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71.
The oxidative cleavage of the known anti-psoriasis drug 1 to give 2 has been reported previously. Due to the importance of accessing medium-sized ring containing systems via oxidative cleavage, this reaction has been revisited revealing additional information about the structure of 2. Alternative reaction products were identified when the reaction was carried out in the presence of water. The conversion of 1 to 2 has also been carried out using ruthenium tetroxide. A detailed variable temperature NMR and computational study of the restricted rotation of the N-aryl ring in 2 is presented. 相似文献
72.
The ASMS conference on ion spectroscopy brought together at Asilomar on October 16–20, 2009 a large group of mass spectrometrists
working in the area of ion spectroscopy. In this introduction to the field, we provide a brief history, its current state,
and where it is going. Ion spectroscopy of intermediate size molecules began with photoelectron spectroscopy in the 1960s,
while electronic spectroscopy of ions using the photodissociation “action spectroscopic” mode became active in the next decade.
These approaches remained for many years the main source of information about ionization energies, electronic states, and
electronic transitions of ions. In recent years, high-resolution laser techniques coupled with pulsed field ionization and
sample cooling in molecular beams have provided high precision ionization energies and vibrational frequencies of small to
intermediate sized molecules, including a number of radicals. More recently, optical parametric oscillator (OPO) IR lasers
and free electron lasers have been developed and employed to record the IR spectra of molecular ions in either molecular beams
or ion traps. These results, in combination with theoretical ab initio molecular orbital (MO) methods, are providing unprecedented
structural and energetic information about gas-phase ions. 相似文献
73.
Threshold photoelectron photoion coincidence has been used to prepare selected internal energy distributions of nitrosobenzene ions [C(6)H(5)NO(+)]. Dissociation to C(6)H(5)(+) + NO products was measured over a range of internal energies and rate constants from 10(3) to 10(7) s(-1) and fitted with the statistical theory of unimolecular decay. A 0 K dissociative photoionization onset energy of 10.607 ± 0.020 eV was derived by using the simplified statistical adiabatic channel model. The thermochemical network of Active Thermochemical Tables (ATcT) was expanded to include phenyl and phenylium, as well as nitrosobenzene. The current ATcT heats of formation of these three species at 0 K (298.15 K) are 350.6 (337.3) ± 0.6, 1148.7 (1136.8) ± 1.0, and 215.6 (198.6) ± 1.5 kJ mol(-1), respectively. The resulting adiabatic ionization energy of phenyl is 8.272 ± 0.010 eV. The new ATcT thermochemistry for phenyl entails a 0 K (298.15 K) C-H bond dissociation enthalpy of benzene of 465.9 (472.1) ± 0.6 kJ mol(-1). Several related thermochemical quantities from ATcT, including the current enthalpies of formation of benzene, monohalobenzenes, and their ions, as well as interim ATcT values for the constituent atoms, are also given. 相似文献
74.
Zachariasova M Cajka T Godula M Malachova A Veprikova Z Hajslova J 《Rapid communications in mass spectrometry : RCM》2010,24(22):3357-3367
The objective of the presented study was to develop and optimize a simple, high-throughput method for the control of 32 mycotoxins (Fusarium and Alternaria toxins, aflatoxins, ergot alkaloids, ochratoxins, and sterigmatocystin) in beer. Due to the broad range of their physicochemical properties, the sample preparation step was simplified as much as possible to avoid analyte losses. The addition of acetonitrile to beer samples enabled precipitation of abundant matrix components. The clean-up efficiency was controlled by ambient mass spectrometry employing a direct analysis in real time (DART) ion source. For determination of analytes, ultra-high-performance liquid chromatography hyphenated with high-resolution mass spectrometry utilizing an orbitrap (U-HPLC-orbitrapMS) or time-of-flight (TOFMS) technology was used. Because of significantly better detection capabilities of the orbitrap technology, the U-HPLC-orbitrapMS method was chosen as a determinative step and fully validated. To compensate matrix effects, matrix-matched calibration was employed. The lowest calibration levels for most of the target mycotoxins ranged from 1 to 8 μg L(-1) beer and the recoveries of analytes were in range from 86 to 124%. 相似文献
75.
