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961.
Dr. Gabriele Di Carlo Dr. Alessio Orbelli Biroli Prof. Maddalena Pizzotti Dr. Francesca Tessore Dr. Vanira Trifiletti Dr. Riccardo Ruffo Prof. Alessandro Abbotto Dr. Anna Amat Dr. Filippo De Angelis Prof. Patrizia R. Mussini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(32):10723-10740
A facile and fast approach, based on microwave‐enhanced Sonogashira coupling, has been employed to obtain in good yields both mono‐ and, for the first time, disubstituted push–pull ZnII porphyrinates bearing a variety of ethynylphenyl moieties at the β‐pyrrolic position(s). Furthermore, a comparative experimental, electrochemical, and theoretical investigation has been carried out on these β‐mono‐ or disubstituted ZnII porphyrinates and meso‐disubstituted push–pull ZnII porphyrinates. We have obtained evidence that, although the HOMO–LUMO energy gap of the meso‐substituted push–pull dyes is lower, so that charge transfer along the push–pull system therein is easier, the β‐mono‐ or disubstituted push–pull porphyrinic dyes show comparable or better efficiencies when acting as sensitizers in DSSCs. This behavior is apparently not attributable to more intense B and Q bands, but rather to more facile charge injection. This is suggested by the DFT electron distribution in a model of a β‐monosubstituted porphyrinic dye interacting with a TiO2 surface and by the positive effect of the β substitution on the incident photon‐to‐current conversion efficiency (IPCE) spectra, which show a significant intensity over a broad wavelength range (350–650 nm). In contrast, meso‐substitution produces IPCE spectra with two less intense and well‐separated peaks. The positive effect exerted by a cyanoacrylic acid group attached to the ethynylphenyl substituent has been analyzed by a photophysical and theoretical approach. This provided supporting evidence of a contribution from charge‐transfer transitions to both the B and Q bands, thus producing, through conjugation, excited electrons close to the carboxylic anchoring group. Finally, the straightforward and effective synthetic procedures developed, as well as the efficiencies observed by photoelectrochemical measurements, make the described β‐monosubstituted ZnII porphyrinates extremely promising sensitizers for use in DSSCs. 相似文献
962.
Dr. Markus Horn Dr. Ludwig H. Schappele Dr. Gabriele Lang‐Wittkowski Prof. Dr. Herbert Mayr Dr. Armin R. Ofial 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(1):249-263
Rates of hydride transfer from several hydride donors to benzhydrylium ions have been measured at 20 °C and used for the determination of empirical nucleophilicity parameters N and sN according to the linear free energy relationship log k20 °C=sN(N+E). Comparison of the rate constants of hydride abstraction by tritylium ions with those calculated from the reactivity parameters sN, N, and E showed fair agreement. Therefore, it was possible to convert the large number of literature data on hydride abstraction by tritylium ions into N and sN parameters for the corresponding hydride donors, and construct a reactivity scale for hydride donors covering more than 20 orders of magnitude. 相似文献
963.
Laura Bertoletti Luca Regazzoni Giancarlo Aldini Raffaella Colombo Franco Abballe Gabriele Caccialanza Ersilia De Lorenzi 《Analytica chimica acta》2013
In this work we present for the first time the use of ion-exchange liquid chromatography to separate the native form and a partially structured intermediate of the folding of the amyloidogenic protein beta2-microglobulin. Using a strong anion-exchange column that accounts for the differences in charge exposure of the two conformers, a LC–UV method is initially optimised in terms of mobile phase pH, composition and temperature. The preferred mobile phase conditions that afford useful information were found to be 35 mM ammonium formate, pH 7.4 at 25 °C. The dynamic equilibrium of the two species is demonstrated upon increasing the concentration of acetonitrile in the protein sample. Then, the chromatographic method is transferred to MS detection and the respective charge state distributions of the separated conformers are identified. The LC–MS results demonstrate that one of the conformers is partially unfolded, compared with the native and more compact species. The correspondence with previous results obtained in free solution by capillary electrophoresis suggest that strong ion exchange LC–MS does not alter beta2-microglobulin conformation and maintains the dynamic equilibrium already observed between the native protein and its folding intermediate. 相似文献
964.
