Synthesis, Thermotropic Behavior, and Permeability Properties of Vesicular Membranes Composed of Cationic Mixed-Chain Surfactants

In order to elucidate the role of the linkage region that connects polar headgroups with hydrophobic segments in a lipid monomer, cationic mixed-chain amphiphiles containing acyl and alkyl hydrophobic segments connected at the level of Me(2)N(+) headgroups 2a-d were synthesized. Related dialkyldimethyl-ammonium ion surfactants 1a-e and diacyl systems 3a-c were also synthesized. Despite mismatch in the connector region, amphiphiles 2a-d form bilayer vesicles like their dialkyl and diacyl counterparts, as revealed by electron microscopy. Introduction of an ester connector function between the polar and hydrophobic parts raises the phase transition temperature (T-m), transition enthalpies, and resistance to ion permeation. Consideration of energy minimized conformations points toward the importance of differences in the depth of chain penetration into the putative bilayer.

The Metal-Nonmetal Transition: A Global Perspective

A wide range of condensed matter systems traverse the metal-nonmetal transition. These include doped semiconductors, metal-ammonia solutions, metal clusters, metal alloys, transition metal oxides, and superconducting cuprates. Certain simple criteria, such as those due to Herzfeld and Mott, have been highly successful in explaining the metallicity of materials. In this article, we demonstrate the amazing effectiveness of these criteria and examine them in the light of recent experimental findings. We then discuss the Limitations in our understanding of the phenomenon of the metal-nonmetal transition.

Interfacial Regions Governing Internal Cavities of Dendrimers. Studies of Poly(alkyl aryl ether) Dendrimers Constituted with Linkers of Varying Alkyl Chain Length

This report deals with a study of the properties of internal cavities of dendritic macromolecules that are capable Of encapsulating and mediating photoreactions of guest molecules. The internal cavity structures of dendrimers are determined by the interfacial regions between the aqueous exterior and hydrocarbon like interior constituted by the linkers that connect symmetrically sited branch points constituting the dendrimer and head groups that cap the dendrimers. Phloroglucinol-based poly(alkyl aryl ether) dendrimers constituted with a homologous series of alkyl linkers were undertaken for the current study. Twelve dendrimers within first, second, and third generations, having ethyl, n-propyl, n-butyl, and n-pentyl groups as the linkers and hydroxyl groups at peripheries in each generation, were synthesized. Encapsulation of pyrene and coumarins by aqueous basic solutions of dendrimers were monitored-by UV-vis and fluorescence spectroscopies, which showed that a lower generation dendrimer with an optimal alkyl linker presented better encapsulation abilities than a higher generation dendrimer. Norrish type I photoreaction of dibenzyl ketone was carried out within the above: series of dendrimers to probe their abilities to hold guests and reactive inthermediate radical pairs within themselves. The extent of cage effect from the series of third generation dendrimers was observed to be higher with dendrimers having an n-pentyl group as the linker.

Learning the global maximum with parameterized learning automata

A feedforward network composed of units of teams of parameterized learning automata is considered as a model of a reinforcement teaming system. The internal state vector of each learning automaton is updated using an algorithm consisting of a gradient following term and a random perturbation term. It is shown that the algorithm weakly converges to a solution of the Langevin equation implying that the algorithm globally maximizes an appropriate function. The algorithm is decentralized, and the units do not have any information exchange during updating. Simulation results on common payoff games and pattern recognition problems show that reasonable rates of convergence can be obtained.

Spin distributions in antiferromagnetically coupled Mn2+Cu2+ systems: from the pair to the infinite chain

Probably the most informative description of the ground slate of a magnetic molecular species is provided by the spin density map. Such a map may be experimentally obtained from polarized neutron diffraction (PND) data or theoretically calculated using quantum chemical approaches. Density functional theory (DFT) methods have been proved to be well-adapted for this. Spin distributions in one-dimensional compounds may also be computed using the density matrix renormalization group (DMRG) formalism. These three approaches, PND, DFT, and DMRG, have been utilized to obtain new insights on the ground state of two antiferromagnetically coupled Mn2+Cu2+ compounds, namely [Mn(Me-6-[14]ane-N-4)Cu(oxpn)](CF3SO3)(2) and MnCu(pba)(H2O)(3) . 2H(2)O, with Me-6-[14]ane-N-4 = (+/-)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, oxpn = N,N'-bis(3-aminopropyl)oxamido and pba = 1,3-propylenebis(oxamato). Three problems in particular have been investigated: the spin distribution in the mononuclear precursors [Cu(oxpn)] and [Cu(pba)](2-), the spin density maps in the two Mn2+Cu2+ compounds, and the evolution of the spin distributions on the Mn2+ and Cu2+ sites when passing from a pair to a one-dimensional ferrimagnet.

