Synthesis and vesicle formation from dimeric pseudoglyceryl lipids with (CH2)(m) spacers: pronounced m-value dependence of thermal properties, vesicle fusion, and cholesterol complexation

Eight new dimeric lipids, in which the two Me2N+ ion headgroups are separated by a variable number of polymethylene units [-(CH2)(m)-], have been synthesized. The electron micrograph (TEM) and dynamic light scattering (DLS) of their aqueous dispersions confirmed the formation of vesicular-type aggregates. The vesicle sizes and morphologies were found to depend strongly on the m value, the method, and thermal history of the vesicle preparation. Information on the thermotropic properties of the resulting vesicles was obtained from microcalorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, the T-m values for these vesicles revealed a nonlinear dependence on spacer chain length (m value). These vesicles were able to entrap riboflavin. The rates of permeation of the OH- ion under an imposed transmembrane pH gradient were also found to depend significantly on the m value. X-Ray diffraction of the cast films of the lipid dispersions elucidated the nature and the thickness of these membrane organizations, and it was revealed that these lipids organize in three different ways depending on the m value. The EPR spin-probe method with the doxylstearic acids 5NS, 12NS, and 16NS, spin-labeled at various positions of stearic acid, was used to establish, the chain-flexibility gradient and homogeneity of these bilayer assemblies. The apparent fusogenic propensities of these bipolar tetraether lipids were investigated in the presence of Na2SO4 with fluorescence-resonance energy-transfer fusion assay. Small unilamellar vesicles formed from 1 and three representative biscationic lipids were also studied with fluorescence anisotropy and H-1 NMR spectroscopic techniques in the absence and the presence of varying amounts of cholesterol.

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.

Synthesis and characterization of novel cationic lipid and cholesterol-coated gold nanoparticles and their interactions with dipalmitoylphosphatidylcholine membranes

Novel gold nanoparticles bearing cationic single-chain, double-chain, and cholesterol based amphiphilic units have been synthesized. These nanoparticles represent size-stable entities in which various cationic lipids have been immobilized through their thiol group onto the gold nanoparticle core. The resulting colloids have been characterized by UV-vis, (1)H NMR, FT-IR spectroscopy, and transmission electron microscopy. The average size of the resultant nanoparticles could be controlled by the relative bulkiness of the capping agent. Thus, the average diameters of the nanoparticles formed from the cationic single-chain, double-chain, and cholesterol based thiolate-coated materials were 5.9,2.9, and 2.04 nm, respectively. We also examined the interaction of these cationic gold nanoparticles with vesicular membranes generated from dipalmitoylphosphatidylcholine (DPPC) lipid suspensions. Nanoparticle doped DPPC vesicular suspensions displayed a characteristic surface plasmon band in their UV-vis spectra. Inclusion of nanoparticles in vesicular suspensions led to increases in the aggregate diameters, as evidenced from dynamic light scattering. Differential scanning calorimetric examination indicated that incorporation of single-chain, double-chain, and cholesteryl-linked cationic nanoparticles exert variable effects on the DPPC melting transitions. While increased doping of single-chain nanoparticles in DPPC resulted in the phases that melt at higher temperatures, inclusion of an incremental amount of double-chain nanoparticles caused the lowering of the melting temperature of DPPC. On the other hand, the cationic cholesteryl nanoparticle interacted with DPPC in membranes in a manner somewhat analogous to that of cholesterol itself and caused broadening of the DPPC melting transition.

