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981.
Cost-effective and rapid monitoring of Salmonella in the meat production chain can contribute to food safety. The objective of this study was to validate an easy-to-use pre-PCR sample preparation method based on a simple boiling protocol for screening of Salmonella in meat and carcass swab samples using a real-time PCR method. The protocol included incubation in buffered peptone water, centrifugation of an aliquot, and a boiling procedure. The validation study included comparative and interlaboratory trials recommended by the Nordic Organization for Validation of Alternative Microbiological Methods (NordVal). The comparative trial was performed against a reference method (NMKL 187, 2007) and a PCR method previously approved by NordVal with a semiautomated magnetic bead-based DNA extraction step using 122 artificially contaminated samples. The LOD was found to be 3.0, 3.2, and 3.4 CFU/sample for the boiling, magnetic bead-based, and NMKL 187 methods, respectively. When comparing the boiling method with the magnetic beads, the relative accuracy (AC), relative sensitivity (SE), and relative specificity (SP) were 98, 102, and 98%, respectively (Cohen's kappa index 0.95). When comparing results obtained by the boiling to the culture-based method, the AC, SE, and SP were found to be 98, 102, and 98%, respectively (kappa index 0.93). In the interlaboratory trial including valid results from 11 laboratories, apart from two false-positive samples by the boiling method combined with PCR, no deviating results were obtained (SP, SE, and AC were 100, 95, and 97%, respectively). This test is under implementation by the Danish meat industry, and can be useful for screening of large number of samples in the meat production, especially for fast release of minced meat with a short shelf life. 相似文献
982.
Dr. Alicja Franke Dr. Christoph Fertinger Prof. Dr. Rudi van Eldik 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(22):6935-6949
The present study focuses on the formation and reactivity of hydroperoxo–iron(III) porphyrin complexes formed in the [FeIII(tpfpp)X]/H2O2/HOO? system (TPFPP=5,10,15,20‐tetrakis(pentafluorophenyl)‐21H,23H‐porphyrin; X=Cl? or CF3SO3?) in acetonitrile under basic conditions at ?15 °C. Depending on the selected reaction conditions and the active form of the catalyst, the formation of high‐spin [FeIII(tpfpp)(OOH)] and low‐spin [FeIII(tpfpp)(OH)(OOH)] could be observed with the application of a low‐temperature rapid‐scan UV/Vis spectroscopic technique. Axial ligation and the spin state of the iron(III) center control the mode of O? O bond cleavage in the corresponding hydroperoxo porphyrin species. A mechanistic changeover from homo‐ to heterolytic O? O bond cleavage is observed for high‐ [FeIII(tpfpp)(OOH)] and low‐spin [FeIII(tpfpp)(OH)(OOH)] complexes, respectively. In contrast to other iron(III) hydroperoxo complexes with electron‐rich porphyrin ligands, electron‐deficient [FeIII(tpfpp)(OH)(OOH)] was stable under relatively mild conditions and could therefore be investigated directly in the oxygenation reactions of selected organic substrates. The very low reactivity of [FeIII(tpfpp)(OH)(OOH)] towards organic substrates implied that the ferric hydroperoxo intermediate must be a very sluggish oxidant compared with the iron(IV)–oxo porphyrin π‐cation radical intermediate in the catalytic oxygenation reactions of cytochrome P450. 相似文献
983.
984.
Nussbaumer S Geiser L Sadeghipour F Hochstrasser D Bonnabry P Veuthey JL Fleury-Souverain S 《Analytical and bioanalytical chemistry》2012,402(8):2499-2509
A simple wipe sampling procedure was developed for the surface contamination determination of ten cytotoxic drugs: cytarabine,
gemcitabine, methotrexate, etoposide phosphate, cyclophosphamide, ifosfamide, irinotecan, doxorubicin, epirubicin and vincristine.
Wiping was performed using Whatman filter paper on different surfaces such as stainless steel, polypropylene, polystyrol,
glass, latex gloves, computer mouse and coated paperboard. Wiping and desorption procedures were investigated: The same solution
containing 20% acetonitrile and 0.1% formic acid in water gave the best results. After ultrasonic desorption and then centrifugation,
samples were analysed by a validated liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS) in selected reaction
monitoring mode. The whole analytical strategy from wipe sampling to LC–MS/MS analysis was evaluated to determine quantitative
performance. The lowest limit of quantification of 10 ng per wiping sample (i.e. 0.1 ng cm−2) was determined for the ten investigated cytotoxic drugs. Relative standard deviation for intermediate precision was always
inferior to 20%. As recovery was dependent on the tested surface for each drug, a correction factor was determined and applied
for real samples. The method was then successfully applied at the cytotoxic production unit of the Geneva University Hospitals
pharmacy. 相似文献
985.