Structural characterization and chain dynamics of poly(alpha-methylstyrene peroxide) by NMR spectroscopy

Poly(alpha-methylstyrene peroxide) has been synthesized and characterized spectroscopically. The H-1 and C-13 NMR spectra are shown to reveal the stereochemical features and the endgroups in the peroxide chain. The preliminary studies on the chain dynamics of the polyperoxide chain has been done by measuring the spin-lattice relaxation times (T-1) of the main chain as well as the side chain carbons. It has been shown from the dependence of the spin-lattice relaxation times that the polyperoxide chain is more flexible compared to the corresponding hydrocarbon-backbone analog.

Statistical thermodynamics of lattice models in zeolites: Implications of local versus global mean field interactions

The statistical thermodynamics of adsorption in caged zeolites is developed by treating the zeolite as an ensemble of M identical cages or subsystems. Within each cage adsorption is assumed to occur onto a lattice of n identical sites. Expressions for the average occupancy per cage are obtained by minimizing the Helmholtz free energy in the canonical ensemble subject to the constraints of constant M and constant number of adsorbates N. Adsorbate-adsorbate interactions in the Brag-Williams or mean field approximation are treated in two ways. The local mean field approximation (LMFA) is based on the local cage occupancy and the global mean field approximation (GMFA) is based on the average coverage of the ensemble. The GMFA is shown to be equivalent in formulation to treating the zeolite as a collection of interacting single site subsystems. In contrast, the treatment in the LMFA retains the description of the zeolite as an ensemble of identical cages, whose thermodynamic properties are conveniently derived in the grand canonical ensemble. For a z coordinated lattice within the zeolite cage, with epsilon(aa) as the adsorbate-adsorbate interaction parameter, the comparisons for different values of epsilon(aa)(*)=epsilon(aa)z/2kT, and number of sites per cage, n, illustrate that for -1 0. We compare the isotherms predicted with the LMFA with previous GMFA predictions [K. G. Ayappa, C. R. Kamala, and T. A. Abinandanan, J. Chem. Phys. 110, 8714 (1999)] (which incorporates both the site volume reduction and a coverage-dependent epsilon(aa)) for xenon and methane in zeolite NaA. In all cases the predicted isotherms are very similar, with the exception of a small steplike feature present in the LMFA for xenon at higher coverages. (C) 1999 American Institute of Physics. [S0021-9606(99)70333-8].

A C-H center dot center dot center dot O hydrogen bond stabilized polypeptide chain reversal motif at the C terminus of helices in proteins

The serendipitous observation of a C-H...O hydrogen bond mediated polypeptide chain reversal in synthetic peptide helices has led to a search for the occurrence of a similar motif in protein structures. From a dataset of 634 proteins, 1304 helices terminating in a Schellman motif have been examined. The C-H...O interaction between the T - 4 (CH)-H-alpha and T + 1 C=O group (C...O 3.5 Angstrom) becomes possible only when the T + 1 residue adopts an extended beta conformation (T is defined as the helix terminating residue adopting an alpha(L) conformation). In all, 111 examples of this chain reversal motif have been identified and the compositional and conformational. preferences at positions T - 4, T, and T + 1 determined. A marked preference for residues like Set, Glu and Gln is observed at T - 4 position with the motif being further stabilized by the formation of a side-chain-backbone O...H-N hydrogen bond involving the side-chain of residue T - 4 and the N-H group of residue T + 3. In as many as 57 examples, the segment following the helix was extended with three to four successive residues in beta conformation. In a majority of these cases, the succeeding beta strand lies approximately antiparallel with the helix, suggesting that the backbone C-H...O interactions may provide a means of registering helices and strands in an antiparallel orientation. Two examples were identified in which extended registry was detected with two sets of C-H...O hydrogen bonds between (T - 4) (CH)-H-alpha...C=O (T + 1) and (T - 8) (CH)-H-alpha...C=O (T + 3). 0 2002 Published by Elsevier Science Ltd.

