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51.
Bernasconi CF Michoff ME de Rossi RH Granados AM 《The Journal of organic chemistry》2007,72(4):1285-1293
The main question addressed in this paper is whether the nucleophilic substitution of the p-nitrophenoxy group in (CO)5Cr=C(OC6H4-4-NO2)Ph (1-NO2) by a series of substituted phenoxide ions is concerted or stepwise. Rate constants, kArO, for these substitution reactions were determined in 50% MeCN-50% water (v/v) at 25 degrees C. A Br?nsted plot of log kArO versus pKa(ArOH) s consistent with a stepwise mechanism. This contrasts with reactions of aryl oxide ions with p-nitrophenyl acetate and with similar acyl transfers which are concerted. The reason for the contrast is that the tetrahedral intermediates formed in the reactions of 1-NO2 are much more stable than those in acyl transfers and the intrinsic barriers to their decomposition are higher than for the ester reactions. The points on the Br?nsted plots for which pKa(ArOH) > or = pKa(PNP) define a straight line with beta(nuc) = -0.39, suggesting that bond formation has made very little progress at the transition state and that partial desolvation of the nucleophile is part of the activation process. The hydrolysis of 1-NO2 and of the unsubstituted analogue (1-H) has also been studied over a wide pH range, providing rate constants for nucleophilic attack by hydroxide ion (kOH), by water (kH2O), and by general base-catalyzed reaction with water (kB). Furthermore, kH2O values were obtained for the hydrolysis of (CO)5Cr=C(OC6H4X)Ph (1-X) as a byproduct of the reactions of 1-NO2 with aryl oxide ions. Structure-reactivity relationships for these reactions are discussed in terms of inductive, pi-donor, and steric effects. 相似文献
52.
Rate constants for the hydrolysis of Fischer carbenes (CO)5Cr=C(OR)Ph (R = n-propyl, neopentyl, isopropyl, and menthyl) in 50% MeCN-50% water (v/v) at 25 degrees C are reported. The rate constants for the addition of -OH to the carbene carbon are 5.3, 3.7, 0.84, and 0.01 M(-1) s(-1), respectively. These rate constants give linear correlations with the corresponding rate constants for the hydrolysis of esters such as acetate, benzoate, and formiate. The slopes of the plots of the observed rate constants for the carbenes vs the rate constants for the esters are 1.4 and 1.2 for acetate and benzoate, respectively, indicating that the factors that decrease the reactivity of the two types of compounds are similar, but the carbenes show higher sensitivity. The rate constants are well correlated with several steric parameters giving a value of -3.84 for the Charton's psi parameter. The results show that the steric bulkiness of the R group is the main factor determining the reactivity differences for these carbene complexes. 相似文献
53.
Granados Carlos Leupold Stefan Perotti Elisabetta 《The European Physical Journal A - Hadrons and Nuclei》2017,53(6):1-82
The European Physical Journal A - The experimental hadronic physics programme at the COoler SYnchrotron of the Forschungszentrum Jülich terminated at the end of 2014. After describing the... 相似文献
54.
Jorge Bustamante José M. Quesada Reinaldo Martínez-Cruz 《Journal of Approximation Theory》2012,164(6):791-802
We find the polynomials of the best one-sided approximation to the Heaviside and sign functions. The polynomials are obtained by Hermite interpolation at the zeros of some Jacobi polynomials. Also we give an estimate of the error of approximation and characterize the extremal points of the convex set of the best approximants. 相似文献
55.
56.
Celeste Garcia Antonio Quesada Manuel Melguizo Justo Cobo Manuel Nogueras Adolfo Snchez Debbie Cannon John Nicolson Low 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(9):1103-1105
The title compound, C9H12N2O3, crystallizes with two molecules in the asymmetric unit. There is extensive hydrogen bonding which results in the formation of a two‐dimensional corrugated sheet. This supramolecular structure is determined by the formation of hydrogen‐bonded chains resulting from the presence of a 6‐amino group and an ethoxycarbonyl group as substituents on a pyridine ring in relative para positions which constitute a π‐electron `push–pull' system. 相似文献
57.
