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41.
Jonas Enebro Dane Momcilovic Matti Siika-aho Sigbritt Karlsson 《Cellulose (London, England)》2009,16(2):271-280
The benefits of applying cellulose selective enzymes as analytical tools for chemical structure characterization of cellulose
derivatives have been frequently addressed over the years. In a recent study the high selectivity of cellulase Cel45A from
Trichoderma reesei (Tr Cel45A) was utilized for relating the chemical structure to the flow properties of carboxymethyl cellulose (CMC). However,
in order to take full advantage of the enzymatic hydrolysis the enzyme selectivity on the cellulose substrate must be further
investigated. Therefore, the selectivity of Tr Cel45A on CMC was studied by chemical sample preparation of the enzyme products
followed by mass spectrometric chemical structure characterization. The results strongly suggest that, in accordance with
recent studies, also this highly selective endoglucanase is able to catalyze hydrolysis of glucosidic bonds adjacent to mono-substituted
anhydroglucose units (AGUs). Furthermore, the results also indicate that substituents on the nearby AGUs will affect the hydrolysis. 相似文献
42.
Anisimova TB Bokach NA Luzyanin KV Haukka M Kukushkin VY 《Dalton transactions (Cambridge, England : 2003)》2010,39(44):10790-10798
The reaction between K[PtCl(3)(Me(2)SO)] or prepared in this work cis- and trans-[PtCl(2)(NCNR(2))(Me(2)SO)] (R(2) = Me(2), 1; C(4)H(8)O, 2; C(5)H(10) 3) with an excess of NCNR(2) in water gives the cationic bischelate [Pt{κ(2)-N,N'-NH=C(NMe(2))OC(NMe(2))=NH}(2)](2+) (4(2+)) and the monochelates [PtCl{κ(2)-N,O-NH=C(NR(2))NC(NR(2))=O}(Me(2)SO)] (R(2) = C(4)H(8)O, 5; C(5)H(10), 6). Complex 4(2+) was released from the reaction mixture as 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2) or it was precipitated as 4·[A](2) (A = pic, 4·[pic](2); PF(6), 4·[PF(6)](2); BPh(4), 4·[BPh(4)](2)·(NH(2)CONMe(2))) by addition of picric acid, NaPF(6), or NaBPh(4), respectively, to the filtrate obtained after separation of 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2). In 2, the dialkylcyanamide ligand undergoes bond cleavage giving the known trans-[PtCl(2){N(H)C(4)H(8)O}(Me(2)SO)] (trans-7). All complexes were characterized by elemental analyses (C, H, N), high resolution ESI-MS, IR, (1)H and (13)C{(1)H} NMR spectroscopic techniques, including 2D NMR correlation experiments ((1)H,(1)H-COSY, (1)H,(13)C-HMQC/(1)H,(13)C HSQC, (1)H,(13)C-HMBC, and (1)H,(1)H-NOESY). The structures of cis-1, cis-3, 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2), 4·[BPh(4)](2)·(NH(2)CONMe(2)) and 5 were determined by a single-crystal X-ray diffraction. 相似文献
43.
Koshevoy IO Haukka M Selivanov SI Tunik SP Pakkanen TA 《Chemical communications (Cambridge, England)》2010,46(47):8926-8928
The assembly of the gold(I)-diphosphine cages occurs via unprecedented transformation of the alkynyls into the μ(4)-methylydine ligands under basic conditions. These compounds demonstrate the equilibrium between the P?M helical isomers and serve as hosts to accommodate small molecules (CH(2)Cl(2) and CS(2)). 相似文献
44.
Martin Beneke Björn Garbrecht Christian Fidler Matti Herranen Pedro Schwaller 《Nuclear Physics B》2011
Within the Closed Time Path (CTP) framework, we derive kinetic equations for particle distribution functions that describe leptogenesis in the presence of several lepton flavours. These flavours have different Standard-Model Yukawa couplings, which induce flavour-sensitive scattering processes and thermal dispersion relations. Kinetic equilibrium, which is rapidly established and maintained via gauge interactions, allows to simplify these equations to kinetic equations for the matrix of lepton charge densities. In performing this simplification, we notice that the rapid flavour-blind gauge interactions damp the flavour oscillations of the leptons. Leptogenesis turns out to be in the parametric regime where the flavour oscillations are overdamped and flavour decoherence is mainly induced by flavour sensitive scatterings. We solve the kinetic equations for the lepton number densities numerically and show that they interpolate between the unflavoured and the fully flavoured regimes within the intermediate parametric region, where neither of these limits is applicable. 相似文献
45.
The generalized trigonometric functions occur as an eigenfunction of the Dirichlet problem for the one-dimensional p-Laplacian. The generalized hyperbolic functions are defined similarly. Some classical inequalities for trigonometric and hyperbolic functions, such as Mitrinovi?–Adamovi?’s inequality, Lazarevi?’s inequality, Huygens-type inequalities, Wilker-type inequalities, and Cusa–Huygens-type inequalities, are generalized to the case of generalized functions. 相似文献
46.
