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71.
Dr. William Herzog Dr. Catherine Bronner Susanne Löffler Dr. Bice He Daniel Kratzert Prof. Dietmar Stalke Prof. Andreas Hauser Prof. Oliver S. Wenger 《Chemphyschem》2013,14(6):1168-1176
Two pyridylphenols with intramolecular hydrogen bonds between the phenol and pyridine units have been synthesized, characterized crystallographically, and investigated by cyclic voltammetry and UV/Vis spectroscopy. Reductive quenching of the triplet metal‐to‐ligand charge‐transfer excited state of the [Re(CO)3(phen)(py)]+ complex (phen=1,10‐phenanthroline, py=pyridine) by the two pyridylphenols and two reference phenol molecules is investigated by steady‐state and time‐resolved luminescence spectroscopy, as well as by transient absorption spectroscopy. Stern–Volmer analysis of the luminescence quenching data provides rate constants for the bimolecular excited‐state quenching reactions. H/D kinetic isotope effects for the pyridylphenols are on the order of 2.0, and the bimolecular quenching reactions are up to 100 times faster with the pyridylphenols than with the reference phenols. This observation is attributed to the markedly less positive oxidation potentials of the pyridylphenols with respect to the reference phenols (≈0.5 V), which in turn is caused by proton coupling of the phenol oxidation process. Transient absorption spectroscopy provides unambiguous evidence for the photogeneration of phenoxyl radicals, that is, the overall photoreaction is clearly a proton‐coupled electron‐transfer process. 相似文献
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74.
Water adsorption and desorption pretreatment of surfaces increases the maximum amount of adsorbed water molecules by a multiple 总被引:1,自引:0,他引:1
Dietmar Neuhaus 《Adsorption》2013,19(6):1127-1135
The amount of adsorbed water on surfaces in an atmosphere with 100 % relative humidity can be increased by a multiple, if the surfaces are pretreated by cycles of adsorption and desorption of water. This was observed on surfaces of diamond, titanium dioxide and silicon dioxide at temperatures around 22 °C. With a sufficient number of such cycles a faster and stronger adsorption of water molecules was obtained, if compared with untreated surfaces. This also means an increased energy transfer from the atmosphere to the surface. Due to the pretreatment the amount of adsorbed water was more than three times increased. The observed effect is explained by small amounts of specially arranged water molecules, which remain on the surface after the desorption process and which support the adsorption of water. The observed effect can be used to moisten surfaces of small particles very efficiently from the gas phase. 相似文献
75.
Dr. Juntao Zhang Prof. Dr. Hak‐Fun Chow Prof. Dr. Man‐Chor Chan Gary Ka‐Wai Chow Prof. Dr. Dietmar Kuck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):15019-15025
A homologous series of oligo(amide–triazole)s (OAT) [ OAT‐CO2H‐2 n and OAT‐COPrg‐(2 n +1) ] with an increasing number of primary amide (CONH) and triazole hydrogen‐bonding functionalities was prepared by an iterative synthetic procedure. It was found that their self‐assembly and thermoreversible gelation strength had a strong correlation to the number of hydrogen‐bonding moieties in the oligomers. There also existed a threshold value of the number of CONH units, above which all the oligomers became organogelators. Hence, oligomers with ≤4 CONH units are devoid of intermolecular hydrogen bonding and also non‐organogelating, whereas those that contain >4 CONH units show intermolecular association and organogelating properties. For the organogelators, the Tgel value increases monotonically with increasing number of CONH units. On the basis of FTIR measurements, both the CONH and triazole C? H groups were involved in the hydrogen‐bonding process. A mixed xerogel that consisted of a 1:1 weight ratio of two oligomers of different lengths ( OAT‐CO2H‐6 and OAT‐CO2H‐12 ) was found to show microphase segregation according to differential scanning calorimetry, thus indicating that oligomers that bear a different number of hydrogen‐bonding units exhibited self‐sorting to maximize the extent of intermolecular hydrogen bonding in the xerogel state. 相似文献
76.
Dr. Ramachandran Azhakar Dr. Rajendra S. Ghadwal Prof. Dr. Herbert W. Roesky Prof. Dr. Ricardo A. Mata Hilke Wolf Regine Herbst‐Irmer Prof. Dr. Dietmar Stalke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(11):3715-3720
Three‐ and five‐membered rings that bear the (Si‐C‐S ) and (Si‐C‐C‐C‐S ) unit have been synthesized by the reactions of L SiCl ( 1 ; L =PhC(NtBu)2) and L′ Si ( 2 ; L′ =CH{(C?CH2)(CMe)(2,6‐iPr2C6H3N)2}) with the thioketone 4,4′‐bis(dimethylamino)thiobenzophenone. Treatment of 4,4′‐bis(dimethylamino)thiobenzophenone with L SiCl at room temperature furnished the [1+2]‐cycloaddition product silathiacyclopropane 3 . However, reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si at low temperature afforded a [1+4]‐cycloaddition to yield the five‐membered ring product 4 . Compounds 3 and 4 were characterized by NMR spectroscopy, EIMS, and elemental analysis. The molecular structures of 3 and 4 were unambiguously established by single‐crystal X‐ray structural analysis. The room‐temperature reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si resulted in products 4 and 5 , in which 4 is the dearomatized product and 5 is formed under the 1,3‐migration of a hydrogen atom from the aromatic phenyl ring to the carbon atom of the C? S unit. Furthermore, the optimized structures of probable products were investigated by using DFT calculations. 相似文献
77.