K. Franke D. Rössler U. Gottschalch H. Kupsch 《Isotopes in environmental and health studies》2013,49(3):223-239
Abstract The modeling of geo-chemical processes needs the detailed and comprehensive knowledge of all chemical interactions existing in the flow path of waste dumps, subsoil and aquifer. This includes the adsorption, displacement and transport of heavy metal species of fulvic and humic acids, which represent the main amount of DOC in the liquid/solid system of the flow path. Comparative measurements of DOC concentrations in the input and output flow at the three waste dumps in the district Schlema/Alberoda indicated that DOC is produced and/or supplied within the waste dumps. The speciation of heavy metal compounds of fulvic and humic acids was achieved by means of sequential chromatographic analysis SCA and isoelectric focusing IEF. Between 5% and 20% of uranium exist in the flow path in the form of stable fulvic and humic acid species. Their distribution coefficients are strongly correlated with the pH values of the geo-chemical system. 相似文献
986.
Birk T Pedersen KS Thuesen CA Weyhermüller T Schau-Magnussen M Piligkos S Weihe H Mossin S Evangelisti M Bendix J 《Inorganic chemistry》2012,51(9):5435-5443
The use of kinetically robust chromium(III) fluorido complexes as synthons for mixed 3d-4f clusters is reported. The tendency toward linear {Cr(III)-F-Ln(III)} units dictates the cluster topology. Specifically, we show that reaction of cis-[Cr(III)F(2)(NN)(2)]NO(3) (NN = 1,10-phenanthroline ("phen") or 2,2'-bipyridine ("bpy")) with Ln(NO(3))(3)·xH(2)O produces isostructural series of molecular {Ln(2)Cr(2)} squares (1-9) with linear fluoride bridges. In a parallel fashion, fac-[Cr(III)F(3)L], where L = N,N',N″-trimethyl-1,4,7-triazacyclononane ("Me(3)tacn"), reacts with Nd(NO(3))(3)·6H(2)O to form a fluoride-centered penta-nuclear complex and fac-[Cr(III)F(3)L'], with L' = 1,1,1-tris-((methylamino)methylethane) ("Me(3)tame"), reacts with [Ln(hfac)(3)(H(2)O)(2)] (hfacH = 1,1,1,5,5,5-hexafluoroacetylacetone) to yield an isostructural series of {Ln(3)Cr(2)} (10-14) trigonal bipyramids with no central ligand. The formation of the latter is accompanied by a partial solvolysis of the Cr(III) precursor but without formation of insoluble LnF(3). The magnetic properties of the gadolinium containing clusters allow quantification of fluoride-mediated, antiferromagnetic Gd-Cr exchange interactions of magnitude between 0.14 cm(-1) and 0.71 cm(-1) (? = J(12)?(1)·?(2) formalism) and vanishingly small J(Gd-Gd) of 0.06(0) cm(-1). The large spin and small anisotropy together with weak exchange interactions in the {Gd(3)Cr(2)} (11) cluster give rise to a very large magneto-caloric effect of -ΔS(m) = 28.7 J kg(-1) K(-1) (μ(0)H = 90 to 0 kOe). 相似文献
987.
Roberts GM Williams CA Young JD Ullrich S Paterson MJ Stavros VG 《Journal of the American Chemical Society》2012,134(30):12578-12589
A combination of ultrafast time-resolved velocity map imaging (TR-VMI) methods and complete active space self-consistent field (CASSCF) ab initio calculations are implemented to investigate the electronic excited-state dynamics in aniline (aminobenzene), with a perspective for modeling (1)πσ* mediated dynamics along the amino moiety in the purine derived DNA bases. This synergy between experiment and theory has enabled a comprehensive picture of the photochemical pathways/conical intersections (CIs), which govern the dynamics in aniline, to be established over a wide range of excitation wavelengths. TR-VMI studies following excitation to the lowest-lying (1)ππ* state (1(1)ππ*) with a broadband femtosecond laser pulse, centered at wavelengths longer than 250 nm (4.97 eV), do not generate any measurable signature for (1)πσ* driven N-H bond fission on the amino group. Between wavelengths of 250 and >240 nm (<5.17 eV), coupling from 1(1)ππ* onto the (1)πσ* state at a 1(1)ππ*/(1)πσ* CI facilitates ultrafast nonadiabatic N-H bond fission through a (1)πσ*/S(0) CI in <1 ps, a notion supported by CASSCF results. For excitation to the higher lying 2(1)ππ* state, calculations reveal a near barrierless pathway for CI coupling between the 2(1)ππ* and 1(1)ππ* states, enabling the excited-state population to evolve through a rapid sequential 2(1)ππ* → 1(1)ππ* → (1)πσ* → N-H fission mechanism, which we observe to take place in 155 ± 30 fs at 240 nm. We also postulate that an analogous cascade of CI couplings facilitates N-H bond scission along the (1)πσ* state in 170 ± 20 fs, following 200 nm (6.21 eV) excitation to the 3(1)ππ* surface. Particularly illuminating is the fact that a number of the CASSCF calculated CI geometries in aniline bear an exceptional resemblance with previously calculated CIs and potential energy profiles along the amino moiety in guanine, strongly suggesting that the results here may act as an excellent grounding for better understanding (1)πσ* driven dynamics in this ubiquitous genetic building block. 相似文献
988.
