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101.
We find conditions for E(W
) to be finite whereW is the stationary waiting time random variable in a stableG/G/1 queue with dependent service and inter-arrival times.Supported in part by KBN under grant 640/2/9, and at the Center for Stochastic Processes, Department of Statistics at the University of North Carolina Chapel Hill by the Air Force Office of Scientific Research Grant No. 91-0030 and the Army Research Office Grant No. DAAL09-92-G-0008. 相似文献
102.
The effect of deuterated solvents in size-exclusion chromatography (SEC) was studied by comparing intrinsic viscosity measurements, SEC calibration curves, and column efficiency using water-soluble polymers. For aqueous SEC, the use of deuterium oxide slightly increases the SEC elution volume. To verify that adsorption onto the packing was absent, data from exclusion experiments were compared at 35 and 50 degrees C. Our results indicate that adsorption is not occurring for pullulan or polyethylene glycol (PEG)/poly(ethylene oxide) (PEO); for the latter, however, the elution volume increased using both D2O and H2O, indicative of slight hydrodynamic volume contraction of PEG/PEO at higher temperatures. A moderate increase in band broadening (moderate decrease in column efficiency) was observed using D2O. Finally, the effects of chloroform versus deuterated chloroform were evaluated, but no hydrodynamic volume changes were observed. 相似文献
103.
Franziska Nehring Dorrit E. Jacob Matthias G. Barth Stephen F. Foley 《Mikrochimica acta》2008,160(1-2):153-163
Trace element determination in rocks by fusion on an iridium strip heater followed by LA-ICP-MS analysis of the glass beads
is extended here to SiO2-rich rocks; rapid fusion of samples with >55 wt% SiO2 is facilitated by dilution by high purity MgO. The method developed here can rapidly and accurately determine numerous trace
elements in a large range of rock compositions in a short time (about 50 samples/day). Systematic evaluation for a large range
of rock compositions (natural rocks and reference materials AGV-2, GSP-2, JG-1a) with SiO2 contents between 45 and 80 wt% shows that reproducibility and accuracy within 10% can be routinely achieved for most of the
28 trace elements investigated (Rb, Sr, Cs, Ba, Ti, Zr, Hf, Nb, Ta, Sc, V, Cr, Ni, Pb, Th, U, REE). The 40 mg sample size
is smaller than for XRF, INAA or solution-ICP-MS, detection limits are lower, and trace element palettes more complete than
XRF and INAA. This microchemical method is thus attractive for the analysis of all natural geological materials as well as
for experimental applications with small samples. Samples with SiO2-contents >55 wt% require hot and long melting to achieve homogeneous glasses and eliminate all residual minerals, particularly
refractory accessory phases. Melting conditions of 1600 °C and 20 s for samples are recommended for SiO2 contents between 55 and 70 wt%, whereas 1800 °C and 20–30 s are often required for samples with >70 wt% SiO2. Problems are encountered for Pb and Cs due to volatilization on the Ir strip, for Sc due to interferences, and Zr and Hf
due to their sequestration in refractory accessory minerals.
Correspondence: Franziska Nehring, Department of Geosciences, University of Mainz, Becherweg 21, 55099 Mainz, Germany 相似文献
104.
Mixed amidinato amido complexes [Me3SiNC(tBu)NSiMe3]M[N(SiMe3)2] (M = Sn 2, Ge 3) were prepared by the reaction of [Me3SiNC(tBu)NSiMe3]Li (1a) with SnCl2 and GeCl2(dioxane) in ether. The N(SiMe3)2 ligand in these compounds is derived from the rearrangement of the [Me3SiNC(tBu)NSiMe3]- anion with extrusion of tBuCN. The susceptibility of [Me3SiNC(tBu)NSiMe3]- to rearrangement appears to be dependent on reaction solvent and on the coordinated metal center. Single-crystal X-ray diffraction studies of 2 and 3 are presented. Replacement of Me for tBu in the ligand allowed [Me3SiNC(Me)NSiMe3]2SnII (4) to be isolated, and an X-ray structure of this compound is reported. The isolation of 4 indicates that steric factors also play a role in the stability of [Me3SiNC(tBu)NSiMe3]-. Compounds 2 and 3 are outstanding catalysts for the cyclotrimerization of phenyl isocyanates to perhydro-1,3,5-triazine-2,4,6-triones (isocyanurates) at room temperature. In contrast, complex 4 catalytically reacts with phenyl isocyanate to produce isocyanate dimer and trimer in a 52:35 ratio. 相似文献
105.
106.
Verma S Sallum UW Athar H Rosenblum L Foley JW Hasan T 《Photochemistry and photobiology》2009,85(1):111-118
5-(Ethylamino)-9-diethylaminobenzo[a]phenothiazinium chloride (EtNBS) is a photosensitizer (PS) with broad antimicrobial photodynamic activity. The objective of this study was to determine the antimicrobial photodynamic effect of side chain/end group modifications of EtNBS on two representative bacterial Gram-type-specific strains. Two EtNBS derivatives were synthesized, each functionalized with a different side-chain end-group, alcohol or carboxylic acid. In solution, both exhibited photochemical properties consistent with those of the EtNBS parent molecule. In vitro photodynamic therapy experiments revealed an initial Gram-type-specificity with two representative strains; both derivatives were phototoxic to Staphylococcus aureus 29,213 but the carboxylic acid derivative was nontoxic to Escherichia coli 25,922. This difference in photodynamic efficacy was not due to a difference in the binding of the two molecules to the bacteria as the amount of both derivatives bound by bacteria was identical. Interestingly, the carboxylic acid derivative produced no fluorescence emission when observed in cultures of E. coli via fluorescence microscopy. These early findings suggest that the addition of small functional groups could achieve Gram-type-specific phototoxicity through altering the photodynamic activity of PSs and deserve further exploration in a larger number of representative strains of each Gram type. 相似文献
107.