965.
Carbonylation of styrenes catalyzed by bioxazoline Pd(II) complexes: mechanism of enantioselectivity
Carfagna C Gatti G Mosca L Natanti P Paoli P Rossi P Gabriele B Salerno G 《Dalton transactions (Cambridge, England : 2003)》2011,40(25):6792-6801
Preliminary studies of the elementary steps involved in the reaction of a chiral methyl carbonyl bioxazoline Pd(II) complex with aromatic olefins and CO have allowed development of a new enantioselective catalytic carbonylation process, leading to γ-ketoester derivatives with high yield and good enantiomeric excess. The intermediate palladacycle complexes have been isolated and characterized by NMR spectroscopy and X-ray diffraction. Factors that govern the stereoselectivity of the olefin carbonylation process are discussed. 相似文献
966.
Singh B Drew MG Kociok-Kohn G Molloy KC Singh N 《Dalton transactions (Cambridge, England : 2003)》2011,40(3):623-631
An uncommon coordination protocol induced by the p-tolylsulfonyl dithiocarbimate ligand (L) [L = p-CH(3)C(6)H(4)SO(2)N[double bond, length as m-dash]CS(2)(2-)] in conjunction with PPh(3) allowed the formation of novel homodimetallic, Cu(2)(PPh(3))(4)L (1), trinuclear heterometallic Cu(2)Ni(L)(2)(PPh(3))(4) (2) and heteroleptic complexes of general formula cis-[M(PPh(3))(2)L] [M = Pd(ii) (3), Pt(ii) (4)]. The complexes have been characterized by microanalysis, mass spectrometry, IR, (1)H, (13)C and (31)P NMR and electronic absorption spectra and single-crystal X-ray crystallography. 2 uniquely consists of square planar, trigonal planar and tetrahedral coordination spheres within the same molecule. In both heteroleptic complexes 3 and 4 the orientation of aromatic protons of PPh(3) ligand towards the Pd(ii) and Pt(ii) center reveals C-HPd and C-HPt rare intramolecular anagostic or preagostic interactions. These complexes exhibit photoluminescent properties in solution at room temperature arising mainly from intraligand charge transfer (ILCT) transitions. The assignment of electronic absorption bands has been corroborated by time dependent density functional theory (TD-DFT) calculations. Complexes 1 and 2 with σ(rt) values ~ 10(-6) S cm(-1) show semi-conductor properties in the temperature range 313-403 K whereas 3 and 4 exhibit insulating behaviour. 相似文献
967.
Gabriele B Mancuso R Lupinacci E Veltri L Salerno G Carfagna C 《The Journal of organic chemistry》2011,76(20):8277-8286
Novel and convenient approaches to benzothiophene derivatives 3 and 5 have been developed, based on heterocyclization reactions of 1-(2-mercaptophenyl)-2-yn-1-ols 2 or 4, respectively, readily available from alkynylation of 2-mercaptobenzaldehydes or 1-(2-mercaptophenyl) ketones 1. In particular, 1-(2-mercaptophenyl)-2-yn-1-ols 2, bearing a CH(2)R substituent on the triple bond (R = alkyl, aryl), were conveniently converted in fair to good yields (55-82%) into (E)-2-(1-alkenyl)benzothiophenes 3 when allowed to react in the presence of catalytic amounts (2 mol %) of PdI(2) in conjunction with KI (KI:PdI(2) molar ratio =10) at 80-100 °C in MeCN as the solvent, through a heterocyclodehydration process. On the other hand, 2-alkoxymethylbenzothiophenes 5 were selectively obtained in fair to excellent yields (49-98%) via a radical-promoted substitutive heterocyclodehydration process, by reacting 1-(2-mercaptophenyl)-2-yn-1-ols 4 (bearing an alkyl or aryl substituent on the triple bond) in alcoholic media at 80-100 °C in the presence of a radical initiator, such as AIBN. 相似文献
968.