Ariaki Murata Kenji Kai Ken Tsutsui Jun Takeuchi Yasushi Todoroki Kazuo Furihata Mineyuki Yokoyama Susanne Baldermann Naoharu Watanabe 《Tetrahedron》2012,68(27-28):5583-5589
Plant oxylipins are an important class of signaling molecules in plants. The cyclic adducts of epinephrine or norepinephrine with the naturally occurring oxylipin (12Z,15Z)-9-hydroxy-10-oxo-octadeca-12,15-dienoic acid (KODA, 1) or its synthetic analogues (2–6) have been reported to possess flower-inducing activity toward Lemna paucicostata. By in vivo and in vitro experiments with seedlings of Pharbitis nil cv. Violet carbonyl groups of the α-ketols (1 and 3) and the ketones (7 and 9) were enantio-selectively reduced to give their corresponding vicinal diols (2 and 4) and alcohols (8 and 10). The stereo-chemistry at the oxymethine carbon was determined based on the long range C–H coupling constants and the modified Mosher's method. Orientation of the adjacent hydroxyl group in (1 and 3) did not affect the enantio-selectivity, whereas the conversion was slightly affected and higher yields were obtained with the R-enantiomers of the α-ketols. 相似文献
989.
Lazarides T Kuhri S Charalambidis G Panda MK Guldi DM Coutsolelos AG 《Inorganic chemistry》2012,51(7):4193-4204
In this report we describe the synthesis of multichromophore arrays consisting of two Bodipy units axially bound to a Sn(IV) porphyrin center either via a phenolate (3) or via a carboxylate (6) functionality. Absorption spectra and electrochemical studies show that the Bodipy and porphyrin chromophores interact weakly in the ground state. However, steady-state emission and excitation spectra at room temperature reveal that fluorescence from both the Bodipy and the porphyrin of 3 are strongly quenched suggesting that, in the excited state, energy and/or electron transfer might occur. Indeed, as transient absorption experiments show, selective excitation of Bodipy in 3 results in a rapid decay (τ ≈ 2 ps) of the Bodipy-based singlet excited state and a concomitant rise of a charge-separated state evolving from the porphyrin-based singlet excited state. In contrast, room-temperature emission studies on 6 show strong quenching of the Bodipy-based fluorescence leading to sensitized emission from the porphyrin moiety due to a transduction of the singlet excited state energy from Bodipy to the porphyrin. Emission experiments at 77 K in frozen toluene reveal that the room-temperature electron transfer pathway observed in 3 is suppressed. Instead, Bodipy excitation in 3 and 6 results in population of the first singlet excited state of the porphyrin chromophore. Subsequently, intersystem crossing leads to the porphyrin-based triplet excited state. 相似文献
990.
Michielsen B Dom JJ van der Veken BJ Hesse S Suhm MA Herrebout WA 《Physical chemistry chemical physics : PCCP》2012,14(18):6469-6478
The formation of C-H···N bonded complexes of halothane with ammonia has been studied using infrared and Raman spectroscopy of solutions in the liquid rare gases argon, krypton and xenon, of supersonic jet expansions and of room temperature vapor phase mixtures. For the solutions and for the vapor phase experiments, the formation of complexes with 1:1 and 1:2 stoichiometry was observed. The complexation enthalpy for the 1:1 complex was determined to be -20 (1) kJ mol(-1) in the vapor phase, -17.0 (5) kJ mol(-1) in liquid xenon and -17.3 (6) kJ mol(-1) in liquid krypton. For the 1:2 complex in liquid xenon, the complexation enthalpy was determined to be -31.5 (12) kJ mol(-1). Using the complexation enthalpies for the vapor phase and for the solutions in liquid xenon and krypton, a critical assessment is made of the Monte Carlo Free Energy Perturbation approach to model solvent influences on the thermodynamical properties of the cryosolutions. The influences of temperature and solvent on the complexation shifts of the halothane C-H stretching mode are discussed. 相似文献