Analogue Models of and for Gravity

Condensed matter systems, such as acoustics in flowing fluids, light in moving dielectrics, or quasiparticles in a moving superfluid, can be used to mimic aspects of general relativity. More precisely these systems (and others) provide experimentally accessible models of curved-space quantum field theory. As such they mimic kinematic aspects of general relativity, though typically they do not mimic the dynamics. Although these analogue models are thereby limited in their ability to duplicate all the effects of Einstein gravity they nevertheless are extremely important—they provide black hole analogues (some of which have already been seen experimentally) and lead to tests of basic principles of curved-space quantum field theory. Currently these tests are still in the realm of gedanken-experiments, but there are plausible candidate models that should lead to laboratory experiments in the not too distant future.     

Labile Interactions Defined in Crystalline Metal Complexes

The problems involved in identifying and quantifying labile interactions considered to influence complex compound structures are highlighted through the assessment of four different families of metal complexes for which extensive crystallographic data are available. Modification of the charge distribution within a ligand molecule as a result of coordination is one factor with a number of ramifications. A detailed analysis of evidence for both intra- and inter-molecular attractions in dimethylsulfoxide complexes of metal perchlorates is used to provide a basis for the consideration of weak interactions between complex ions involving forces including phenyl-group attractions, hydrogen bonding and cavity inclusion.     

Correction: Phytol-based novel adjuvants in vaccine formulation: 1. assessment of safety and efficacy during stimulation of humoral and cell-mediated immune responses

This is a correction article.     

3D molecular imaging SIMS

Thin monolayer and bilayer films of spin cast poly(methyl methacrylate) (PMMA), poly(2-hydroxyethyl methacrylate) (PHEMA), poly(lactic) acid (PLA) and PLA doped with several pharmaceuticals have been analyzed by dynamic SIMS using SF₅⁺ polyatomic primary ion bombardment. Each of these systems exhibited minimal primary beam-induced degradation under cluster ion bombardment allowing molecular depth profiles to be obtained through the film. By combing secondary ion imaging with depth profiling, three-dimensional molecular image depth profiles have been obtained from these systems. In another approach, bevel cross-sections are cut in the samples with the SF₅⁺ primary ion beam to produce a laterally magnified cross-section of the sample that does not contain the beam-induced damage that would be induced by conventional focussed ion beam (FIB) cross-sectioning. The bevel surface can then be examined using cluster SIMS imaging or other appropriate microanalysis technique.     

Multifunctional Calix[4]arenes Containing Pendant Amide and Phosphoryl Groups: Their Use as Extracting Agents and Carriers for Alkali Cations

The complexing, extracting and mobile carrier properties of the tetra(phosphine oxide)-calix[4]arene 1 and the hybrid diamide-di(phosphine oxide)-calix[4]arene 2 were studied. Both ligands give 1 : 1 complexes with alkali cations in THF as shown by the picrate method. 1H NMR experiments were run to follow encapsulation of sodium and potassium cations. The corresponding spectra indicate C2-symmetrical structure. The observed extraction orders of the alkali picrates were as follows K+>Rb+>Li+>Cs+>Na+ for 1 and Li+>Na+>K+>Rb++ for 2. Transport kinetics was analysed by means of a model which assumes pure diffusion and which allows the evaluation of mass transfer coefficients in all systems. These coefficients and their influences on the transport rate are discussed in terms of size of the transporting species in the liquid membrane.     

Feeble forces and gravity

We develop a scenario in which feeble intermediate range forces emerge as an effect resulting from the compactification (à la Kaluza-Klein) of multidimensional theories. These feeble forces compete with gravity and in general permit different bodies to fall to earth with different accelerations. We show that these feeble forces are mediated by vectors (V) and/or scalars (S), whose dimensionless coupling constants are typically of order g_v g_s 10^–10 Under certain plausible assumptions the ranges of these feeble forces are expected to be of order 1 m to 1 km. It is conjectured that the general strategy will prove applicable to realistic multidimensional theories such as the 10-dimensional superstring theories. We speculate that deviations from the standard gravitational force-similar to the ones reported recently as a fifth force-may be interpreted as evidence for higher dimensions.This essay received the second award from the Gravity Research Foundation for the year 1986.Supported by the U.S. Department of Energy under grant # DE-FG03-84ER-40168.     

