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731.
Billon A Picaut J Foy C Valeau V Sakout A 《The Journal of the Acoustical Society of America》2008,123(6):4040-4043
This paper presents an extension of a diffusion model for room acoustics to handle the atmospheric attenuation. This phenomenon is critical at high frequencies and in large rooms to obtain correct acoustic predictions. An additional term is introduced in the diffusion equation as well as in the diffusion constant, in order to take the atmospheric attenuation into account. The modified diffusion model is then compared with the statistical theory and a cone-tracing software. Three typical room-acoustic configurations are investigated: a proportionate room, a long room and a flat room. The modified diffusion model agrees well with the statistical theory (when applicable, as in proportionate rooms) and with the cone-tracing software, both in terms of sound pressure levels and reverberation times. 相似文献
732.
Molecular imaging by Mid-IR laser ablation mass spectrometry 总被引:1,自引:0,他引:1
Akos Vertes Peter Nemes Bindesh Shrestha Alexis A. Barton Zhaoyang Chen Yue Li 《Applied Physics A: Materials Science & Processing》2008,93(4):885-891
Mid-IR laser ablation at atmospheric pressure (AP) produces a mixture of ions, neutrals, clusters, and particles with a size
distribution extending into the nanoparticle range. Using external electric fields the ions can be extracted and sampled by
a mass spectrometer. In AP infrared (IR) matrix-assisted laser desorption ionization (MALDI) experiments, the plume was shown
to contain an appreciable proportion of ionic components that reflected the composition of the ablated target and enabled
mass spectrometric analysis. The detected ion intensities rapidly declined with increasing distance of sampling from the ablated
surface to ∼4 mm. This was rationalized in terms of ion recombination and the stopping of the plume expansion by the background
gas. In laser ablation electrospray ionization (LAESI) experiments, the ablation plume was intercepted by an electrospray.
The neutral particles in the plume were ionized by the charged droplets in the spray and enabled the detection of large molecules
(up to 66 kDa). Maximum ion production in LAESI was observed at large (∼15 mm) spray axis to ablated surface distance indicating
a radically different ion formation mechanism compared to AP IR-MALDI. The feasibility of molecular imaging by both AP IR-MALDI
and LAESI was demonstrated on targets with mock patterns.
Presented at the 9-th International Conference on Laser Ablation, 2007 Tenerife, Canary Islands, Spain 相似文献
733.
Ghasemi SA Goedecker S Baratoff A Lenosky T Meyer E Hug HJ 《Physical review letters》2008,100(23):236106
Atomistic simulations considering larger tip structures than hitherto assumed reveal novel dissipation mechanisms in noncontact atomic force microscopy. The potential energy surfaces of realistic silicon tips exhibit many energetically close local minima that correspond to different structures. Most of them easily deform, thus causing dissipation arising from hysteresis in force versus distance characteristics. Furthermore, saddle points which connect local minima can suddenly switch to connect different minima. Configurations driven into metastability by the tip motion can thus suddenly access lower energy structures when thermal activation becomes allowed within the time required to detect the resulting average dissipation. 相似文献
734.
Yeljair Monascal Eliana Gallardo Loriett Cartaya Alexis Maldonado Yenner Bentarcurt Gabriel Chuchani 《Molecular physics》2018,116(2):194-203
Keto–enol tautomeric equilibrium and the mechanism of thermal conversion of 2- and 4-hydroxyacetophenone in gas phase have been studied by means of electronic structure calculations using density functional theory (DFT). A topological analysis of electron density evidence that the structure of keto and enol forms of 2-hydroxyacetophenone are stabilised by a relatively strong intramolecular hydrogen bond. 2- and 4-hydroxyacetophenone undergo deacetylation reactions yielding phenol and ketene. Two possible mechanisms are considered for these eliminations: the process takes place from the keto form (mechanism A), or occurs from the enolic form of the substrate (mechanism B). Quantum chemical calculations support the mechanism B, being found a good agreement with the experimental activation parameters. These results suggest that the rate-limiting step is the reaction of the enol through a concerted, non-synchronous, semi-polar, four-membered cyclic transition state (TS). The most advanced reaction coordinate in the TS is the rupture of O1···H1 bond, with an evolution in the order of 79.7%–80.9%. Theoretical results also suggest a three-step mechanism for the phenyl acetate formation from 2-hydroxyacetophenone. 相似文献
735.
Jacobi polynomials were introduced by Ozeki in analogy with Jacobi forms of lattices. They are useful to compute coset weight
enumerators, and weight enumerators of children. We determine them in most interesting cases in length at most 32, and in
some cases in length 72. We use them to construct group divisible designs, packing designs, covering designs, and (t,r)-designs in the sense of Calderbank-Delsarte. A major tool is invariant theory of finite groups, in particular simultaneous
invariants in the sense of Schur, polarization, and bivariate Molien series. A combinatorial interpretation of the Aronhold
polarization operator is given. New rank parameters for spaces of coset weight distributions and Jacobi polynomials are introduced
and studied here. 相似文献
736.
