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61.
Coating hydrogel films or microspheres by an adsorbed colloidal shell is one synthesis method for forming colloidosomes. The colloidal shell allows control of the release rate of encapsulated materials, as well as selective transport. Previous studies found that the packing density of self-assembled, adsorbed colloidal monolayers is independent of the colloidal particle size. In this paper we develop an equilibrium model that correlates the packing density of charged colloidal particles in an adsorbed shell to the particle dimensions in monodisperse and bidisperse systems. In systems where the molar concentration in solution is fixed, the increase in adsorption energy with increasing particle size leads to a monotonic increase in the monolayer packing density with particle radius. However, in systems where the mass fraction of the particles in the adsorbing solutions is fixed, increasing particle size also reduces the molar concentration of particles in solution, thereby reducing the probability of adsorption. The result is a nonmonotonic dependence of the packing density in the adsorbed layer on the particle radius. In bidisperse monolayers composed of two particle sizes, the packing density in the layer increases significantly with size asymmetry. These results may be utilized to design the properties of colloidal shells and coatings to achieve specific properties such as transport rate and selectivity. 相似文献
62.
The synthesis of the novel nucleotide analogues 5'-deoxynucleoside-5'-S-methylphosphonates, starting from 5'-deoxy-5'-haloribonucleosides, 5'-O-tosylribonucleosides, and 2'-O-triflylnucleosides, is described. The phosphonothiolation of these compounds was achieved using S-(diisopropylphosphonomethyl)isothiouronium tosylate, a new, odourless, and efficient equivalent of mercaptomethylphosphonate. The thiolate anion of mercaptomethylphosphonate was generated in situ from the isothiouronium salt in both protic and aprotic solvents using two equivalents of sodium iso-propoxide. The prepared nucleoside 5'-S-methylphosphonates were deprotected, and the free phosphonic acids were transformed into diphosphoryl derivatives (the NTP analogues). Both mononucleotides and NTP analogues were studied as substrates/inhibitors of several enzymes that are involved in the nucleoside/nucleotide metabolism. 相似文献
63.
The absorption spectra and excited state dipole moments of four differently substituted fulvenes have been investigated both experimentally and computationally. The results reveal that the excited state dipole moment of fulvenes reverses in the first excited singlet state when compared to the ground state. The oppositely polarized electron density distributions, which dominate the ground state and the first excited singlet state of fulvenes, respectively, reflect the reversed π-electron counting rules for aromaticity in the two states (4n + 2 vs. 4n, respectively). The results show that substituents indeed influence the polarity of fulvenes in the two states, however, cooperative interactions between the substituents and the fulvene moiety are most pronounced in the ground state. 相似文献
64.
CLAUDIA L. PARKER OSCAR N. VENTURA STAN K. BURT RAÚL E. CACHAU 《Molecular physics》2013,111(17):2659-2668
We present a general purpose QM-MM-MD engine (DYNGA) designed to test alternative hybrid Hamiltonians geared towards the treatment of problems of interest in structural biology including the use of experimental data constraints. In this first presentation we use DYNGA to explore the behaviour of a traditional QM-MM approach in the treatment of the water—water interaction. We find the potential energy hypersurface for the water dimer computed with the HF 4–31G*/TIP3P hybrid Hamiltonian tends to be too flat. We also explore the effect of using traditional QM-MM techniques on proton wires and conclude there is a need for improvement, possibly addressed by using polarizable force fields. 相似文献
65.
Fluorimetry is a relatively fast and accurate means of determining the dissociation constants of sparingly soluble heterocyclic bases. Complications can arise, however, from the dependence of fluorescence on excited-state as well as ground-state acid-base chemistry. Several approaches to circumventing or compensating for this difficulty are discussed. To demonstrate the utility of the methods, the pK(a), values of the conjugate acids of two bases are evaluated by the methods described. 相似文献
66.
R. J. Rosenberg 《Journal of Radioanalytical and Nuclear Chemistry》1981,62(1-2):145-149
A simple method for the determination of uranium and thorium by delayed neutron counting is described. One portion of the
sample is irradiated in a reactor and the delayed neutrons are counted. Another portion of the sample is mixed with B4 C powder absorbing the thermal neutrons, and irradiated in the same position. From those data, both uranium and thorium can
be calculated when a quantitative calibration has been made beforehand. The detection limits for the pure elements are 0.07
ppm for uranium and 2 ppm for thorium with the minimum analyzing time being 2 min. The accuracy of the method is investigated
by comparing results obtained by the method described here with results obtained by epithermal activation analysis. 相似文献
67.
68.
Winske D. Rosenberg M. 《IEEE transactions on plasma science. IEEE Nuclear and Plasma Sciences Society》1998,26(1):92-99
We study the nonlinear behavior of the low-frequency dust acoustic instability in a collisional dusty plasma by means of particle simulations. The instability arises due to the streaming of plasma ions and neutrals relative to charged dust grains. According to linear theory, the presence of collisions between the plasma ions and a neutral gas background reduces the growth rate of the instability. Nonlinearly, however, the presence of drifting neutrals maintains the initial relative drift between plasma and dust ions until the unstable waves grow to large amplitude and collisions due to wave-particle interactions exceed the neutral collisions. As a result, stronger nonlinear effects, as manifested by enhanced fluctuations, larger amounts of plasma and dust heating, and a temporary reduction of the relative drift velocity, can occur in the presence of collisions 相似文献
69.
70.
Rosenberg M. Mendis D.A. Sheehan D.P. 《IEEE transactions on plasma science. IEEE Nuclear and Plasma Sciences Society》1996,24(6):1422-1430
A scheme for forming a Coulomb lattice of positively charged dust grains in a high-pressure (P>torr) gas is discussed theoretically. The grains are charged positively by photoemission in the presence of a flux of ultraviolet (UV) photons with energy larger than the work function of the grains, but lower than the ionization potential of the background gas. Methods for levitating and containing the dust using photophoretic forces (both UV and non-UV), gas drag, and electrostatic forces are considered 相似文献