Two new 1D chains of Ni(2)Na(2) heterometallic double half-cubane building units: Synthesis, structures and variable temperature magnetic study

An equimolar mixture of Ni(NO(3))(2)center dot 6H(2)O and pyridine-2-aldehyde with two equivalents of NaN(3) in methanol in the presence of NaOMe resulted in the formation of light green precipitate which upon crystallization from dimethylformamide (DMF) yielded light green single crystals [{Ni(2)Na(2)(pic)(4)(N(3))(2)(H(2)O)(2)(MeOH)}center dot MeOH center dot 3H(2)O](n) (1) and [{Ni(2)Na(2)(pic)(4)(N(3))(2)(H(2)O)(4)}center dot 2DMF center dot H(2)O](n) (2) (pic = pyridine-2-carboxylate) at room temperature and high temperature (100 degrees C), respectively. Variable temperature magnetic studies revealed the existence of overall ferromagnetic behaviour with J approximate to + 10 cm(-1) and D approximate to -2 to -7 cm(-1) for 1 and 2, respectively. Negative D values as well as variation of D upon slight distortion of structure by varying reaction temperature were observed. The X-band Electron Paramagnetic Resonance (EPR) spectra of both 2 and 3 were recorded below 50 K. The structural distortion was also implicated from the EPR spectra. Density Functional Theory (DFT) calculations on both complexes were performed in two different ways to corroborate the magnetic results. Considering only Ni(2)(II) dimeric unit, results were J = + 20.65 cm(-1) and D = -3.16 cm(-1) for 1, and J = +24.56 cm(-1) and D = -4.67 cm(-1) for 2. However, considering Ni(2)(II)Na(2)(I) cubane as magnetic core the results were J = +16.35 cm(-1) (1), +19.54 cm(-1) (2); D = -3.05 cm(-1) (1), -4.25 cm(-1) (2).

Intensity profile of light scattered from a rough surface

We present in this paper, approximate analytical expressions for the intensity of light scattered by a rough surface, whose elevation. xi(x,y) in the z-direction is a zero mean stationary Gaussian random variable. With (x,y) and (x',y') being two points on the surface, we have h. = 0 with a correlation, = sigma(2)g(r), where r = (x - x')(2) + ( y - y')(2)](1/2) is the distance between these two points. We consider g(r) = exp-r/l)(beta)] with 1 <= beta <= 2, showing that g(0) = 1 and g(r) -> 0 for r >> l. The intensity expression is sought to be expressed as f(v(xy)) = {1 + (c/2y)v(x)(2) + v(y)(2)]}(-y), where v(x) and v(y) are the wave vectors of scattering, as defined by the Beckmann notation. In the paper, we present expressions for c and y, in terms of sigma, l, and beta. The closed form expressions are verified to be true, for the cases beta = 1 and beta = 2, for which exact expressions are known. For other cases, i.e., beta not equal 1, 2 we present approximate expressions for the scattered intensity, in the range, v(xy) = (v(x)(2) + v(y)(2))(1/2) <= 6.0 and show that the relation for f(v(xy)), given above, expresses the scattered intensity quite accurately, thus providing a simple computational methods in situations of practical importance.

Dynamical localization in a chain of hard core bosons under periodic driving

We study the dynamics of a one-dimensional lattice model of hard core bosons which is initially in a superfluid phase with a current being induced by applying a twist at the boundary. Subsequently, the twist is removed, and the system is subjected to periodic delta-function kicks in the staggered on-site potential. We present analytical expressions for the current and work done in the limit of an infinite number of kicks. Using these, we show that the current (work done) exhibits a number of dips (peaks) as a function of the driving frequency and eventually saturates to zero (a finite value) in the limit of large frequency. The vanishing of the current (and the saturation of the work done) can be attributed to a dynamic localization of the hard core bosons occurring as a consequence of the periodic driving. Remarkably, we show that for some specific values of the driving amplitude, the localization occurs for any value of the driving frequency. Moreover, starting from a half-filled lattice of hard core bosons with the particles localized in the central region, we show that the spreading of the particles occurs in a light-cone-like region with a group velocity that vanishes when the system is dynamically localized.