França EJ Andrade CG Furlaneto-Maia L Serpa R Oliveira MT Quesada RM Furlaneto MC 《Micron (Oxford, England : 1993)》2011,42(7):726-732
Candida tropicalis has been identified as one of the most prevalent pathogenic yeast species of the Candida-non-albicans (CNA) group. Study of switching in C. tropicalis has not been the subject of extensive research. Therefore, we investigated switching event and characterized the ultrastructural architecture of different phenotypes and biofilm produced in a C. tropicalis clinical strain. Cells switched heritably, reversibly, and at a high frequency between four phenotypes readily distinguishable by the shape of colonies formed on agar at 25°C. SEM analysis was used to verify the architecture of whole Candida colonies at ultrastructural level. The smooth phenotype (parental phenotype) colony showed a hemispherical shape character, while the semi-smooth was characterized by the presence of shallow marginal depressions. The ring and rough phenotypes exhibited more complex architecture and were characterized by the presence of deep central and peripheral depressions areas. The biofilm-forming ability varied among the switch phenotypes. After 12h incubation, the smooth phenotype formed less biofilm compared to the other phenotypes (P<0.05). The electron microscopy analysis revealed that filamentation (pseudohyphae) was associated with ring and rough colonies. The ultrastructural analysis allowed the observation of the arrangement of individual cells within the colonies. At the deep central and peripheral depressions areas of the ring and rough colonies extracellular material was seen in different arrangements. The data presented here open new avenues to study a possible role for extracellular material in the formation and maintenance of the architecture of switch phenotypes in C. tropicalis. It is therefore essential that more strains be investigated to determine the biological significance of extracellular material in C. tropicalis phenotypic switching phenomenon. 相似文献
58.
59.
Alejandro M. Fracaroli O. Fernando Silva Alejandro M. Granados Rita H. de Rossi 《Journal of Physical Organic Chemistry》2008,21(11):1007-1013
The UV–Vis spectrum of 5‐(1‐butylthio)‐3H‐1,2‐dithiole‐3‐thione (1a) and that of the chromium pentacarbonyl complex of 5‐methyl‐3H‐1,2‐dithiole‐3‐thione (3) present significant changes with the solvent polarity. The two absorption bands shown by the compounds in the region above 300 nm were identified by theoretical calculations. For Compound 1a these are n→π* and →π* transitions and for Compound 3 the longest wavelength absorption corresponds to a charge transfer band and shows a remarkably negative solvatochromism. Not only has the wavelength of maximum absorption changed with the solvent but also the ratio of the absorbances at the two wavelengths. The effect of solvents was correlated with solvatochromic parameters such as π* and α. The spectrum of 5‐(1‐butylthio)‐3H‐1,2‐dithiole‐3‐one ( 2 ) was also measured in different solvents but in this case the changes observed are less significant than for the other two compounds. The spectra of 1a and 3 were also determined in the presence of anionic (SDS), cationic (CTAB), and neutral surfactants (Brig‐35) and it is shown that these compounds can be used as probes for the polarity of the binding sites of organized assemblies. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
60.
W. Ouerghui J. Martinez-Pastor J. Gomis M. A. Maaref D. Granados J. M. García 《The European Physical Journal B - Condensed Matter and Complex Systems》2006,54(2):217-223
Exciton recombination dynamics in vertical stacks of InGaAs quantum rings have been studied by means of continuous wave and
time resolved
photoluminescence under low excitation density conditions. We have paid
special attention to the effect of the carrier coupling on the exciton
radiative lifetime: weak (14 nm spacer sample), intermediate (4.5 nm spacer
sample), where the size filtering effects (towards small rings) compensate
partially that arising from carrier coupling (towards lower energies), and
strong electron and hole coupling (1.5 nm spacer sample) between layers.
Experimental decay times in the latter two cases have been compared to the
times simulated with a multi-quantum well based model, which accounts for
the observed change of carrier coupling regime. The most important effect is
observed when the hole wave function overlap along the growth direction
becomes important (1.5 nm spacer sample). This situation makes important the
lateral tunneling of excitons between rings, given their large lateral size,
which is characterized by times around 5 ns at the emission peak energy
(rings with the most probable size of the distribution). 相似文献