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排序方式: 共有217条查询结果,搜索用时 15 毫秒
1.
Alessandro Cecchi Giuditta Bartalucci Cinzia Chiappe Roberto Bianchini 《国际化学动力学杂志》2007,39(4):197-203
The kinetics of the electrophilic bromination of three allylic ethers in a nonprotic solvent, 1,2‐dichloroethane, has been investigated. Two of them followed a prevalent second‐order pathway, while the third one exhibited a classical, clean third order. The second‐order pathway in the first two olefins is attributed to electrophilic assistance of the ethereal oxygen to the attacking bromine molecule. In the molecular bromination of 2,4‐cis‐dimethyl‐8‐oxabicyclo[3.2.1]‐6‐octen‐3‐cis‐ol, opposite temperature dependences were found for the two different kinetic pathways. An exoergonic process for the second‐order reaction was explained by the lesser stability of the bromiranium–bromide ionic intermediate, compared to the bromiranium–tribromide in the third‐order profile. © 2007 Wiley Periodicals, Inc. 39: 197–203, 2007 相似文献
2.
Riccò M Shiroka T Carretta S Bolzoni F Femoni C Iapalucci MC Longoni G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2856-2861
The magnetic behaviour of the even-electron [Ni16Pd16(CO)40]4- cluster, in its [NnBu4]+ salt, has been investigated by magnetometry and muon spin rotation/relaxation (muSR) spectroscopy. The susceptibility measurements show an exceptionally high magnetic moment corresponding to a total spin value J=2. This suggests a Hund filling of a quadruplet ground state, quite unique in carbonyl-metal clusters. SQUID magnetometry shows a departure from the Curie-Weiss law, for T>150 K, and strong deviation from a Brillouin behaviour of the magnetisation curves. muSR spectroscopy in zero applied field shows a temperature independent decay of the muon spin polarisation, similar to that of a purely paramagnetic system. The observed muon spin repolarisation in a moderate external longitudinal field, however, invalidates this simple picture and suggests the presence of a local anisotropy field acting on the cluster's magnetic moment. A consistent interpretation of magnetometry and muSR results implies the occurrence of an additional interaction of the cluster spin with an effective crystalline field. The inclusion of this interaction in a model Hamiltonian allows us to successfully reproduce both the susceptibility and magnetisation data. 相似文献
3.
Copper bronze catalyzed Heck reaction in ionic liquids 总被引:1,自引:0,他引:1
Heck reaction of aryl iodides and activated aryl bromides catalyzed by copper bronze in tetrabutylammonium bromide as solvent and tetrabutylammonium acetate as base was developed. The effective catalysts are Cu nanoparticles deriving from the reaction of iodobenzene with copper bronze. These nanoparticles are very stable in tetraalkylammonium salts, are easily recycled, and can be stored for months without a loss of catalytic efficiency. [reaction: see text] 相似文献
4.
Bischelate platinum(II) complexes of the type [Pt(H-R(2)-N(2)C(2)S(2))(2)] (H-R(2)-N(2)C(2)S(2)(-) = dialkyl-dithioxamidate) are ditopic receptors which, after coordination of the first Pd(eta(3)-allyl)(+) moiety, induce the orientation of the second palladium-allyl fragment. Thus, a series of trimetallic complexes of formula bis-[(eta(3)-allyl)-palladium(II)](mu-bis-dialkyl-dithioxamidate-platinum(II) kappa-S,S-kappa-S',S'-Pt-kappa-N,N-Pd-kappa-N',N'-Pd') has been prepared in which the allyl fragments are oriented toward the same side of the molecular plane. We have also prepared the trimetallic complex using a dithioxamide obtained from the racemic phenylethylamine. Only two isomers were produced in equimolar ratio: the racemate that has four homochiral alkyl substituents and the mesoform containing the meso-dithioxamide that has homochiral substituents on the same side of molecular plane. Under the effect of the temperature, the trimetallic Pd-Pt-Pd complexes undergo rapid allyl isomerization; the mechanism of the isomerization, which is similar to that found by us in an analogue Pt-Pd bimetallic complex, is discussed. The crystal and molecular structure of bis-[(eta(3)-allyl)-palladium(II)](mu-bis-[S]-phenylethyl-dithioxamidate-platinum(II) kappa-S,S-kappa-S',S'-Pt-kappa-N,N-Pd-kappa-N',N'-Pd') has been reported. 相似文献
5.
6.
