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481.
The syntheses of an important class of hitherto unreported novel pyrazoles are described. The regioselective synthesis of 1,3,4,5-tetrasubstituted pyrazoles was achieved by the Huisgen cyclization of nitrile imines with a trisubstituted bromoalkene. The substituted bromoalkene functions as an alkyne synthon which was used to construct 5,5-disubstituted bromopyrazoline intermediates that undergo aromatization to the analogous pyrazoles through the loss of HBr. The cycloaddition regioselectivity was confirmed through single X-ray crystal data of one of the pyrazoles. 相似文献
482.
W. Michael Kochemba S. Michael Kilbey II Deanna L. Pickel 《Journal of polymer science. Part A, Polymer chemistry》2012,50(14):2762-2769
The ability to prepare well‐defined semiconducting polymers is essential for understanding the link between structure and function in organic photovoltaic devices. A general, one‐pot method for altering the degree of functionality of end‐functionalized poly(3‐hexylthiophene)s (P3HT) prepared by Grignard metathesis (GRIM) polymerization has been developed. In the absence of additives, the degree of functionality of end‐functional P3HTs prepared by quenching of the GRIM polymerization with a Grignard reagent is dependent on the Grignard reagent utilized. In this study, additives such as styrene and 1‐pentene are shown to alter the end‐group composition of tolyl‐functionalized P3HTs as determined by Matrix‐assisted Laser Desorption Ionization Time‐of‐flight Mass Spectrometry. In particular, when quenching the GRIM polymerization with tolylmagnesium bromide, a modest decrease in the difunctional product is observed, and the yield of the monofunctional product increases significantly. Temperature and lithium chloride (LiCl) addition also play impactful roles. Monofunctional P3HT is found to be the major product (72% abundance) when the functionalization is done in the presence of LiCl and styrene at 0 °C, whereas in the absence of additives the monofunctional product is present at only 11% abundance. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
483.
Smith JN V White G White MI Bernstein R Hochrein JM 《Journal of the American Society for Mass Spectrometry》2012,23(9):1579-1592
Aged materials, such as polymers, can exhibit modifications to their chemical structure and physical properties, which may render the material ineffective for its intended purpose. Isotopic labeling was used to characterize low-molecular weight volatile thermal-oxidative degradation products of nylon 6.6 in an effort to better understand and predict changes in the aged polymer. Headspace gas from aged (up to 243 d at 138?°C) nylon 6.6 monomers (adipic acid and 1,6-hexanediamine) and polymer were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). Observations regarding the relative concentrations observed in each chromatographic peak with respect to aging time were used in conjunction with mass spectra for samples aged under ambient air to determine the presence and identity of 18 degradation products. A comparison of the National Institute of Standards and Technology (NIST) library, unlabeled, and isotopically labeled mass spectra (C-13 or N-15) and expected fragmentation pathways of each degradation product were used to identify the location of isotopically labeled atoms within the product's chemical structure, which can later be used to determine the exact origin of the species. In addition, observations for unlabeled nylon 6.6 aged in an O-18 enriched atmosphere were used to determine if the source of oxygen in the applicable degradation products was from the gaseous environment or the polymer. Approximations for relative isotopic ratios of unlabeled to labeled products are reported, where appropriate. 相似文献
484.
Rabindra N. Roy Lakshmi N. Roy Michael S. Fuge Chandra N. Roy Curtis A. Himes Paul A. Bryant Kyle T. Robinson Daniel A. Kaufmann II Colby H. Grove Toshi Gosh Adonis Bwashi 《Journal of solution chemistry》2009,38(4):471-483
The values of the second dissociation constant, pK
2, and related thermodynamic quantities of [N-(2-acetamido)-2-aminoethanesulfonic acid] (ACES) have already been reported over
the temperature range 5 to 55 °C including 37 °C. This paper reports the pa
H values of four chloride ion free buffer solutions and eight buffer solutions with I=0.16 mol⋅kg−1, matching closely that of the physiological sample. Conventional pa
H values for all twelve buffer solutions from 5 to 55 °C are reported. The residual liquid-junction potential correction for
two widely used temperatures, 25 and 37 °C, has been made. The flowing-junction calomel cell method has been utilized to measure
E
j
, the liquid-junction potential. The operational pH values for four buffer solutions at 25 and 37 °C are calculated using
the physiological phosphate buffer standard based on the NBS/NIST convention. These solutions are recommended as pH standards
in the pH range of 6.8 to 7.2 for physiological fluids. 相似文献
485.