The relatively high electronegativity of nitrogen makes N–N bond forming cross-coupling reactions particularly difficult, especially in an intermolecular fashion. The challenge increases even further when considering the case of dehydrogenative N–N coupling reactions, which are advantageous in terms of step and atom economy, but introduce the problem of the oxidant in order to become thermodynamically feasible. Indeed, the oxidizing system must be designed to activate the target N–H bonds, while at the same time avoid undesired N–N homocoupling as well as C–N and C–C coupled side products. Thus, preciously few intermolecular hetero N–N cross-dehydrogenative couplings exist, in spite of the central importance of N–N bonds in organic chemistry. This review aims at analyzing these few rare cases and provides a perspective for future developments.For more than a century, the dehydrogenative formation of N–N bonds has remained mostly confidential. Several cross-dehydrogenative N–N coupling methods have appeared recently, promising a soon to come broad applicability of the concept. 相似文献
737.
Alexis St-Gelais Eliana M. Maldonado Gloria Saavedra Samuel Siles-Alvarado Jrme Alsarraf Guy Collin Andr Pichette 《Molecules (Basel, Switzerland)》2021,26(19)
Over 15 years, with the support of a Canadian funding agency, the Universidad Mayor de San Simón, in Bolivia, undertook a large survey of aromatic plants of the South American country. More than a hundred species were studied under various aspects, including the production and characterization of essential oils. As part of this survey, the chemical composition of an essential oil sample obtained from Pentacalia herzogii (Asteraceae) growing wild in the High Valley region of the department of Cochabamba was determined by a combination of GC and GC-MS measurements. α-Pinene was the main constituent of this essential oil (34%), accompanied by limonene (22%) and germacrene D (7.5%) as well as an important fraction of methoxylated monoterpenoids. They were mainly isomers of thymol methyl ether, accounting for 13% of the chromatogram. A new quantitatively important compound (9%) was identified through NMR and chemical synthesis as 4-isopropyl-6-methylbenzo[d][1,3]dioxole, and designated herzogole, alongside the minor related compound 1-isopropyl-2,3-dimethoxy-5-methylbenzene. The monoterpene benzodioxole featured a distinctive green-phenolic aroma which could raise interest for fragrance use. Since these compounds were not known naturally, a biosynthetic mechanism of their formation was proposed and put in perspective to illustrate the metabolic originality of P. herzogii. 相似文献
738.
Morin D Grasland B Vallée-Réhel K Dufau C Haras D 《Journal of chromatography. A》2003,1002(1-2):79-92
A protocol using reversed-phase liquid chromatography coupled with positive-ion electrospray ionization and ion trap mass spectrometry is described for the identification and quantification of N-acylhomoserine lactones (HSLs) in crude cell-free supernatants of bacterial cultures. The HSLs are produced by gram-negative bacteria and act as intercellular signals inducing density-dependent gene expression. Compared with the multi-step procedures previously reported, which included chemical extraction, purification and the use of Escherichia coli HSL biosensors, this on-line LC-MS-MS method is fast and detects 11 HSLs. Its speed and robustness allow the analysis of a large number of samples without loss of performance (no signal variation for a control sample after 90 chromatographic injections). The selectivity is based on the MS-MS fragment ions of the molecular [M+H]- ions and on their relative intensities. For quantification, the m/z 102 ion, specific for the lactone ring and detected with a good signal-to-noise ratio, allows low detection limits even in complex matrix samples (0.28 up to 9.3 pmol). Moreover, this method allows the quantification of 11 HSLs whatever their chemical structure, substituted or not. The protocol was applied to Vibrio vulnificus, a marine bacterium. Six HSLs were detected and quantified with relative standard deviations for repeatability of < 10%. 相似文献
739.
Dr. Denis Leshchev Dr. Andrew J. S. Valentine Dr. Pyosang Kim Dr. Alexis W. Mills Dr. Subhangi Roy Dr. Arnab Chakraborty Dr. Elisa Biasin Prof. Kristoffer Haldrup Dr. Darren J. Hsu Dr. Matthew S. Kirschner Dr. Dolev Rimmerman Dr. Matthieu Chollet Dr. J. Michael Glownia Dr. Tim B. van Driel Prof. Felix N. Castellano Prof. Xiaosong Li Prof. Lin X. Chen 《Angewandte Chemie (International ed. in English)》2023,62(28):e202304615
Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited-state trajectories of a diplatinum complex featuring photo-activated metal–metal σ-bond formation and associated Pt−Pt stretching motions were detected in real time using femtosecond wide-angle X-ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt−Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited-state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non-equilibrium processes along excited-state trajectories involving multiple excited-state PESs. 相似文献
740.
Yves Grohens Stephane Ulvé Karine Vallée-Réhel Jean Jacques Péron Dominique Haras 《Macromolecular Symposia》2003,203(1):271-276
Contact angle measurements (captive bubble and sessile drop techniques) were used to determine the surface energy of several acrylic based polymers at the early stage of immersion (t0) in pure and salt water or after several days (tx). The sessile drop technique using various liquid probes allows the calculation of the dispersive, acid and basic components of the surface energy. Significant differences of wettability are observed between the polymers at t0 which tend to remain after immersion along with a general increase of the surface hydrophilicity. The same trend is observed by the “in-situ” captive bubble technique. The surfaces become more hydrophilic with a final contact angle, θ, ranging from 110 to 150 ± 3° in pure water and 130 to 150 ± 4° in 0,51 M salt water. The modifications of surface energy between t0 and tx are not only dependent on water diffusion. One assumption is that the degree of swelling of the immersed surface layer along with the particular dynamics resulting from a surface gel-like structure are significant factors in the measured surface thermodynamics. 相似文献