Broadband Sheet Parametric Oscillator for x~((2)) Optical Frequency Comb Generation via Cavity Phase Matching 下载免费PDF全文
Xin Ni Kunpeng Jia Xiaohan Wang Huaying Liu Jian Guo Shu-Wei Huang Baicheng Yao Nicolò Sernicola Zhenlin Wang Xinjie Lv Gang Zhao Zhenda Xie Shi-Ning Zhu 《中国物理快报》2021,(6):37-49
We demonstrate a broadband optical parametric oscillation, using a sheet cavity, via cavity phase-matching. A21.2 THz broad comb-like spectrum is achieved, with a uniform line spacing of 133.0 GHz, despite a relatively large dispersion of 275.4 fs~2/mm around 1064 nm. With 22.6% high slope efficiency, and 14.9 kW peak power handling, this sheet optical parametric oscillator can be further developed for x~((2)) comb. 相似文献
7.
Giovanni Amelino-Camelia Leonardo Barcaroli Niccoló Loret 《International Journal of Theoretical Physics》2012,51(11):3359-3375
We investigate some aspects of relativistic classical theories with “relative locality”, in which pairs of events established to be coincident by nearby observers may be described as non-coincident by distant observers. While previous studies focused mainly on the case of longitudinal relative locality, where the effect occurs along the direction connecting the distant observer to the events, we here focus on transverse relative locality, in which instead the effect is found in a direction orthogonal to the one connecting the distant observer to the events. Our findings suggest that, at least for theories of free particles, transverse relative locality is as significant as longitudinal relative locality both conceptually and quantitatively. And we observe that “dual gravity lensing” can be viewed as one of two components of transverse relative locality. We also speculate about a type of spacetime noncommutativity for which transverse relative locality could be particularly significant. 相似文献
8.
Jordan De Jesus Silva Niccolò Bartalucci Benson Jelier Samantha Grosslight Tobias Gensch Claas Schünemann Bernd Müller Paul C. J. Kamer Christophe Copéret Matthew S. Sigman Antonio Togni 《Helvetica chimica acta》2021,104(12):e2100200
A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts. 相似文献
9.
Poly‐l‐Lactic Acid Nanofiber–Polyamidoamine Hydrogel Composites: Preparation,Properties, and Preliminary Evaluation as Scaffolds for Human Pluripotent Stem Cell Culturing 下载免费PDF全文
Chiara Gualandi Nora Bloise Nicolò Mauro Paolo Ferruti Amedea Manfredi Maurilio Sampaolesi Anna Liguori Romolo Laurita Matteo Gherardi Vittorio Colombo Livia Visai Maria Letizia Focarete Elisabetta Ranucci 《Macromolecular bioscience》2016,16(10):1533-1544
Electrospun poly‐l ‐lactic acid (PLLA) nanofiber mats carrying surface amine groups, previously introduced by nitrogen atmospheric pressure nonequilibrium plasma, are embedded into aqueous solutions of oligomeric acrylamide‐end capped AGMA1, a biocompatible polyamidoamine with arg‐gly‐asp (RGD)‐reminiscent repeating units. The resultant mixture is finally cured giving PLLA‐AGMA1 hydrogel composites that absorb large amounts of water and, in the swollen state, are translucent, soft, and pliable, yet as strong as the parent PLLA mat. They do not split apart from each other when swollen in water and remain highly flexible and resistant, since the hydrogel portion is covalently grafted onto the PLLA nanofibers via the addition reaction of the surface amine groups to a part of the terminal acrylic double bonds of AGMA1 oligomers. Preliminary tested as scaffolds, the composites prove capable of maintaining short‐term undifferentiated cultures of human pluripotent stem cells in feeder‐free conditions.
10.
Tiziana Benincori Prof. Andrea Marchesi Dr. Patrizia Romana Mussini Prof. Tullio Pilati Dr. Alessandro Ponti Dr. Simona Rizzo Dr. Francesco Sannicolò Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(1):86-93
Two new tris(aryl)phosphane oxides existing as configurationally stable residual enantiomers have been synthesised and their racemates resolved by semipreparative HPLC on a chiral stationary phase (CSP HPLC). One of them, recognised as a conglomerate, could be resolved by fractional crystallisation at a preparative scale level. In this case, the absolute configuration of the propeller‐shaped molecule was determined by anomalous X‐ray scattering. The problem of the correlative assignment of the absolute configuration to all known C3‐symmetric three‐bladed propeller‐shaped molecules existing as stable residual enantiomers is discussed. The configurational stability of the new chiral phosphane oxides and of the corresponding phosphanes was evaluated by CD signal decay kinetics and dynamic 1H NMR spectroscopy. The racemisation barriers in phosphanes were found about 10 kcal mol?1 lower than those found for the corresponding oxides, though geometry and inter‐ring gearing would be very similar in the two series. Configurational stability of residual tris(aryl)phosphanes was found to be influenced by the electronic availability of the phosphorus centre, as evaluated by electrochemical CV experiments. 相似文献