II 《Journal of organometallic chemistry》1993,450(1-2):263-267
Treatment of [Pd{CH2C(CH3)CH2}(Ph2PPy)Cl] (Ph2PPy = 2-(diphenylphosphino)pyridine) with cis-[Pd(tBuNC)2Cl2] in dichloromethane affords the mixed isocyanide-tertiary phosphine complex cis-[Pd(tBuNC)Ph2PPy)Cl2], in which the Ph2PPy is a monodentate P-donor, and [{Pd[CH2C(CH3)CH2]Cl}2]. The steric effects of the Ph2PPy bridging ligand in determining the reaction course is discussed. The complex cis-[Pd(tBuNC)(Ph2PPy)Cl2] was crystallographically characterized: P21/n, a = 15.143(2), b = 9.527(1), c = 17.517(4) Å, β = 113.96(1)°, V= 2309.4(7) Å3, Z = 4. The final R value was 0.044, Rw= 0.046 for the 3078 reflections with I > 3σ(I). 相似文献
486.
The alkylation of tetrazoles using Mitsunobu conditions and alcohols is reported. The methodology is superior to the base-promoted reaction with alkyl halides for the installation of a secondary alkyl group because it results in higher yields and facilitates the construction of chiral centers bearing tetrazole. 相似文献
487.
Low‐Temperature CO Oxidation over a Ternary Oxide Catalyst with High Resistance to Hydrocarbon Inhibition 下载免费PDF全文
Dr. Andrew J. Binder Dr. Todd J. Toops Dr. Raymond R. Unocic Dr. James E. Parks II Prof. Sheng Dai 《Angewandte Chemie (International ed. in English)》2015,54(45):13263-13267
Platinum group metal (PGM) catalysts are the current standard for control of pollutants in automotive exhaust streams. Aside from their high cost, PGM catalysts struggle with CO oxidation at low temperatures (<200 °C) due to inhibition by hydrocarbons in exhaust streams. Here we present a ternary mixed oxide catalyst composed of copper oxide, cobalt oxide, and ceria (dubbed CCC) that outperforms synthesized and commercial PGM catalysts for CO oxidation in simulated exhaust streams while showing no signs of inhibition by propene. Diffuse reflectance IR (DRIFTS) and light‐off data both indicate low interaction between propene and the CO oxidation active site on this catalyst, and a separation of adsorption sites is proposed as the cause of this inhibition resistance. This catalyst shows great potential as a low‐cost component for low temperature exhaust streams that are expected to be a characteristic of future automotive systems. 相似文献
488.
489.
490.
Gregory F. Meyers Michael T. Dineen Edward O. Shaffer II Ted Stokich Jr. Jang‐hi Im 《Macromolecular Symposia》2001,167(1):213-226
Scanning probe microscopy (SPM) techniques are used to characterize surfaces related to the processing of benzocyclobutene (BCB) dielectric thin films. Thermally cured resins and photodefineable resins are sold under the trade name CYLCOTENETM1) for electronic applications. TappingMode AFM (TMAFM) imaging is used to follow changes in adhesion promoter morphology upon baking to help explain adhesion performance. Power spectral density (PSD) analysis of TMAFM images of plasma treated BCB surfaces are unique and can be used to ‘fingerprint’ processes. Selective oxidation of the BCB surface can be used to fabricate a phase imaging standard for TMAFM. Near surface modulus of the BCB materials is 3.6 ± 0.2 GPa and the hardness is 0.38 ± 0.2 GPa measured by depth‐sensing nanoindentation. Creep recovery of indents can be used to qualitatively distinguish between thermal and photocureable materials. A heated tip in a scanning thermal microscope can induce the thermal curing of BCB over micron sized areas. Local thermal analysis with the same probe allows the measurement of the changes in the glass transition, Tg, at the surface with cure temperature. 相似文献