Estimation of rating classes and default probabilities in credit risk models with dependencies
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Let Y = m(X) + ε be a regression model with a dichotomous output Y and a one‐step regression function m . In the literature, estimators for the three parameters of m , that is, the breakpoint θ and the levels a and b , are proposed for independent and identically distributed (i.i.d.) observations. We show that these standard estimators also work in a non‐i.i.d. framework, that is, that they are strongly consistent under mild conditions. For that purpose, we use a linear one‐factor model for the input X and a Bernoulli mixture model for the output Y . The estimators for the split point and the risk levels are applied to a problem arising in credit rating systems. In particular, we divide the range of individuals' creditworthiness into two groups. The first group has a higher probability of default and the second group has a lower one. We also stress connections between the standard estimator for the cutoff θ and concepts prevalent in credit risk modeling, for example, receiver operating characteristic. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
78.
Nucleophile‐Dependent Regio‐ and Stereoselective Ring Opening of 1‐Azoniabicyclo[3.1.0]hexane Tosylate
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Mi‐Kyung Ji Dietmar Hertsen Doo‐Ha Yoon Heesung Eum Hannelore Goossens Prof. Dr. Michel Waroquier Prof. Dr. Veronique Van Speybroeck Prof. Dr. Matthias D'hooghe Prof. Dr. Norbert De Kimpe Prof. Dr. Hyun‐Joon Ha 《化学:亚洲杂志》2014,9(4):1060-1067
1‐[(1R)‐(1‐Phenylethyl)]‐1‐azoniabicyclo[3.1.0]hexane tosylate was generated as a stable bicyclic aziridinium salt from the corresponding 2‐(3‐hydroxypropyl)aziridine upon reaction with p‐toluenesulfonyl anhydride. This bicyclic aziridinium ion was then treated with various nucleophiles including halides, azide, acetate, and cyanide in CH3CN to afford either piperidines or pyrrolidines through regio‐ and stereoselective ring opening, mediated by the characteristics of the applied nucleophile. On the basis of DFT calculations, ring‐opening reactions under thermodynamic control yield piperidines, whereas reactions under kinetic control can yield both piperidines and pyrrolidines depending on the activation energies for both pathways. 相似文献
79.
Johannes Kretsch Anne-Kathrin Kreyenschmidt Timo Schillmöller Dr. Märt Lõkov Dr. Regine Herbst-Irmer Prof. Dr. Ivo Leito Prof. Dr. Dietmar Stalke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(38):9858-9865
A novel sterically demanding bis(4-benzhydryl-benzoxazol-2-yl)methane ligand 6 (4−BzhH2BoxCH2) was gained in a straightforward six-step synthesis. Starting from this ligand monomeric [M(4-BzhH2BoxCH)] (M=Na ( 7 ), K ( 81 )) and dimeric [{M(4-BzhH2BoxCH)}2] (M=K ( 82 ), Rb ( 9 ), Cs ( 10 )) alkali metal complexes were synthesised by deprotonation. Abstraction of the potassium ion of 8 by reaction with 18-crown-6 resulted in the solvent separated ion pair [{(THF)2K@(18-crown-6)}{bis(4-benzhydryl-benzoxazol-2-yl)methanide}] ( 11 ), including the energetically favoured monoanionic (E,E)-(4-BzhH2BoxCH) ligand. Further reaction of 4−BzhH2BoxCH2 with three equivalents KH and two equivalents 18-crown-6 yielded polymeric [{(THF)2K@(18-crown-6)}{K@(18-crown-6)K(4-BzhBoxCH)}]n (n→∞) ( 12 ) containing a trianionic ligand. The neutral ligand and herein reported alkali complexes were characterised by single X-ray analyses identifying the latter as a promising precursor for low-valent main group complexes. 相似文献
80.
Propane‐1,2‐diols from Dilactides,Oligolactides, or Poly‐L‐lactic Acid (PLLA): From Plastic Waste to Chiral Bulk Chemicals
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Dr. Ivan A. Shuklov Dr. Natalia V. Dubrovina Dr. Joachim Schulze Wolfgang Tietz Prof. Dr. Klaus Kühlein Prof. Dr. Armin Börner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):957-960
The preparation of racemic or enantioenriched propane‐1,2‐diol from dilactides, oligolactides, or poly‐L ‐lactic acid (PLLA) is described. The transformation is carried out as tandem reactions in MeOH, covering hydrolysis and subsequent hydrogenation by using copper chromite as a catalyst. The starting material present undesired side products of the PLLA synthesis or PLLA waste. 相似文献