect, which prevents the transformation in the presence of excess Cu(2+) of the 1:2 Cu(2+):Q-PNA complexes into 1:1 complexes. EPR spectroscopy gives further support for the existence in the duplexes of [CuQ(2)] moieties that are similar to the corresponding square planar synthetic complex formed between Cu(2+) and 8-hydroxyquinoline. As PNA duplexes show a preferred handedness due to the chiral induction effect of a C-terminal l-lysine, which is transmitted through stacking interactions within the duplex, only if the metal-containing duplex has complementary strands, does it show a chiral excess measured by CD spectroscopy. The strong effect of the metal-ligand moiety is suggestive of an increased correlation length in PNA duplexes that contain such moieties. These results indicate that strong metal-ligand alternative base pairs significantly diminish the importance of Watson-Crick base pairing for the formation of a stable PNA duplex and lead to high mismatch tolerance, a principle that can be used in the construction of hybrid inorganic-nucleic acid nanostructures. 相似文献
212.
Berlinguette CP Dragulescu-Andrasi A Sieber A Güdel HU Achim C Dunbar KR 《Journal of the American Chemical Society》2005,127(18):6766-6779
A series of bimetallic, trigonal bipyramidal clusters of type {[Co(N-N)(2)](3)[Fe(CN)(6)](2)} are reported. The reaction of {Co(tmphen)(2)}(2+) with [Fe(CN)(6)](3)(-) in MeCN affords {[Co(tmphen)(2)](3)[Fe(CN)(6)](2)} (1). The cluster can exist in three different solid-state phases: a red crystalline phase, a blue solid phase obtained by exposure of the red crystals to moisture, and a red solid phase obtained by desolvation of the blue solid phase in vacuo. The properties of cluster 1 are extremely sensitive to both temperature and solvent content in each of these phases. Variable-temperature X-ray crystallography; (57)Fe Mossbauer, vibrational, and optical spectroscopies; and magnetochemical studies were used to study the three phases of 1 and related compounds, Na{[Co(tmphen)(2)](3)[Fe(CN)(6)](2)}(ClO(4))(2) (2), {[Co(bpy)(2)](3)[Fe(CN)(6)](2)}[Fe(CN)(6)](1/3) (3), and {[Ni(tmphen)(2)](3)[Fe(CN)(6)](2)} (4). The combined structural and spectroscopic investigation of 1-4 leads to the unambiguous conclusion that 1 can exist in different electronic isomeric forms, {Co(III)(2)Co(II)Fe(II)(2)} (1A), {Co(III)Co(II)(2)Fe(III)Fe(II)} (1B), and {Co(II)(3)Fe(III)(2)} (1C), and that it can undergo a charge-transfer-induced spin transition (CTIST). This is the first time that such a phenomenon has been observed for a Co/Fe molecule. 相似文献
213.
Pardo E Bernot K Julve M Lloret F Cano J Ruiz-García R Delgado FS Ruiz-Pérez C Ottenwaelder X Journaux Y 《Inorganic chemistry》2004,43(9):2768-2770
Two new hexanuclear oxamatocopper(II) complexes 3 and 4 have been synthesized from the binuclear copper(II) complexes of the meta- and para-phenylenebis(oxamate) ligands, respectively. Complexes 3 and 4 possess an overall ladderlike structure made up of two oxamate-bridged linear trinuclear units ("rails") connected through two phenylenediamidate bridges ("rungs") between the central copper atoms to give metallacyclic cores of the meta- and para-cyclophane type, respectively. They show different ground spin states, S = 1 (3) or S = 0 (4), depending on the substitution pattern in the aromatic spacers. The triplet state molecule 3 containing two spin doublet Cu(II)3 units connected by two m-phenylenediamidate bridges represents a successful extension of the concept of "ferromagnetic coupling units" to metal complexes, which is a well-known approach toward high spin organic radicals. 相似文献
214.