Associated jet and subjet rates in light-quark and gluon jet discrimination

We show that in studies of light quark- and gluon-initiated jet discrimination, it is important to include the information on softer reconstructed jets (associated jets) around a primary hard jet. This is particularly relevant while adopting a small radius parameter for reconstructing hadronic jets. The probability of having an associated jet as a function of the primary jet transverse momentum (PT) and radius, the minimum associated jet pi, and the association radius is computed up to next-to-double logarithmic accuracy (NDLA), and the predictions are compared with results from Herwig++, Pythia6 and Pythia8 Monte Carlos (MC). We demonstrate the improvement in quark-gluon discrimination on using the associated jet rate variable with the help of a multivariate analysis. The associated jet rates are found to be only mildly sensitive to the choice of parton shower and hadronization algorithms, as well as to the effects of initial state radiation and underlying event. In addition, the number of k(t) subjets of an anti-k(t) jet is found to be an observable that leads to a rather uniform prediction across different MC's, broadly being in agreement with predictions in NDLA, as compared to the often used number of charged tracks observable.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Signal transduction with hybridization chain reactions

Some of the most exciting developments in the field of nucleic acid engineering include the utilization of synthetic nucleic acid molecular devices as gene regulators, as disease marker detectors, and most recently, as therapeutic agents. The common thread between these technologies is their reliance on the detection of specific nucleic acid input markers to generate some desirable output, such as a change in the copy number of an mRNA (for gene regulation), a change in the emitted light intensity (for some diagnostics), and a change in cell state within an organism (for therapeutics). The research presented in this thesis likewise focuses on engineering molecular tools that detect specific nucleic acid inputs, and respond with useful outputs.

Four contributions to the field of nucleic acid engineering are presented: (1) the construction of a single nucleotide polymorphism (SNP) detector based on the mechanism of hybridization chain reaction (HCR); (2) the utilization of a single-stranded oligonucleotide molecular Scavenger as a means of enhancing HCR selectivity; (3) the implementation of Quenched HCR, a technique that facilitates transduction of a nucleic acid chemical input into an optical (light) output, and (4) the engineering of conditional probes that function as sequence transducers, receiving target signal as input and providing a sequence of choice as output. These programmable molecular systems are conceptually well-suited for performing wash-free, highly selective rapid genotyping and expression profiling in vitro, in situ, and potentially in living cells.

Surface plasmons and effects of losses in propagating modes in a chain of silver nanoparticles

In this work a chain of 4000 silver nanoparticles embedded in a glass medium is considered, and its leftmost particle is excited by an electric field pulse of Gaussian shape. Considering Drude’s model, losses of the system are taken into account by γ factor, which stands for the Ohmic losses, and different quantities, such as frequencies of excited modes and group velocities are calculated. Besides, these results are compared to those obtained from the dispersion relation of an infinite chain. The increase of losses affects the lifetime and propagation length of the plasmon; besides, although the response dispersion relation for an infinite chain seems to remain invariable, this is not the case for a finite chain. The mismatches are bigger for higher losses. Furthermore, plasmon propagation velocities are analysed, and an explanation for the mismatch of longitudinal modes close to the intersection point with the dispersion of light is suggested. Finally, some concepts to treat this problem from the energy transport point of view are introduced.

Efficient Synthesis of Single-Chain Polymer Nanoparticles via Amide Formation

Single-chain technology (SCT) allows the transformation of individual polymer chains to folded/collapsed unimolecular soft nanoparticles. In this work we contribute to the enlargement of the SCT toolbox by demonstrating the efficient synthesis of single-chain polymer nanoparticles (SCNPs) via intrachain amide formation. In particular, we exploit cross-linking between active methylene groups and isocyanate moieties as powerful "click" chemistry driving force for SCNP construction. By employing poly(methyl methacrylate)- (PMMA-) based copolymers bearing beta-ketoester units distributed randomly along the copolymer chains and bifunctional isocyanate cross-linkers, SCNPs were successfully synthesized at r.t. under appropriate reaction conditions. Characterization of the resulting SCNPs was carried out by means of a combination of techniques including size exclusion chromatography (SEC), infrared (IR) spectroscopy, proton nuclear magnetic resonance (H-1 NMR) spectroscopy, dynamic light scattering (DLS), and elemental analysis (EA).

