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51.
52.
Polyvinyl alcohol coated magnetic particles (PVA ferrofluids) have been synthesized by chemical co-precipitationof Fe(Ⅱ)/Fe(Ⅲ) salts in 1.5 mol/L NH_4OH solution at 70℃ in the presence of PVA. The resultant colloidal particles havecore-shell structures, in which the iron oxide crystallites form the cores and PVA chains form the shells. The hydrodynamicdiameter of the colloidal particles is in the range of 108 to 155 nm, which increases with increasing PVA concentration from5 wt% to 20 wt%. The size of the magnetic cores is ca. 5~10 nm, which is relatively independent of PVA concentration.Under transmission electron microscopic (TEM) examination, the magnetic cores exhibit somewhat irregular shapes varyingfrom spherical, oval, to cubic. Magnetometry measurement revealed that the PVA coated magnetic particles aresuperparamagnetic. The saturation magnetization of 5 wt% and 20 wt% PVA ferrofluids at 300 K is 54 and 49 emu/g.respectively. All the PVA ferrofluids exhibited excellent colloidal stability in pure water and phosphate buffer saline (PBS,pH=7.4). The ferrofluids can remain stable in above solutions for more than three months at 4℃. 相似文献
53.
Francoise Rogalewicz Gilles Ohanessian Nohad Gresh 《Journal of computational chemistry》2000,21(11):963-973
The interaction of Zn2+ with glycine (Gly) in the gas phase is studied by a combination of ab initio and molecular mechanics techniques. The structures and energetics of the various isomers of the Gly–Zn2+ complex are first established via high‐level ab initio calculations. Two low‐energy isomers are characterized: one in which the metal ion interacts with the carboxylate end of zwitterionic glycine, and another in which it chelates the amino nitrogen and the carbonyl oygen of neutral glycine. These calculations lead to the first accurate value of the gas‐phase affinity of glycine for Zn2+. Ab initio calculations were also used to evaluate the performance of various implementations of the SIBFA force field. To assess the extent of transferability of the distributed multipoles and polarizabilities used in the SIBFA computations, two approaches are followed. In the first, approach (a), these quantities are extracted from the ab initio Hartree–Fock wave functions of glycine or its zwitterion in its entirety, and for each individual Zn2+‐binding conformation. In the second, approach (b), they are assembled from the appropriate constitutive fragments, namely methylamine and formic acid for neutral glycine, and protonated methylamine and formate for the zwitterion; they undergo the appropriate vector or matrix rotation to be assembled in the conformation studied. The values of the Zn2+–glycine interaction energies are compared to those resulting from ab initio SCF and MP2 computations using both the all‐electron 6‐311+G(2d,2p) basis set and an effective core potential together with the valence CEP 4‐31G(2d) basis set. Approach (a) values closely reproduce the ab initio ones, both in terms of the total interaction energies and of the individual components. Approach (b) can provide a similar match to ab initio interaction energies as does approach (a), provided that the two constitutive Gly building blocks are considered as separate entities having mutual interactions that are computed simultaneously with those occurring with Zn2+. Thus, the supermolecule is treated as a three‐body rather than a two‐body system. These results indicate that the current implementation of the SIBFA force field should be adequate to undertake accurate studies on zinc metallopeptides. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 963–973, 2000 相似文献
54.
Dr. Hülya Aldemir Shuangjie Shu Dr. Francoise Schaefers Dr. Hanna Hong Dr. René Richarz Dr. Sabrina Harteis Manuel Einsiedler Dr. Tobias M. Milzarek Dr. Sabine Schneider Prof. Tobias A. M. Gulder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(2):e202103389
The arylomycin antibiotics are potent inhibitors of bacterial type I signal peptidase. These lipohexapeptides contain a biaryl structural motif reminiscent of glycopeptide antibiotics. We herein describe the functional and structural evaluation of AryC, the cytochrome P450 performing biaryl coupling in biosynthetic arylomycin assembly. Unlike its enzymatic counterparts in glycopeptide biosynthesis, AryC converts free substrates without the requirement of any protein interaction partner, likely enabled by a strongly hydrophobic cavity at the surface of AryC pointing to the substrate tunnel. This activity enables chemo-enzymatic assembly of arylomycin A2 that combines the advantages of liquid- and solid-phase peptide synthesis with late-stage enzymatic cross-coupling. The reactivity of AryC is unprecedented in cytochrome P450-mediated biaryl construction in non-ribosomal peptides, in which peptidyl carrier protein (PCP)-tethering so far was shown crucial both in vivo and in vitro. 相似文献
55.