F. R. Diaz L. H. Tagle F. Garcia R. Sastre M. Conde J. L. Mateo F. Catalina 《Journal of polymer science. Part A, Polymer chemistry》1990,28(12):3499-3511
Several models of monomers, homopolymers, and copolymers containing a photosensitizer group, 4-nitro-1-naphthyl-carbamoyl (NNC), have been synthesized. Synthetic methods are described, in addition to two routes for copolymers preparation. First, the radical copolymerization between monomers with the photosensitizer group built-in and comercial monomers such as styrene and methyl acrylate and, second, polymer modification by nucleophilic reaction between carbonyl group polymer supported and nitro-naphthyl amine. All products were characterized and one of the resulting soluble polymeric photosensitizer and its model compound, were tested as triplet energy donors against trans- stilbene and their Stern–Volmer constants were determined. Results show that the sensitizer efficiency is closer to that of the well known benzophenone sensitizer and higher than that of the acetophenone, while the sensitizer efficiency disminished when the chromophore is bonded to the polymer. 相似文献
215.
S. Gaspard M. Oujja E. Rebollar C. Abrusci F. Catalina M. Castillejo 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1612-1617
The emulsion-coated transparent plastic-base film has been the main carrier for production and preservation of motion picture contents since the 19th century. The knowledge of the composition of black and white silver gelatine cinematographic films is of great importance for the characterization of the photographic process and for identifying the optimum conditions for conservation. A cinematographic film is a multi-component system that consists of a layer of photographic emulsion overcoating a polymeric support (plasticized cellulose triacetate) and a protective transparent cross-linked gelatine layer coating the emulsion. In the present work, Laser Induced Breakdown Spectroscopy (LIBS) is used to characterize the composition of the materials of cinematographic films. LIB spectra of film samples and of different individual film components, polymeric support and reference gelatines, were acquired in vacuum by excitation at 266 nm (Q-switched Nd:YAG laser, 6 ns, 10 Hz). In the cinematographic film, silver lines from the light-sensitive silver halide salts of the photographic emulsion are accompanied by iron, lead, chrome and phosphorus lines. Iron and lead are constituents of film developers, chrome is included in the composition of the hardening agents and phosphorus has its origin in the plasticizer used in the polymeric support. By applying successive pulses on the same spot of the film sample, it was possible to observe through stratigraphic analysis the different layers composition. Additionally, the results obtained reveal the analytical capacity of LIBS for the study and classification of the different gelatine types and qualities used for the protecting layer and the photographic emulsion. 相似文献
216.
Kristenson EM Kamminga DA Catalina MI Espiga C Vreuls RJ Brinkman UA 《Journal of chromatography. A》2002,975(1):95-104
In the present study the retaining precolumn, which is commonly used in a set-up for large-volume on-column injections, or when solid-phase extraction (SPE) or liquid chromatography is coupled to gas chromatography (CC), was removed after varying its length from the standard length of 3 m down to zero. A dramatic increase of the evaporation rate of the injected organic solvent was obtained from a typical value of 100 microl/min up to 300 microl/min. The increased evaporation rate allowed (i) injection of a larger volume in the same retention gap, (ii) faster injection/transfer of the organic solvent and (iii) reduction of the transfer temperature. As volatile compounds under partially concurrent solvent evaporation conditions are easily lost once the organic solvent has been removed via a solvent-vapour exit (SVE), the parameters for large-volume injection, i.e. the evaporation rate and injection speed, were optimised using accurate measurements of the real flow-rate of the carrier gas into the GC system. All these options have been evaluated over the last 4 years. In order to demonstrate that omitting the retaining precolumn had no effect on the application range of the on-column interface, analytes as volatile as benzene were injected into GC-MS using 50-200 microl of n-pentane solutions. Contaminants were extracted from river water and wastewater into n-pentane using in-vial liquid-liquid extraction. The detection limits for benzene, toluene, ethylbenzene and m-xylene were approximately 10 ng/l. To obtain optimum results the SVE had to be closed 1 s before the end of evaporation. Several brands of n-pentane were analysed to check for the presence of benzene. Most of them contained interfering compounds and benzene at the low microg/l level and therefore had to be cleaned by means of column chromatography. As another example C8-C17 alkylphenones were extracted from wastewater with n-hexane. Detection limits were 10-40 ng/l. 相似文献
217.
Margarita G. Prolongo C. Arribas Catalina Salom Rosa M. Masegosa 《Journal of Thermal Analysis and Calorimetry》2007,87(1):33-39
Diglycidyl
ether of bisfenol-A (DGEBA)/poly(vinyl acetate) (PVAc)/poly(4-vinyl phenol)
brominated (PVPhBr) ternary blends cured with 4,4’-diaminodiphenylmethane
(DDM) were investigated by differential scanning calorimetry (DSC), dynamic
mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM).
