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1.
Ozonolysis of a Series of Methylated Alkenes: Reaction Rate Coefficients and Gas‐Phase Products
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Tristan Braure Véronique Riffault Alexandre Tomas Romeo Iulian Olariu Cecilia Arsene Yuri Bedjanian Patrice Coddeville 《国际化学动力学杂志》2015,47(9):596-605
The gas‐phase ozonolysis of three methylated alkenes, i.e., trans‐2,2‐dimethyl‐3‐hexene (22dM3H), trans‐2,5‐dimethyl‐3‐hexene (25dM3H), and 4‐methyl‐1‐pentene (4M1P), has been investigated in the presence of sufficient hydroxyl radical scavenger in a laminar flow reactor at ambient temperature (296 ± 2 K) and P = 1 atm of dry air (RH ≤ 5%). Ozone levels in the reactor were monitored by an automatic analyzer. Alkene and gas‐phase product concentrations were determined via online sampling either on three‐bed adsorbent cartridges followed by thermodesorption and GC/FID‐MS analysis or on 2,4‐dinitrophenylhydrazine (DNPH) cartridges for subsequent HPLC/UV analysis. Reaction rate coefficients of (3.38 ± 0.12) × 10?17 for 22dM3H and (2.71 ± 0.26) × 10?17 for 25dM3H, both in cm3 molecule?1 s?1 units, have been obtained under pseudo–first‐order conditions. Primary carbonyl products have been identified for the three investigated alkenes, and branching ratios are reported. In the case of 4M1P ozonolysis, the yield of a Criegee intermediate was indirectly determined. Kinetics and product study results are compared to those of literature when available. This work represents the first investigation of reaction products in the ozonolysis of 22dM3H, 25dM3H, and 4M1P in a flow reactor. 相似文献
2.
Ortiz Adolfo Yang Jianhua Coccolo Mattia Seoane Jesús M. Sanjuán Miguel A. F. 《Nonlinear dynamics》2020,102(4):2323-2337
Nonlinear Dynamics - The main purpose of this paper is to study both the underdamped and the overdamped dynamics of the nonlinear Helmholtz oscillator with a fractional-order damping. For that... 相似文献
3.
4.
Adolfo M. Nemirovsky Maurício D. Coutinho-Filho 《Journal of statistical physics》1988,53(5-6):1139-1153
A field-theoretic representation is presented to count the number of configurations of a single self-avoiding walk on a hypercubic lattice ind dimensions with periodic boundary conditions. We evaluate the connectivity constant as a function of the fractionf of sites occupied by the polymer chain. The meanfield approximation is exact in the limit of infinite dimensions, and corrections to it in powers ofd
–1 can be systematically evaluated. The connectivity constant and the site entropy calculated throughout second order compare well with known results in two and three dimensions. We also find that the entropy per site develops a maximum atf1–(2d)–1. Ford=2 (d=3), this maximum occurs atf~0.80 (f~0.86) and its value is about 50% (30%) higher than the entropy per site of a Hamiltonian walk (f=1). 相似文献
5.
The thermal decomposition of some mixed uranyl complexes with Schiff bases and DMSO, EtOH or (Ph)3PO as neutral ligand, were investigated and the corresponding activation energy, E*a, and enthalpy of dissociation, ΔHd, values were calculated.
The results obtained indicate that for the same neutral ligand, the thermal stability of the uranyl complexes is influenced by the Schiff base used; for the same Schiff base, the presence of (Ph)3PO results in a greater thermal stability of the mixed complexes than when the other two neutral ligands are present. 相似文献
6.
Treatment of 2,3-diketo-cholestane (1) with thallium triacetate in acetic acid afforded mainly 3α-carbomethoxy-A-nor-5α-cholestan-2-one (2). Under similar conditions, the 3,4-diketo steroids (3 and 4) underwent extensive rearrangement affording spiro-lactones (9 and 10), in low yields. The structural assignment of the spiro-cholestane derivative was supported by crystallographic X-ray analysis. This product was the result of A and B-ring contractions followed by acid-catalysed cyclization of an unsaturated carboxy intermediate. 相似文献
7.
Antonino Mazzaglia Domenico Garozzo Raffaello Romeo 《Journal of organometallic chemistry》2005,690(8):1978-1985
MALDI and ESI-MS have been applied to the characterization of the reaction products between the labile cis-[Pt(DMSO)2Cl2] (1) and trans-[Pt(DMSO)2Cl(CH3)] (2) complexes with the simplest poly(amidoamine) ligand (PAMAM, G = 0, 1,2-diaminoethane as core). The comparison of the mass spectra of the starting G0 and those of the metallo-dendrimers formed upon mixing of the reagents in an equimolecular ratio, and the analysis of the isotopic distribution in the ESI spectra, have revealed the formation of cationic and neutral mononuclear complexes with PAMAM as ligand, e.g., cis-[Pt(DMSO)(PAMAM)Cl]Cl or trans-(C,N)[Pt(DMSO)(PAMAM)Cl(CH3)], together with various minor components, which have been identified as derivatives from defective structures of PAMAM. The geometry of the main products has been deduced from the values of the protons coupling constants with the isotopically abundant 195Pt. The metal-to-ligand bond is restricted to the peripheral amino groups of PAMAM which shows sufficient flexibility to involve either one or two branches in the coordination bonding. 相似文献
8.
Adolfo Sanchez-Flores 《Order》1995,12(2):173-187
Letn>0 be an element of the setN of nonnegative integers, and lets(x)=x
1+...+x
n
, forx=(x
1, ...,x
n
) N
n
. Adiagonal polynomial order inN
n
is a bijective polynomialp:N
n
N (with real coefficients) such that, for allx,y N
n
,p(x)<p(y) whenevers(x)<s(y). Two diagonal polynomial orders areequivalent if a relabeling of variables makes them identical. For eachn, Skolem (1937) found a diagonal polynomial order. Later, Morales and Lew (1992) generalized this polynomial order, obtaining a family of 2
n–2 (n>1) inequivalent diagonal polynomial orders. Here we present, for eachn>0, a family of (n – 1)! diagonal polynomial orders, up to equivalence, which contains the Morales and Lew diagonal orders. 相似文献
9.
10.
Ficarra P. Ficarra R. Chimirri A. Romeo G. Tommasini S. Calabrò M. L. Costantino D. Monforte A. M. Carulli M. 《Chromatographia》1994,38(1-2):57-61
Summary Anti-HIV enantiomeric 1H, 3H-thiazolo[3, 4-a] benzimidazoles have been stereospecifically analyzed by elution on a column of cellulose tris-(4-methyl-phenylbenzoate)ester adsorbed on macroporous silica (ChiralcelR OJ).The enantiomeric resolution of the compounds examined is linked to a complex and competitive contribution of different factors. 相似文献