Characterization of alkyl chain conformation in an intercalated cationic lipid bilayer by IR spectroscopy

A structural analysis of alkyl chain conformation of an intercalated cationic lipid bilayer is described. Dialkyl dimethylammonium ions (di-C(n)DA) were ion exchanged into the galleries of layered cadmium thiophosphate to give Cd0.83PS3(di-C(n)DA)(0.34). The grafting density and interlayer expansions were identical to those for the intercalated single chain alkyl trimethylammonium (C(n)TA) bilayers. The increased methylene chain density in the galleries, however, forces the intercalated lipid to adopt a more trans ordered structure. Progression bands arising from the coupling of vibrational modes of trans methylene units are used to establish the extent of trans registry. Two types of ordered structures of the intercalated cationic lipid may be distinguished. One in which both alkyl chains adopt an all-trans geometry, and one in which the methylene bond adjacent to the headgroup on one of the alkyl chains is gauche. The latter structure is typically found in the crystalline state of these cationic lipids. The concentrations of the two structures were determined from the ratio of the intensities of the progression bands and were found to remain unchanged with temperature.

Synthesis, properties, and comparative analyses on the chain flexibility of an ultrastable vinyl polyperoxide

The most stable vinyl polyperoxide, namely, poly(indene peroxide) (PINDP), an alternating copolymer of indene and oxygen, was synthesized by the oxidative polymerization of indene. It was characterized by H-1-NMR and C-13-NMR, Fourier transform infrared, differential scanning calorimetry, direct pyrolysis mass spectrometry, and gas chromatography mass spectrometry studies. The overall activation energy for the degradation and the glass-transition temperature of PINDP were 47 kcal/mol and 327 K respectively, which were very high compared to those of other vinyl polyperoxides. (C) 2002 Wiley Periodicals, Inc.

One-dimensional zinc phosphates with linear chain structure

Three one-dimensional zinc phosphates, [C5N2H14][Zn(HPO4)2], I, [C10N4H26][Zn(HPO4)2].2H2O II, and [C4N2H6]2[Zn(HPO4)], III, have been prepared employing hydro/solvothermal methods in the presence of organic amines. While I and II consist of linear chains of corner-shared four-membered rings, III is a polymeric wire where the amine molecule is directly bonded to the metal center. The wire, as well as the chain in these structures, are held together by hydrogen bond interactions involving the amine and the framework oxygens. The polymeric zinc phosphate with wire-like architecture, III, is only the second example of such architecture. Crystal data: I, monoclinic, P21/c (no. 14), a=8.603(2), b=13.529(2), c=10.880(1) Å, β=94.9(1)°, V=1261.6(1) Å3, Z=4, ρcalc.=1.893 gcm−3, μ(MoKα)=2.234 mm−1, R1=0.032, wR2=0.086, [1532 observed reflections with I>2σ(I)], II, orthorhombic, Pbca (no. 61), a=8.393(1), b=15.286(1), c=22.659(1) Å, V=2906.9(2) Å3, Z=8, ρcalc.=1.794 gcm−3, μ(MoKα)=1.957 mm−1, R1=0.055, wR2=0.11, [1565 observed reflections with I>2σ(I) and III, monoclinic, P21/c (no. 14), a=8.241(1), b=13.750(2), c=10.572(1) Å, β=90.9(1)°, V=1197.7(2) Å3, Z=4, ρcalc.=1.805 gcm−3, μ(MoKα)=2.197 mm−1, R1=0.036, wR2=0.10, [1423 observed reflections with I>2σ(I)].