Homogeneous (DGEBA+DDM)/PVPhBr networks with a unique T
g
are generated. Ternary blends (DGEBA+DDM)/PVAc/PVPhBr are initially miscible
and phase separate upon curing arising two T
gs
that correspond to a PVAc-rich phase and to epoxy network phase. Increasing
the PVPhBr content the T
gof
the PVAc phase move to higher temperatures as a consequence of the PVAc-PVPhBr
interactions. Different morphologies are generated as a function of the blend
composition. 相似文献
218.
C. Curceanu S. Bartalucci A. Bassi M. Bazzi S. Bertolucci C. Berucci A. M. Bragadireanu M. Cargnelli A. Clozza L. De Paolis S. Di Matteo S. Donadi A. D’Uffizi J.-P. Egger C. Guaraldo M. Iliescu T. Ishiwatari M. Laubenstein J. Marton E. Milotti A. Pichler D. Pietreanu K. Piscicchia T. Ponta E. Sbardella A. Scordo H. Shi D. L. Sirghi F. Sirghi L. Sperandio O. Vazquez Doce J. Zmeskal 《Foundations of Physics》2016,46(3):263-268
219.
Fabelo O Pasán J Cañadillas-Delgado L Delgado FS Lloret F Julve M Ruiz-Pérez C 《Inorganic chemistry》2008,47(18):8053-8061
The hydrothermal preparation, crystal structure determination, and magnetic study of two isomers made up of 1,2,4,5-benzenetetracarboxylate and high-spin Co(II) ions of formula [Co2(bta)(H2O)4]n x 2n H2O (1 and 2; H4bta = 1,2,4,5-benzenetetracarboxylic acid) are reported. 1 and 2 are three-dimensional compounds whose structures can be described as (4,4) rectangular layers of trans-diaquacobalt(II) units with the bta(4-) anion acting as tetrakis-monodentate ligand through the four carboxylate groups, which are further connected through other trans-[Co(H2O)2](2+) (1) and planar [Co(H2O)4](2+) (2) entities, with the bridging units being a carboxylate group in either the anti-syn (1) or syn-syn (2) conformations and a water molecule (2). The study of the magnetic properties of 1 and 2 in the temperature range 1.9-300 K shows the occurrence of weak antiferromagnetic interactions between the high-spin Co(II) ions, with the strong decrease of chi(M)T upon cooling being mainly due to the depopulation of the higher energy Kramers doublets of the six-coordinated Co(II) ions. The computed values of the exchange coupling between the Co(II) ions across anti-syn carboxylate (1) and syn-syn carboxylate/water (2) bridges are J = -0.060 (1) and -1.90 (2) cm(-1) (with the Hamiltonian being defined as H = -Jsigma(i,j)S(i) x S(j)). These values follow the different conformations of the carboxylate bridge in 1 (anti-syn) and 2 (syn-syn) with the occurrence of a double bridge in 2 (water/carboxylate). 相似文献
220.
Hamzah Basil Mohammed Sajjad Mohsin I. Rayyif Carmen Curutiu Alexandra Catalina Birca Ovidiu-Cristian Oprea Alexandru Mihai Grumezescu Lia-Mara Ditu Irina Gheorghe Mariana Carmen Chifiriuc Grigore Mihaescu Alina-Maria Holban 《Molecules (Basel, Switzerland)》2021,26(8)
Efficient antibiotics to cure Pseudomonas aeruginosa persistent infections are currently insufficient and alternative options are needed. A promising lead is to design therapeutics able to modulate key phenotypes in microbial virulence and thus control the progression of the infectious process without selecting resistant mutants. In this study, we developed a nanostructured system based on Fe3O4 nanoparticles (NPs) and eugenol, a natural plant-compound which has been previously shown to interfere with microbial virulence when utilized in subinhibitory concentrations. The obtained functional NPs are crystalline, with a spherical shape and 10–15 nm in size. The subinhibitory concentrations (MIC 1/2) of the eugenol embedded magnetite NPs (Fe3O4@EUG) modulate key virulence phenotypes, such as attachment, biofilm formation, persister selection by ciprofloxacin, and the production of soluble enzymes. To our knowledge, this is the first report on the ability of functional magnetite NPs to modulate P. aeruginosa virulence and phenotypic resistance; our data highlights the potential of these bioactive nanostructures to be used as anti-pathogenic agents. 相似文献