Gabriele Milani 《International Journal of Solids and Structures》2011,48(2):326-345
A homogenization model for periodic masonry structures reinforced with continuous FRP grids is presented. Starting from the observation that a continuous grid preserves the periodicity of the internal masonry layer, rigid-plastic homogenization is applied directly on a multi-layer heterogeneous representative element of volume (REV) constituted by bricks, finite thickness mortar joints and external FRP grids. In particular, reinforced masonry homogenized failure surfaces are obtained by means of a compatible identification procedure, where each brick is supposed interacting with its six neighbors by means of finite thickness mortar joints and the FRP grid is applied on the external surfaces of the REV. In the framework of the kinematic theorem of limit analysis, a simple constrained minimization problem is obtained on the unit cell, suitable to estimate – with a very limited computational effort – reinforced masonry homogenized failure surfaces.A FE strategy is adopted at a cell level, modeling joints and bricks with six-noded wedge shaped elements and the FRP grid through rigid infinitely resistant truss elements connected node by node with bricks and mortar. A possible jump of velocities is assumed at the interfaces between contiguous wedge and truss elements, where plastic dissipation occurs. For mortar and bricks interfaces, a frictional behavior with possible limited tensile and compressive strength is assumed, whereas for FRP bars some formulas available in the literature are adopted to reproduce the delamination of the truss from the support.Two meaningful structural examples are considered to show the capabilities of the procedure proposed, namely a reinforced masonry deep beam (0°/90° continuous reinforcement) and a masonry beam in simple flexion for which experimental data are available. Good agreement is found between present model and alternative numerical approaches. 相似文献
969.
Alice Senizza Gabriele Rocchetti Juana I. Mosele Vania Patrone Maria Luisa Callegari Lorenzo Morelli Luigi Lucini 《Molecules (Basel, Switzerland)》2020,25(23)
Plant polyphenols are a broad group of bioactive compounds characterized by different chemical and structural properties, low bioavailability, and several in vitro biological activities. Among these compounds, lignans (a non-flavonoid polyphenolic class found in plant foods for human nutrition) have been recently studied as potential modulators of the gut–brain axis. In particular, gut bacterial metabolism is able to convert dietary lignans into therapeutically relevant polyphenols (i.e., enterolignans), such as enterolactone and enterodiol. Enterolignans are characterized by various biologic activities, including tissue-specific estrogen receptor activation, together with anti-inflammatory and apoptotic effects. However, variation in enterolignans production by the gut microbiota is strictly related to both bioaccessibility and bioavailability of lignans through the entire gastrointestinal tract. Therefore, in this review, we summarized the most important dietary source of lignans, exploring the interesting interplay between gut metabolites, gut microbiota, and the so-called gut–brain axis. 相似文献
970.
Alice Santoro Jenifer S. Calvo Manuel David Peris‐Díaz Artur Krel Gabriele Meloni Peter Faller 《Angewandte Chemie (International ed. in English)》2020,59(20):7830-7835
Copper complexes are of medicinal and biological interest, including as anticancer drugs designed to cleave intracellular biomolecules by O2 activation. To exhibit such activity, the copper complex must be redox active and resistant to dissociation. Metallothioneins (MTs) and glutathione (GSH) are abundant in the cytosol and nucleus. Because they are thiol‐rich reducing molecules with high CuI affinity, they are potential competitors for a copper ion bound in a copper drug. Herein, we report the investigation of a panel of CuI/CuII complexes often used as drugs, with diverse coordination chemistries and redox potentials. We evaluated their catalytic activity in ascorbate oxidation based on redox cycling between CuI and CuII, as well as their resistance to dissociation or inactivation under cytosolically relevant concentrations of GSH and MT. O2‐activating CuI/CuII complexes for cytosolic/nuclear targets are generally not stable against the GSH/MT system, which creates a challenge for their future design. 相似文献