Linear scaling computation of the Fock matrix. VII. Periodic density functional theory at the Gamma point

Linear scaling quantum chemical methods for density functional theory are extended to the condensed phase at the Gamma point. For the two-electron Coulomb matrix, this is achieved with a tree-code algorithm for fast Coulomb summation [M. Challacombe and E. Schwegler, J. Chem. Phys. 106, 5526 (1997)], together with multipole representation of the crystal field [M. Challacombe, C. White, and M. Head-Gordon, J. Chem. Phys. 107, 10131 (1997)]. A periodic version of the hierarchical cubature algorithm [M. Challacombe, J. Chem. Phys. 113, 10037 (2000)], which builds a telescoping adaptive grid for numerical integration of the exchange-correlation matrix, is shown to be efficient when the problem is posed as integration over the unit cell. Commonalities between the Coulomb and exchange-correlation algorithms are discussed, with an emphasis on achieving linear scaling through the use of modern data structures. With these developments, convergence of the Gamma-point supercell approximation to the k-space integration limit is demonstrated for MgO and NaCl. Linear scaling construction of the Fockian and control of error is demonstrated for RBLYP6-21G* diamond up to 512 atoms.     

Functionalized organosilica microspheres via a novel emulsion-based route

Thiol-functionalized organosilica microspheres were synthesized via a two-step process: (1) acid-catalyzed hydrolysis and condensation of 3-mercaptopropyltrimethoxysilane (MPTMS), followed by (2) base-catalyzed condensation, which led to the rapid formation of emulsion droplets with a narrow size distribution. These droplets continued to condense to form solid microspheres. Solution (29)Si NMR and optical microscopy were applied to study the mechanism of this novel synthetic route. Solid-state (29)Si NMR, SEM, zeta potential titration, and Coulter counter measurements were used to study the bulk and surface properties and to determine the particle size distributions of the final microspheres. Compared to conventional St?ber silica particles, these microspheres were shown to have a lower degree of cross-linking (average degree of condensation, r = 1.25), a larger average size (up to 6 microm), and a higher isoelectric point (pH = 4.4). Confocal microscopy of dye-labeled microspheres showed an even distribution of dye molecules throughout the interior, characteristic of a readily accessible and permeable organosilica network. These findings have implications for the production of functionalized solid supports for use in catalysis and biological applications, such as optically encoded carriers for combinatorial synthesis.     

Using wavelets to analyze AFM images of thin films: surface micelles and supported lipid bilayers

This paper presents micro- and nanoanalysis of thin films based on images obtained by atomic force microscopy (AFM). The analysis exploits the discrete wavelet transform and the resulting wavelet spectrum to study surface features. It is demonstrated that the wavelet technique can characterize micro- and nanosurface features and distinguish between similar surface structures. The use of a feature extraction method is shown. The method involves the separation of certain frequency content from the original AFM images and analyzing the data independently to gain quantitative information about the images. By using the feature extraction method, soft surfaces in water are analyzed and nanofeatures are measured. The packing of surface micelles of sodium dodecyl sulfate on a self-assembled monolayer is analyzed. The characteristics of pore formation, due to penetration of the antibacterial peptide protegrin, into a solid-supported lipid bilayer are quantified. The sizes of the pores are obtained, and it is observed that the line tension of the pores reduces the fluctuations of the lipid bilayer.     

Cyclodextrin Solubilization of the Antibacterial Agents Triclosan and Triclocarban: Effect of Ionization and Polymers

The natural β-cyclodextrin (βCD) and its complexes have limited solubility in aqueous solutions. This low aqueous solubility, as well as low aqueous solubility of the guest molecule (i.e. triclosan or triclocarban (TCC)), can result in low complexation efficiency (CE). The purpose of this study was to enhance the apparent intrinsic solubility (S ₀) of the guest molecule and its βCD complexes through ionization and addition of auxiliary compounds such as polymers, amino acids and metal ions. Both triclosan (pK _a 7.9) and TCC (pK _a 12.7) are weak acids. Addition of ethanol to the complexation medium enhanced S ₀ of both triclosan and TCC but at the same time ethanol lowered the stability constant (K _c ) of their βCD complexes resulting in overall lowering of CE. Addition of small amount of water-soluble polymers enhanced the βCD solubilization of both guests, and addition lysine enhanced the solubilization of TCC. Ionization of triclosan resulted in significant enhancement of CE and enhanced triclosan release from tablets containing triclosan/βCD complex. The effect of ionization was not as pronounced in the case of TCC.This revised version was published online in July 2005 with a corrected issue number.