Mark Cronly Patrice Behan Barry Foley Edward Malone Liam Regan 《Journal of chromatography. A》2009,1216(46):8101-8109
A rapid confirmatory method has been developed and validated for the simultaneous identification, confirmation and quantitation of 11 nitroimidazoles in eggs by liquid chromatography tandem mass spectrometry (LC–MS/MS). The method is validated in accordance with Commission Decision 2002/657/EC and is capable of analysing metronidazole (MNZ), dimetridazole (DMZ), ronidazole (RNZ), ipronidazole (IPZ) and their hydroxy metabolites MNZ-OH, HMMNI (hydroxymethyl, methyl nitroimidazole), IPZ-OH. The method is also capable of analysing carnidazole (CRZ), ornidazole (ORZ), tinidazole (TNZ) and ternidazole (TRZ). MNZ, DMZ and RNZ have been assigned a recommended level (RL) of 3 μg kg−1 by the Community Reference Laboratory (CRL) in Berlin. The developed method described in this study is easily able to detect all the nitroimidazole compounds investigated at this level and below. Egg samples are extracted with acetonitrile, and NaCl is added to help remove matrix contaminants. The acetonitrile extract undergoes a liquid–liquid wash step with hexane; it is then evaporated and reconstituted in mobile phase. The reconstituted samples are analysed by liquid chromatography tandem mass spectrometry (LC–MS/MS). The decision limits (CCα) range from 0.33 to 1.26 μg kg−1 and the detection capabilities (CCβ), range from 0.56 to 2.15 μg kg−1. The results of the inter-assay study, which was performed by fortifying hen egg samples (n = 18) on three separate days, show the accuracy calculated for the various analytes to range between 87.2 and 106.2%. The precision of the method, expressed as %CV values for the inter-assay variation of each analyte at the three levels of fortification (3, 4.5 and 6.0 μg kg−1), ranged between 3.7 and 11.3%. A Day 4 analysis was carried out to examine species variances in eggs from different birds such as duck and quail and investigating differences in various battery and free range hen eggs. 相似文献
108.
Marcaurelle LA Comer E Dandapani S Duvall JR Gerard B Kesavan S Lee MD Liu H Lowe JT Marie JC Mulrooney CA Pandya BA Rowley A Ryba TD Suh BC Wei J Young DW Akella LB Ross NT Zhang YL Fass DM Reis SA Zhao WN Haggarty SJ Palmer M Foley MA 《Journal of the American Chemical Society》2010,132(47):16962-16976
An aldol-based build/couple/pair (B/C/P) strategy was applied to generate a collection of stereochemically and skeletally diverse small molecules. In the build phase, a series of asymmetric syn- and anti-aldol reactions were performed to produce four stereoisomers of a Boc-protected γ-amino acid. In addition, both stereoisomers of O-PMB-protected alaninol were generated to provide a chiral amine coupling partner. In the couple step, eight stereoisomeric amides were synthesized by coupling the chiral acid and amine building blocks. The amides were subsequently reduced to generate the corresponding secondary amines. In the pair phase, three different reactions were employed to enable intramolecular ring-forming processes: nucleophilic aromatic substitution (S(N)Ar), Huisgen [3+2] cycloaddition, and ring-closing metathesis (RCM). Despite some stereochemical dependencies, the ring-forming reactions were optimized to proceed with good to excellent yields, providing a variety of skeletons ranging in size from 8- to 14-membered rings. Scaffolds resulting from the RCM pairing reaction were diversified on the solid phase to yield a 14?400-membered library of macrolactams. Screening of this library led to the discovery of a novel class of histone deacetylase inhibitors, which display mixed enzyme inhibition, and led to increased levels of acetylation in a primary mouse neuron culture. The development of stereo-structure/activity relationships was made possible by screening all 16 stereoisomers of the macrolactams produced through the aldol-based B/C/P strategy. 相似文献
109.
110.
Li X Foley EA Molloy KR Li Y Chait BT Kapoor TM 《Journal of the American Chemical Society》2012,134(4):1982-1985
Post-translational modifications (PTMs) (e.g., acetylation, methylation, and phosphorylation) play crucial roles in regulating the diverse protein-protein interactions involved in essentially every cellular process. While significant progress has been made to detect PTMs, profiling protein-protein interactions mediated by these PTMs remains a challenge. Here, we report a method that combines a photo-cross-linking strategy with stable isotope labeling in cell culture (SILAC)-based quantitative mass spectrometry to identify PTM-dependent protein-protein interactions. To develop and apply this approach, we focused on trimethylated lysine-4 at the histone H3 N-terminus (H3K4Me(3)), a PTM linked to actively transcribed gene promoters. Our approach identified proteins previously known to recognize this modification and MORC3 as a new protein that binds H3M4Me(3). This study indicates that our cross-linking-assisted and SILAC-based protein identification (CLASPI) approach can be used to profile protein-protein interactions mediated by PTMs, such as lysine methylation. 相似文献