Synthesis and Properties of a Novel (Main-Chain)– (Side-Chain) Polymeric Peroxide

A novel (main-chain)-(side-chain) vinyl polyperoxide, poly(dipentene peroxide)(PDP), an alternating copolymer of dipentene (DP) and oxygen, has been synthesized by thermal oxidative polymerization of DP. The PDP was characterized by 1H NMR, 13C NMR, FTIR, DSC, TGA, and EI-MS studies. The overall activation energies of the degradation from Kissinger’s method were 28 and 33 kcal/mol, respectively, for the endocyclic and acyclic peroxide units. The side-chain peroxy groups were found to be thermally more stable than the main chain. Above 45°C the rate of polymerization increases sharply at a particular instant showing an “autoacceleration” with the formation of knee point. The kinetics of autoacceleration has been studied at various temperatures (45–70°C) and pressures (50–250 psi). © 2000 John Wiley&Sons, Inc. J Appl Polym Sci 79: 1549–1555, 2001

Synthesis, structural characterization, thermal studies and chain dynamics of poly(methacrylonitrile peroxide) by NMR spectroscopy

Poly(methacrylonitrile peroxide) (PMNP) has been synthesized from methacrylonitrile by free radical initiated oxidative polymerization and characterized by different spectroscopic methods. NMR spectroscopy confirmed the alternating copolymer structure with labile peroxy bonds in the main chain. The extreme instability of PMNP was noted from FTIR spectroscopy. Thermal degradation studies by using differential scanning calorimetry and thermogravimetry have revealed that PMNP degrades highly exothermically and the heat of degradation, 42.5 kcal mol−1, is of the same order as that reported for other vinyl polyperoxides. Mass spectral fragmentation pattern under electron impact (EI) condition has also been investigated. The mechanism of the primary exothermic degradation has been substantiated by thermochemical calculations. The chain dynamics of the polyperoxide chain has been studied by means of 13C spin–lattice relaxation times (T1) of the main chain as well as the side chain carbons. The temperature dependence of the spin–lattice relaxation times shows that the PMNP is more flexible compared to the analogous poly(styrene peroxide).

Phase transitions in the anchored organic bilayers of long-chain alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4; n=12, 16, 18

The single perovskite slab alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4, n = 12, 16, 18, display two phase transitions, just above room temperature, associated with changes in the alkylammonium chains. We have followed these two phase transitions using scanning calorimetry, X-ray powder diffraction, and IR and Raman spectroscopies. We find the first phase transition to be associated with symmetry changes arising from a dynamic rotational disordering of the ammonium headgroup of the chain whereas the second transition, the melting of the chains in two dimensions, is characterized by an increased conformational disorder of the methylene units of the alkyl chains. We examine these phase transitions in light of the interesting optical properties of these materials, as well as the relevance of these systems as models for phase transitions in lipid bilayers.

Albedo enhancement of marine clouds to counteract global warming: impacts on the hydrological cycle

Recent studies have shown that changes in solar radiation affect the hydrological cycle more strongly than equivalent CO(2) changes for the same change in global mean surface temperature. Thus, solar radiation management ``geoengineering'' proposals to completely offset global mean temperature increases by reducing the amount of absorbed sunlight might be expected to slow the global water cycle and reduce runoff over land. However, proposed countering of global warming by increasing the albedo of marine clouds would reduce surface solar radiation only over the oceans. Here, for an idealized scenario, we analyze the response of temperature and the hydrological cycle to increased reflection by clouds over the ocean using an atmospheric general circulation model coupled to a mixed layer ocean model. When cloud droplets are reduced in size over all oceans uniformly to offset the temperature increase from a doubling of atmospheric CO(2), the global-mean precipitation and evaporation decreases by about 1.3% but runoff over land increases by 7.5% primarily due to increases over tropical land. In the model, more reflective marine clouds cool the atmospheric column over ocean. The result is a sinking motion over oceans and upward motion over land. We attribute the increased runoff over land to this increased upward motion over land when marine clouds are made more reflective. Our results suggest that, in contrast to other proposals to increase planetary albedo, offsetting mean global warming by reducing marine cloud droplet size does not necessarily lead to a drying, on average, of the continents. However, we note that the changes in precipitation, evaporation and P-E are dominated by small but significant areas, and given the highly idealized nature of this study, a more thorough and broader assessment would be required for proposals of altering marine cloud properties on a large scale.