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排序方式: 共有321条查询结果,搜索用时 15 毫秒
311.
Doonan CJ Wilson HL Bennett B Prince RC Rajagopalan KV George GN 《Inorganic chemistry》2008,47(6):2033-2038
Valuable information on the active sites of molybdenum enzymes has been provided by Mo(V) electron paramagnetic resonance (EPR) spectroscopy. In recent years, multiple resonance techniques have been extensively used to examine details of the active-site structure, but basic continuous-wave (CW) EPR has not been re-evaluated in several decades. Here, we present a re-examination of the CW EPR spectroscopy of the sulfite oxidase low-pH chloride species and provide evidence for direct coordination of molybdenum by chloride. 相似文献
312.
Fangyuan Zhang Florian Rauch Asim Swain Todd B. Marder Prince Ravat 《Angewandte Chemie (International ed. in English)》2023,62(16):e202218965
Narrow-band emission is essential for applicable circularly polarized luminescence (CPL) active materials in ultrahigh-definition CP-OLEDs. One of the most promising classes of CPL active molecules, helicenes, however, typically exhibit broad emission with a large Stokes shift. We present, herein, a design strategy capitalizing on intramolecular donor-acceptor interactions between nitrogen and boron atoms to address this issue. 1,4-B,N-embedded configurationally stable single- and double helicenes were synthesized straightforwardly. Both helicenes show unprecedentedly narrow fluorescence and CPL bands (full width at half maximum between 17–28 nm, 0.07–0.13 eV) along with high fluorescence quantum yields (72–85 %). Quantum chemical calculations revealed that the relative localization of the natural transition orbitals, mainly on the rigid core of the molecule, and small values of root-mean-square displacements between S0 and S1 state geometries, contribute to the narrower emission. 相似文献
313.
Gandhi S Sharma P Capalash N Verma RS Suri CR 《Analytical and bioanalytical chemistry》2008,392(1-2):215-222
A novel carboxylic acid derivative of monoacetylmorphine (MAM-COOH) was synthesized and conjugated with bovine serum albumin (BSA) for generating polyclonal antibodies against the target molecule heroin and its major metabolites. The conjugate was characterized by fluorescence spectroscopy, polyacrylamide gel electrophoresis, and mass spectrometry to confirm the extent of haptenization of the carrier protein. A high titer (1:64,0000) of antibody was obtained by using the conjugate with an optimum protein/hapten molar ratio of 1:100. The generated antibody showed good binding affinity with heroin and its metabolites monoacetylmorphine (MAM) and morphine. The relative affinity constant (K (aff)) of the antibody was 3.1 x 10(7) l mol(-1), and the IC(50) values obtained for heroin, MAM, morphine, and codeine were 0.01, 0.013, 0.012, and 0.014 ng ml(-1), respectively. A fluorescence-based competitive inhibition immunoassay procedure was developed for the estimation of heroin and its major metabolites in standard and biofludic samples over a concentration range up to 0.01 ng ml(-1) with good signal reproducibility (p < 0.05). The method can be used as a convenient quantitative tool for the sensitive screening of major metabolites of heroin in biological samples. 相似文献
314.
Karakalos S Skala T Plekan O Ladas S Prince K Matolin V Chab V Siokou A 《The Journal of chemical physics》2012,136(22):224703
Photoelectron spectroscopy with synchrotron radiation, low energy electron diffraction, and ion-scattering spectroscopy were used in order to study the Ti/MgCl(2) interface grown on an atomically clean Si(111) 7 × 7 substrate. A series of high resolution spectra after deposition of a thick MgCl(2) layer, step by step deposition of Ti and gradual annealing, indicated a very reactive interface even at room temperature. Strong interaction between the incoming Ti atoms and the MgCl(2) layer, leads to the formation of Ti(2+) and Ti(4+) oxidation states. The interfacial interaction continues even at multilayer Ti coverage mainly by the partial disruption of Mg-Cl bonds and the formation of Ti-Cl sites, rendering this interface a very promising UHV-compatible model of a pre-catalyst for olefin polymerization. After the final annealing, the MgCl(2) multilayers desorb while Ti remains on the surface forming a silicide layer on which Cl and Mg atoms are attached. 相似文献
315.
Enoch Cobbina Julius Yao Agbezudor Prince Sodoke Amuzu Thomas K. Gyampomah 《Accreditation and quality assurance》2012,17(6):613-619
High-quality and reliable laboratory services are important components of effective and well-functioning health systems. Accurate, reliable and timely medical laboratory testing is crucial to patient care and disease surveillance. Unfortunately, in many sub-Saharan African countries, medical laboratory systems are adversely affected by the unavailability of medical laboratories, poor laboratory infrastructure and lack of well-trained personnel [1]. Quality in the laboratory is only achieved in a systematic way through the implementation of a quality management system. The results of the study showed that approximately 60?% of the 78 respondents were unaware of the requirements of ISO 15189:2007. A trial of proficiency testing, termed ??blind proficiency testing??, was carried out in which 19 laboratories determined the concentrations of urea and cholesterol in a proficiency testing material. Of the 19 laboratories that determined the concentration of urea, 63?% produced satisfactory results with scores between ?2 and +2. Similarly, 63?% of the participating laboratories obtained satisfactory z scores for cholesterol determination. Some of the laboratories that obtained satisfactory scores for urea determination had unsatisfactory scores for cholesterol determination and vice versa. It is recommended that the Ghanaian government pass a law and establish a standard to regulate medical laboratories in Ghana in order to improve quality in a significant way. 相似文献
316.