The 66 k-Da protein identified as a light meromyosin is involved in the setting of surimi

The 66 kilo-Dalton (k-Da) protein split off from the cross linked myosin heavy chain (CMHC) formed due to the setting of Alaska pollack surimi, frozen-storage of Pacific cod flesh, and vinegar-curing of Pacific mackerel mince was identified as a light meromyosin (LMM). Puncture and stress-relaxation tests showed that the actomyosin subunits (AMS) of Alaska pollack surimi, upon setting at 30°C, transformed into gel, although the elasticity of this gel was very low when compared to the gels from surimi or actomyosin (AM). Electrophoretic studies showed that the band due to LMM in the gel from AMS gradually disappeared with the progress of setting but higher molecular weight polymer did not form. The intensity of the bands due to other myosin sub-fragments decreased a little. The findings suggest that at setting temperature, LMM of MHC molecule leads to an unfolding resulting in an intramolecular aggregation through non-covalent interactions, and thus plays a significant role in the crosslinking of MHC.

Thylakoid terminal oxidases are essential for the cyanobacterium Synechocystis sp. PCC 6803 to survive rapidly changing light intensities.

Cyanobacteria perform photosynthesis and respiration in the thylakoid membrane, suggesting that the two processes are interlinked. However, the role of the respiratory electron transfer chain under natural environmental conditions has not been established. Through targeted gene disruption, mutants of Synechocystis sp. PCC 6803 were generated that lacked combinations of the three terminal oxidases: the thylakoid membrane-localized cytochrome c oxidase (COX) and quinol oxidase (Cyd) and the cytoplasmic membrane-localized alternative respiratory terminal oxidase. All strains demonstrated similar growth under continuous moderate or high light or 12-h moderate-light/dark square-wave cycles. However, under 12-h high-light/dark square-wave cycles, the COX/Cyd mutant displayed impaired growth and was completely photobleached after approximately 2 d. In contrast, use of sinusoidal light/dark cycles to simulate natural diurnal conditions resulted in little photobleaching, although growth was slower. Under high-light/dark square-wave cycles, the COX/Cyd mutant suffered a significant loss of photosynthetic efficiency during dark periods, a greater level of oxidative stress, and reduced glycogen degradation compared with the wild type. The mutant was susceptible to photoinhibition under pulsing but not constant light. These findings confirm a role for thylakoid-localized terminal oxidases in efficient dark respiration, reduction of oxidative stress, and accommodation of sudden light changes, demonstrating the strong selective pressure to maintain linked photosynthetic and respiratory electron chains within the thylakoid membrane. To our knowledge, this study is the first to report a phenotypic difference in growth between terminal oxidase mutants and wild-type cells and highlights the need to examine mutant phenotypes under a range of conditions.

Making the deployment of pico-PV more sustainable along the value chain

Pico-PV is an excellent technology for bringing electric light to rural areas in the developing world and replacing kerosene lanterns and candles. However, as pico-PV is a comparatively new technology, relatively little is known about appropriate methods for sustainable product development and deployment. For this reason current dissemination methods are often ineffective and unsustainable. This research aims to help project developers deploy pico-PV technologies successfully and in a sustainable manner. To achieve this, a conceptual framework of key sustainability criteria along the value chain was developed and tested. The analysis revealed that the most important criteria for the sustainable deployment of pico-PV systems are: (a) easy and safe operation of the product; (b) that a system for product return is established; (c) the retailer understands the target market and (d) the end-user is aware of the product's existence and its benefits. This research reveals that criteria (b) and (c) are of greatest concern. In light of these findings, the authors propose to focus on the following five factors; namely: (a) raising awareness for certification and creating market reassurance; (b) introducing support mechanisms to facilitate local repair; (c) using existing supply channels and establishing in-country (dis)assembly; (d) introducing financial support mechanisms at product supply stages and; (e) undertaking marketing campaigns. © 2013 Elsevier Ltd. All rights reserved.