Bokach NA Kukushkin VY Kelly PF Haukka M Pombeiro AJ 《Dalton transactions (Cambridge, England : 2003)》2005,(8):1354-1356
Imino(triphenyl)phosphorane, Ph3P=NH (1), reacts with nitrile complexes of Pt(IV) to generate hydrolytically sensitive [PtCl4{NH=C(R)N=PPh3}2](R=Me 2a, Et 2b, Ph 2c), and with the Pt(II) complex [PtCl2(EtCN)2] to give [PtCl2(EtCN){NH=C(Et)N=PPh3}](3) and [PtCl2{NH=C(Et)N=PPh3}2](4); X-ray crystallography performed upon (2b) and (3) confirms the presence of an imine/nitrile addition ligand bound by the terminal nitrogen. 相似文献
47.
Makarycheva-Mikhailova AV Bokach NA Kukushkin VY Kelly PF Gilby LM Kuznetsov ML Holmes KE Haukka M Parr J Stonehouse JM Elsegood MR Pombeiro AJ 《Inorganic chemistry》2003,42(2):301-311
Pt(IV)-mediated addition of the sulfimide Ph2S = NH and the mixed sulfide/sulfimides o- and p-[PhS(=NH)](PhS)-C6H4 by the S=NH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4[NH=C(R)N=SR'Ph]2] (R' = Ph, R = Me, Et, CH2Ph, Ph; R' = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2S=NH leads exclusively to trans-[PtCl4[NH=C(R)N=SPh2]2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4[NH=C(Me)N=SPh2]2] and the latter have been separated by column chromatography. Theoretical calculations at both HF/HF and MP2//HF levels for the cis and trans isomers of [PtCl4[NH=C(Me)N=SMe2]2] indicate a higher stability for the latter. Compounds trans-[PtCl4[E-NH=C(R)N=SPh2]2] (R = Me, Et) and cis-[PtCl4[E-NH=C(Me)N=SPh2][Z-NH=C(Me)N=SPh2]] have been characterized by X-ray crystallography. The complexes [PtCl4[NH=C(R)N=SPh2]2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4[NH=C(NH2)R]2] the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4[NH=C(R)N=SR'Ph]2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NH=C(R)=SR'Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-[PhS(=NH)](PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the coupling--in contrast to the Pt(IV) species--gives the chelates [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh]]. The X-ray crystal structure of [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh-o]] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum. 相似文献
48.
Unoccupied titanium 3d states due to subcluster formation in stoichiometric TiO2 nanoparticles 下载免费PDF全文
Sami Auvinen Matti Lahti Matti Alatalo 《International journal of quantum chemistry》2015,115(17):1175-1180
The source of unoccupied Ti 3d states in the case of stoichiometric anatase structured (TiO2)n clusters has been investigated using ab initio methods. These unoccupied gap states appear for example in the case of a stoichiometric (TiO2)38 cluster. We show that the origin of these gap states is related to effective subcluster formation which gives rise to empty defect‐like gap states, when these states are split off from conduction band. © 2015 Wiley Periodicals, Inc. 相似文献
49.
Tuorila J Silveri M Sillanpää M Thuneberg E Makhlin Y Hakonen P 《Physical review letters》2010,105(25):257003
A superconducting qubit was driven in an ultrastrong fashion by an oscillatory microwave field, which was created by coupling via the nonlinear Josephson energy. The observed Stark shifts of the "atomic" levels are so pronounced that corrections even beyond the lowest-order Bloch-Siegert shift are needed to properly explain the measurements. The quasienergies of the dressed two-level system were probed by resonant absorption via a cavity, and the results are in agreement with a calculation based on the Floquet approach. 相似文献
50.
Pradip K. Bhowmik Tae S. Jo Jung J. Koh Jongwon Park Bidyut Biswas Ronald Carlo G. Principe Haesook Han Andrs F. Wacha Matti Knaapila 《Molecules (Basel, Switzerland)》2021,26(6)
A series of poly(pyridinium salt)s-fluorene main-chain ionic polymers with various organic counterions were synthesized by using ring-transmutation polymerization and metathesis reactions. Their chemical structures were characterized by Fourier Transform Infrared (FTIR), proton (1H), and fluorine 19 (19F) nuclear magnetic resonance (NMR) spectrometers. These polymers showed a number-average molecular weight (Mns) between 96.5 and 107.8 kg/mol and polydispersity index (PDI) in the range of 1.12–1.88. They exhibited fully-grown lyotropic phases in polar protic and aprotic solvents at different critical concentrations. Small-angle X-ray scattering for one polymer example indicates lyotropic structure formation for 60–80% solvent fraction. A lyotropic smectic phase contains 10 nm polymer platelets connected by tie molecules. The structure also incorporates a square packing motif within platelets. Thermal properties of polymers were affected by the size of counterions as determined by differential scanning calorimetry and thermogravimetric analysis measurements. Their ultraviolet-visible (UV-Vis) absorption spectra in different organic solvents were essentially identical, indicating that the closely spaced π-π* transitions occurred in their conjugated polymer structures. In contrast, the emission spectra of polymers exhibited a positive solvatochromism on changing the polarity of solvents. They emitted green lights in both polar and nonpolar organic solvents and showed blue light in the film-states, but their λem peaks were dependent on the size of the counterions. They formed aggregates in polar aprotic and protic solvents with the addition of water (v/v, 0–90%), and their λem peaks were blue shifted. 相似文献