采用低温CO吸附-原位红外光谱法对硫化态和经过氢还原处理的W/Al2O3,Ni/Al2O3以及不同Ni含量的NiW/Al2O3催化剂进行了表征. 结果表明,在WS2相上的两个CO特征吸收峰分别位于2117和2066 cm-1处; 硫化镍上吸附CO的特征峰位于2098 cm-1处; NiW/Al2O3催化剂中引入的助剂Ni与WS2相之间相互作用,并分别在2128,2096和2078 cm-1处出现三个新的谱峰,标志着NiWS活性相的形成,并且NiWS相的量随着助剂Ni含量的增加而增大. 在不同温度下对NiW/Al2O3催化剂进行氢还原处理时发现,NiWS活性相在高温下逐步分解,并发生烧结. 以上结果有力地支持了前文中通过XPS,HREM和TPR等方法所获得的有关催化剂活性相的形成及其还原分解过程的表征结果. 相似文献
56.
We consider the problem of vanishing of the momentswith Ω a compact domain in Rn and P(x), q(x) complex polynomials in x∈Ω (MVP). The main stress is on relations of this general vanishing problem to the following conjecture which has been studied recently in Mathieu (1997) [22], Duistermaat and van der Kallen (1998) [17], Zhao (2010) [34] and [35] and in other publications in connection with the vanishing problem for differential operators and with the Jacobian conjecture:
Conjecture A.
For positive μ ifmk(P,1)=0fork=1,2,… , thenmk(P,q)=0fork?1for any q. 相似文献
57.
Dubois J Lethimonnier F Vaufrey F Robert P Le Bihan D 《Magnetic resonance imaging》2005,23(3):453-462
A novel mechanism of MRI contrast enhancement, based on the detection by a balanced steady-state free precession (SSFP) sequence of the proton resonance frequency shift induced by bulk magnetic susceptibility (BMS) contrast agents, was investigated. The potential for this contrast mechanism to image blood vessels was explored. The relaxation time and the frequency shift effects of gadolinium- and dysprosium-DOTA on SSFP signal was first simulated and evaluated on a water phantom at 1.5 T. In vitro, a 5-mM concentration in contrast agent induced a 20-Hz frequency shift, leading to a signal increase of 92% for Dy-DOTA, and a 10-Hz frequency shift, leading to a signal increase of 58% for Gd-DOTA at the reference frequency, taking into account the nonlinear SSFP signal response on frequency offset. The concept was then evaluated in vivo on anesthetized rabbits. Low doses of dysprosium-DOTA were injected in their vascular system, and imaging was performed at the level of neck vessels. Following a bolus injection, mean signal changes of 31%, 20% and 14% were observed in the carotid arteries, the vertebral veins and the jugular veins, respectively. The bolus peak times in arteries and veins were consistent with the rabbit vascular circulation. This frequency-shift based contrast mechanism presents interesting potential for contrast-enhanced MR angiography (CE-MRA) compared to usual relaxation-based contrast, but further investigations on reproducibility will be necessary. 相似文献
58.
59.
The crystal and molecular structure of (+)-tetracarbonyl(methyl-1-naphthyl- phenylgermyl)cobalt was solved from three dimensional X-ray diffraction data by Patterson and Fourier syntheses and refined by full-matrix least-squares method to a final unweighted R of 0.047, excluding zeroes. The crystal is mono-clinic. space group P21, with a = 9.950(4), b = 6.860(3), c = 14.792(6) », β = 99.89(5)°, Z = 2. 1990 independent reflexions were recorded at room temperature with Ni-filtered Cu-Kα radiation. The determination of absolute configuration confirmed chemical assumptions. 相似文献
60.
Marie Francoise Bottin Micheline Boudeulle Jacques Guillet 《Journal of Polymer Science.Polymer Physics》1983,21(3):401-411
Orientation studies of hot-drawn polypropene films were performed using small-angle light scattering and wide-angle and small-angle x-ray scattering over a wide range of deformation. At low deformation, the classical scheme of affine deformation, as several authors have pointed out, seems to be quite realistic. However, for high deformations, i.e., up to 500%, a new conception of the microfibrillar state is proposed. The microfibrils are formed of fully extended crystals which have a high degree of parallel orientation, but deviations of the units from their ideal position occur. “Wrong” chains are embedded in the lattice, long-range order is lost, and paracrystallinity appears. A nematic arrangement develops gradually, and we suppose that the “needlelike entities” have some cylindrical symmetry with a crystalline core. The true amorphous component acts as a connection between these zones. 相似文献