Plekan O Feyer V Richter R Moise A Coreno M Prince KC Zaytseva IL Moskovskaya TE Soshnikov DY Trofimov AB 《The journal of physical chemistry. A》2012,116(23):5653-5664
The electronic structures of the purine derivatives xanthine, hypoxanthine and caffeine have been investigated in the gas phase using C, N, and O 1s X-ray photoemission (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results have been interpreted by means of ab initio calculations using the third-order algebraic-diagrammatic construction (ADC(3)) method for the one-particle Green's function and the second-order ADC method (ADC(2)) for the polarization propagator. The carbon, nitrogen and oxygen K-edge NEXAFS spectra of xanthine and caffeine are very similar, since the molecules differ only by substitution of three hydrogen atoms by methyl groups. For hypoxanthine, the electronic structure and spectra differ considerably from xanthine as the purine ring is more highly conjugated, and there is one less oxo group. Effects due to oxo-hydroxy tautomerism were not observed. However, the two oxo tautomeric forms of hypoxanthine oxo-N(9)-H and oxo-N(7)-H are populated in the gas phase, and the C 1s spectra can be simulated only by taking account of these two tautomers, with appropriate Boltzmann population ratios which we have also calculated. For xanthine and caffeine, single tautomeric forms were observed. 相似文献
317.
The development of a time-resolved coherent anti-Stokes Raman scattering (CARS) variant for use as a probe of excited electronic state Raman-active modes following excitation with an ultrafast pump pulse is detailed. Application of this technique involves a combination of broadband fs-time scale pulses and a narrowband pulse of ps duration that allows multiplexed detection of the CARS signal, permitting direct observation of molecular Raman frequencies and intensities with time resolution dictated by the broadband pulses. Thus, this nonlinear optical probe, designated fs/ps CARS, is suitable for observation of Raman spectral evolution following excitation with a pump pulse. Because of the spatial separation of the CARS output signal relative to the three input beams inherent in a folded BOXCARS arrangement, this technique is particularly amenable to probing low-frequency vibrational modes, which play a significant role in accepting vibrational energy during intramolecular vibrational energy redistribution within electronically excited states. Additionally, this spatial separation allows discrimination against strong fluorescence signal, as demonstrated in the case of rhodamine 6G. 相似文献
318.
Roland De Marco Elaine Jee Kathryn Prince Ernö Pretsch Eric Bakker 《Journal of Solid State Electrochemistry》2009,13(1):137-148
High-integrity solid-contact (SC) polymeric ion sensors have been produced by using spin casting and electropolymerization
techniques in the preparation of the SC employing the conductive polymer, poly(3-octylthiophene) (POT). The physical and chemical
integrity of the POT SCs have been evaluated using scanning electron microscopy (SEM), atomic force microscopy (AFM), secondary
ion mass spectrometry (SIMS), and X-ray photoelectron spectroscopy (XPS). Furthermore, the electrochemical stability of SC
polymeric ion sensors has been investigated using electrochemical impedance spectroscopy (EIS). The results of this study
demonstrate that electropolymerization and spin casting methods also comprising annealing of the synthesized SC film are capable
of producing SCs that are relatively free of imperfections such as pores and pinholes. This leads to electrochemically stable
and robust polymeric ion sensors where the SC/sensor interface is resistant to the formation of a detrimental water layer
that normally gives rise to spurious ion fluxes and a degradation in the sensitivity and selectivity of the SC polymeric ion
sensor. 相似文献
319.
Catone D Stener M Decleva P Contini G Zema N Prosperi T Feyer V Prince KC Turchini S 《Physical review letters》2012,108(8):083001
A sizable enhancement of the circular dichroism in photoelectron spectroscopy has been measured and computed for the metal complex Δ-cobalt(III) tris-acetylacetonate highest occupied molecular orbital state in the region of the Co 3p→3d Fano resonance. In the resonance the dichroism reaches the maximum value of 5% and even changes its sign as compared to the direct photoionization channel. We ascribe this enhancement to electron correlation processes, namely, with the coupling between discrete excitations and the continuum, which is correctly described in the time dependent density functional theory (TDDFT) framework. These findings open new physical aspects of photoelectron circular dichroism that now can be interpreted not only via the simple direct ionization, but also through more complex electron correlation processes. 相似文献
320.
This article studies the unstructured and structured backward error analysis of specified eigenpairs for matrix polynomials. The structures we discuss include -symmetric, -skew-symmetric, Hermitian, skew Hermitian, -even, -odd, -even, -odd, -palindromic, -anti-palindromic, -palindromic, and -anti-palindromic matrix polynomials. Minimally structured perturbations are constructed with respect to Frobenius norm such that specified eigenpairs become exact eigenpairs of an appropriately perturbed matrix polynomial that also preserves sparsity. Further, we have used our results to solve various quadratic inverse eigenvalue problems that arise from real-life applications. 相似文献