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121.
The crystal structures of the cyclic amines azetidine (C3H7N), pyrrolidine (C4H9N) and hexamethyleneimine (homopiperidine, C6H13N), of the series (CH2)nNH, with n = 3, 4 and 6, respectively, have been determined at 170 K, following in situ crystallization from the melt. These structures provide crystallographic data to complete the homologous series of cyclic amines (CH2)nNH, for n = 2–6. Azetidine and pyrrolidine contain chains propagating along 21 screw axes, in which the molecules are linked by co-operative N—H...N hydrogen bonds. Azetidine has two molecules in its asymmetric unit, while pyrrolidine has only one. Hexamethyleneimine contains tetrameric hydrogen-bonded rings formed about crystallographic inversion centres, with two molecules in its asymmetric unit. The observation of crystallographically distinct molecules in the hydrogen-bonded chains of azetidine and cyclic hydrogen-bonded motifs in hexamethyleneimine is consistent with expectations derived from comparison with monoalcohols forming chains or rings by co-operative O—H...O hydrogen bonds. The next member of the cyclic amine series, heptamethyleneimine, forms a cubic plastic phase on cooling from the melt.  相似文献   
122.
The synthesis and magnetic properties of three new members of a family of salicyaldoxime based [Mn6] single-molecule magnets possessing new structural types, core topologies and Mn oxidation state distributions are reported. The isostructural complexes [MnIII6O2(R-sao)6(X)2(EtOH)6] (R = Et, X = Br (1); R = Me, X = I (2)) exhibit single-molecule magnet behaviour with spin Hamiltonian parameters S = 12, g = 1.98 and D = -0.36 cm(-1) in both cases. The hexametallic cluster [MnIII4MnIV2O2(OMe)(4-)(Et-sao)6(MeOH)2].MeOH (3.MeOH) possesses a planar rod-like topology and a mixed valent [MnIV4MnIII2] core, which is unprecedented in this family of [Mn6] SMMs.  相似文献   
123.
We report the synthesis of a series of mixed valence Mn(II/IV) tetranuclear clusters [Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(EtOH)(6)Br(2)]Br(2) (), [Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(H(2)O)(2)Cl(4)].2EtOH.H(2)O (.2EtOH.H(2)O), [Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(heedH(2))(2)](ClO(4))(4) (), [Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(MeCN)(2)(H(2)O)(2)(bpy)(2)](ClO(4))(4) () and [Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(bpy)(2)Br(4)].2MeOH (.2MeOH). Clusters are constructed from the tripodal ligand N,N-bis(2-hydroxyethyl)ethylene diamine (heedH(2)) and represent rare examples of tetranuclear Mn clusters possessing the linear trans zig-zag topology, being the first Mn(II/IV) mixed-valent clusters of this type. The molecular clusters can then be used as building blocks in tandem with the (linear) linker dicyanamide ([N(CN)(2)](-), dca(-)) for the formation of a novel extended network {[Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(H(2)O)(2)(MeOH)(2)(dca)(2)]Br(2)}(n) (), which exhibits a rare form of the 2D herring bone topology.  相似文献   
124.
125.
The threat associated with chemical warfare agents (CWAs) motivates the development of new materials to provide enhanced protection with a reduced burden. Metal–organic frame‐works (MOFs) have recently been shown as highly effective catalysts for detoxifying CWAs, but challenges still remain for integrating MOFs into functional filter media and/or protective garments. Herein, we report a series of MOF–nanofiber kebab structures for fast degradation of CWAs. We found TiO2 coatings deposited via atomic layer deposition (ALD) onto polyamide‐6 nanofibers enable the formation of conformal Zr‐based MOF thin films including UiO‐66, UiO‐66‐NH2, and UiO‐67. Cross‐sectional TEM images show that these MOF crystals nucleate and grow directly on and around the nanofibers, with strong attachment to the substrates. These MOF‐functionalized nanofibers exhibit excellent reactivity for detoxifying CWAs. The half‐lives of a CWA simulant compound and nerve agent soman (GD) are as short as 7.3 min and 2.3 min, respectively. These results therefore provide the earliest report of MOF–nanofiber textile composites capable of ultra‐fast degradation of CWAs.  相似文献   
126.
There is a growing interest in using biomonitoring of tooth and bone specimens to assess human exposure to manganese (Mn). Information on historical exposure to Mn can be obtained through micro-spatial analysis of such specimens by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The principal aim of this study was to compare several calibration strategies for determining Mn content in tooth and bone by LA-ICP-MS including: (a) a six-point calibration curve based on synthesized hydroxyapatite (HA) materials, and single-point calibrations based on (b) NIST SRM 1400 Bone Ash, (c) NIST SRM 1486 Bone Meal, and (d) NIST SRM 612 Trace Elements in Glass. Performance was similar between different ICP-MS platforms (quadrupole ICP-MS, dynamic reaction cell ICP-MS, and sector field ICP-MS). Data based on calibration using the 55Mn count rate were compared to that based on using the 55Mn/43Ca count rate ratio to obtain results as the Mn mass fraction. Reasonable performance was obtained by calibration using either SRM 612 or SRM 1400, in combination with the 55Mn/43Ca count rate ratio and using either the synthesized HA standards or SRM 1400 as calibrators, combined with 55Mn count rate. By contrast, calibration based on SRM 1486 resulted in a systematic low bias. While there are several options for quantifying the Mn content of tooth and bone using LA-ICP-MS, users should be aware of the potential for strong matrix effects that may affect results. Overall, determining the 55Mn/43Ca count rate ratio, rather than the mass fraction, may represent a better approach for reporting the content of Mn in tooth and bone by LA-ICP-MS.  相似文献   
127.
A synthesis of highly functionalized nitroalkenes is reported that utilizes a cross metathesis (CM) reaction between simple aliphatic nitro compounds and a range of substituted alkenes. This chemistry offers a simple and attractive route to nitroalkenes that would otherwise be difficult to prepare, and that have a very useful application as precursors to a variety of heterocyclic entities.  相似文献   
128.
129.
The complex [Mn(6)O(2)(Et-sao)(6)(O(2)C(11)H(15))(2)(EtOH)(6)] has U(eff) = 80 K.  相似文献   
130.
The bis-complexes [Cu(L(dt))(2)](OTf)(2) (1) and [Cu(L(ot))(2)](OTf)(2) (2), where L(dt) = 1-dodecyl-1,4,7-triazacyclononane, L(ot) = 1-octadecyl-1,4,7-triazacyclononane and OTf = trifluoromethanesulfonate, formed a novel class of metallo-liposomes in water that transfect pEGFP-N1 plasmids into HEK 293-T cells at 38% and 4% efficiency, respectively.  相似文献   
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