The nucleophilic addition of both silyl ketene acetals and lithium enolates derived from methyl acetate to chiral non-racemic N-(benzyloxyethyl)nitrones has been studied both experimentally and theoretically. Aromatic nitrones showed lower reactivity that aliphatic nitrones and the addition of the silyl ketene acetal led to lower selectivities than the addition of the corresponding lithium enolate. Whereas low selectivity was obtained for the addition of the silyl ketene acetal, only one diastereomer could be detected in all cases for the addition of lithium enolate to aliphatic nitrones. The synthetic utility of the two chiral auxiliaries employed lies in the preparation of enantiomeric compounds. DFT theoretical calculations confirmed the stepwise mechanism for the addition of silyl ketene acetals to nitrones and are in good agreement with the observed experimental results. 相似文献
76.
77.
The topics of this paper are Fredholm properties and the applicability of the finite section method for band operators onl
p
-spaces as well as for their norm limits which we call band-dominated operators. The derived criteria will be established in terms of the limit operators of the given band-dominated operator. After presenting the general theory, we present its specifications to concrete classes of band-dominated operators.To the memory of Professor Mark KreinSupported by the DFG grant 436 RUS/17/148/95Supported by a DFG Heisenberg grant 相似文献
78.
C. Tomas J.P. Girardeau-Montaut M. Afif M. Romand M. Charbonnier T.M. Duc 《Applied Physics A: Materials Science & Processing》1997,64(5):467-471
3+ :YAG laser with 5th harmonic generator, generating 16 ps duration pulses at 213 nm, with energies up to 0.5 mJ. Experimental results concerning
the action of laser pulses, as well as the effects of residual pressure on the cleanliness of the photocathodes surface are
presented and discussed. Influence of laser pulses and residual pressure on the work function of the metal are also investigated.
Received: 15 April 1996/Accepted: 5 November
1996 相似文献
79.
Tomas de Paulis Nabil El Tayar Pierre-Alain Carrupt Bernard Testa Han van de Waterbeemd 《Helvetica chimica acta》1991,74(2):241-254
A large series of orthopramides (= 2-methoxybenzamides), 6-methoxysalicylamides, and 2,6-dimethoxy-benzamides were examined for their affinity to the dopamine D2 receptor. The binding data were correlated with physicochemical parameters and 13C-NMR chemical shifts using the cross-validated partial least-squares method and multiple linear regression analysis. The results quantitate the influence of electronic factors and lipophilicity to D2 receptor binding. They also show that the N-[(1-ethylpyrroIidin-2-yl)methyl] and N-(1-benzylpiperidin-4-yl) side-chains affect the mode of binding of these compounds. 相似文献
80.
We provide solution techniques for the analysis of multiplexers with periodic arrival streams, which accurately account for the effects of active and idle periods and of gradual arrival. In the models considered in this paper, it is assumed that each source alternates (periodically) between active and idle periods of fixed durations. Incoming packets are transmitted on the network link and excess information is stored in the multiplexing buffer when the aggregate input rate exceeds the capacity of the link. We are interested in the probability distribution of the buffer content for a given network link speed as a function of the number of sources and their characteristics, i.e., rate and duration of idle and active periods. We derive this distribution from two models: discrete time and continuous time systems. Discrete time systems operate in a slotted fashion, with a slot defining the base unit for data generation and transmission. In particular, in each slot the link is capable of transmitting one data unit and conversely an active source generates one data unit in that time. The continuous time model of the paper falls in the category of fluid models. Compared to previous works we allow a more general model for the periodic packet arrival process of each source. In discrete time, this means that the active period of a source can now extend over several consecutive slots instead of a single slot as in previous models. In continuous time, packet arrivals are not required to be instantaneous, but rather the data generation process can now take place over the entire duration of the active period. In both cases, these generalizations allow us to account for the progressive arrival of source data as a function of both the source speed and the amount of data it generates in an active period.This work was done while at the IBM T.J. Watson Research Center.This work was done while at the IBM T.J. Watson Research Center.Part of the work was done while visiting the IBM T.J. Watson Research Center. 相似文献