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61.
Dehydropolymerisation of methylamine borane (H3B⋅NMeH2) using the well-known iron amido complex [(PNP)Fe(H)(CO)] (PNP=N(CH2CH2PiPr2)2) ( 1 ) gives poly(aminoborane)s by a chain-growth mechanism. In toluene, rapid dehydrogenation of H3B⋅NMeH2 following first-order behaviour as a limiting case of a more general underlying Michaelis–Menten kinetics is observed, forming aminoborane H2B=NMeH, which selectively couples to give high-molecular-weight poly(aminoborane)s (H2BNMeH)n and only traces of borazine (HBNMe)3 by depolymerisation after full conversion. Based on a series of comparative experiments using structurally related Fe catalysts and dimethylamine borane (H3B⋅NMe2H) polymer formation is proposed to occur by nucleophilic chain growth as reported earlier computationally and experimentally. A silyl functionalised primary borane H3B⋅N(CH2SiMe3)H2 was studied in homo- and co-dehydropolymerisation reactions to give the first examples for Si containing poly(aminoborane)s.  相似文献   
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1‐Butyl‐4‐methylpyridinium hexachloridotantalate(V), [BMPy][TaCl6] ( 1 ), tetrakis(1‐butyl‐4‐methylpyridinium) bis(hexachloridotantalate(V) (μ‐oxido)‐decachloridotantalate(V), [BMPy]4[(TaCl6)2(Ta2OCl10)] ( 2 ), and bis(1‐ethyl‐3‐methylimidazolium)‐(μ‐oxido)‐decachloridoditantalate(V), [EMIm]2[Ta2OCl10] ( 3 ) were synthesized and characterized by single‐crystal X‐ray diffraction and vibrational spectroscopy. Compounds 1 and 3 crystallize in the monoclinic space group P21/c (no. 14), whereas compound 2 crystallizes in the triclinic space group P (no. 2). All compounds are built up by the mentioned bulky organic cations and octahedral [TaCl6] respective linear [Ta2OCl10]2– anions. Coulomb interactions are dominant between the ionic species. FT‐IR and FT‐Raman spectra were recorded and interpreted, especially with respect to the inorganic species [TaCl6] (Oh) and [Ta2OCl10]2– (Ci symmetry, approximately D4h). The melting temperatures of compounds 1 – 3 are given.  相似文献   
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Herein the syntheses of three novel ligands, in which an azaheterocycle is connected with a thiazole subunit: 4‐methoxy‐5‐methyl‐2‐pyridine‐2‐yl‐1,3‐thiazole ( 1 ), 4‐methoxy‐5‐methyl‐2‐pyrimidine‐2‐yl‐1,3‐thiazole ( 2 ) and 4‐methoxy‐5‐phenyl‐2‐pyridine‐2‐yl‐1,3‐thiazole ( 3 ) are reported. Because these ligands are cyclic versions of 1,4‐diazadienes, they offer good prerequisites for the synthesis of metal complexes and were employed as chelating ligands. Three novel heteroleptic cationic complexes of the type Ru(bpy)2( L ), with bpy = 2,2′‐bipyridine were successfully synthesised. The RuII complexes as well as the ligands were characterised by means of mass spectrometry, NMR, UV/Vis and IR spectroscopy and elemental analysis. Furthermore, an X‐ray structure of Ru(bpy)2 2 (PF6), as far as we know the first example where a thiazole is directly connected to a RuII core, is presented in this paper.  相似文献   
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In a time series {Xt,t1}, Xj is said to be an upper record if Xj>max?{X1,,Xj?1}. Some popular models for records are the Yang–Nevzorov and the Linear Drift models. In this note, we introduce for these models the joint likelihood of the record sequence and the indicators of their occurrence. This likelihood can then be used to obtain estimators of the unknown parameters in the models. It can also be used to derive inferential procedures associated with the selection of a proper model for such data.  相似文献   
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Simple, sensitive, and selective detection of specific biopolymers is critical in a broad range of biomedical and technological areas. We present a design of turn‐on near‐infrared (NIR) fluorescent probes with intrinsically high signal‐to‐background ratio. The fluorescent signal generation mechanism is based on the aggregation/de‐aggregation of phthalocyanine chromophores controlled by selective binding of small‐molecule “anchor” groups to a specific binding site of a target biopolymer. As a proof‐of‐concept, we demonstrate a design of a sensor for EGFR tyrosine kinase—an important target in cancer research. The universality of the fluorescent signal generation mechanism, as well as the dependence of the response selectivity on the choice of the small‐molecule “anchor” group, make it possible to use this approach to design reliable turn‐on NIR fluorescent sensors for detecting specific protein targets present in the low‐nanomolar concentration range.  相似文献   
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Temperature dependences of the dielectric properties of ultrathin polyvinylidene fluoride films prepared using the Langmuir-Blodgett method were studied by linear and nonlinear dielectric spectroscopy. It is shown that ultrathin Langmuir films of polyvinylidene fluoride exhibit a manifestation of a first-order ferroelectric phase transition, which can be assigned to the interaction between the spontaneous polarization and the surfaces bounding the film. As the film thickness increases, the effect of the surfaces decreases and the ferroelectric phase transition shifts to high temperatures to vanish altogether when the temperature region of the transition rises above the melting point.  相似文献   
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