Short-chain Poly Research Articles

Carbon based porous materials from particle stabilized wet foams

In this work, a method is proposed for the production of carbon porous materials based on the foaming of a carbon colloidal dispersion in the presence of a short chain ionic surfactant (CTAB) and Poly(vinyl alcohol) followed by the in situ polymerization by cross-linking with 2,5-dimethoxy-2,5-dihydrofuran (DHF). The particle stabilized wet foams are used as templates for the gel-casting providing porous materials with carbon particles mainly distributed at the surface of the cells. This sample so obtained is then submitted to a high temperature treatment to remove all organic components from the matrix and get a compact carbon solid foam. The morphology of the samples obtained according to this procedure have been analyzed via Scanning Electron Microscopy (SEM) and different aspects regarding both the procedure and the composition of the initial dispersion have been investigated such as the role of the surfactant, the dependence on the particle concentration and the temperature adopted during the thermal treatment.

Solvent-like ligand-coated ultrasmall cadmium selenide nanocrystals: strong electronic coupling in a self-organized assembly.

Strong inter-nanocrystal electronic coupling is a prerequisite for delocalization of exciton wave functions and high conductivity. We report 170 meV electronic coupling energy of short chain poly(ethylene glycol) thiolate-coated ultrasmall (<2.5 nm in diameter) CdSe semiconductor nanocrystals (SNCs) in solution. Cryo-transmission electron microscopy analysis showed the formation of a pearl-necklace assembly of nanocrystals in solution with regular inter-nanocrystal spacing. The electronic coupling was studied as a function of CdSe nanocrystal size where the smallest nanocrystals exhibited the largest coupling energy. The electronic coupling in spin-cast thin-film (<200 nm in thickness) of poly(ethylene glycol) thiolate-coated CdSe SNCs was studied as a function of annealing temperature, where an unprecedentedly large, ∼400 meV coupling energy was observed for 1.6 nm diameter SNCs, which were coated with a thin layer of poly(ethylene glycol) thiolates. Small-angle X-ray scattering measurements showed that CdSe SNCs maintained an order array inside the films. The strong electronic coupling of SNCs in a self-organized film could facilitate the large-scale production of highly efficient electronic materials for advanced optoelectronic device application.

Modification of Membrane and Organelle Proteins by Short-chain Poly-(R)-3-hydroxybutyrates

cPHB-modified proteins are found in all organisms – prokaryotes and eukaryotes. The presence of cPHB can be determined by analysis of the protein, isolated from cells or tissues, via a chemical assay [2], an antibody assay [3] or mass spectroscopy [4]. If cPHB is found, all further studies of the folding and function(s) of the protein should also be conducted with protein isolated from cells or tissues and not with protein obtained by overexpression, since post-translational modifications by cPHB may be absent or incomplete in the overexpressed protein.

Fast extraction of amphenicols residues from raw milk using novel fabric phase sorptive extraction followed by high-performance liquid chromatography-diode array detection

A simple, sensitive, reliable, and fast analytical method was developed for the simultaneous determination of amphenicols residues in raw milk by combining fabric phase sorptive extraction (FPSE) and high-performance liquid chromatography-diode array detection. FPSE, a new generation green sample preparation technique, efficiently incorporates the advanced and tunable material properties of sol–gel derived microextraction sorbents with the rich surface chemistry of a cellulose fabric substrate, resulting in a flexible, highly sensitive, and fast microextraction device capable of extracting target analytes directly from complicated sample matrices. Due to the strong chemical bonding between the sol–gel sorbent and substrate, the microextraction device demonstrates a very high chemical and solvent stability. Therefore, any organic solvent/solvent mixture can be used as the eluent/back-extraction solvent.Herein, a highly polar polymer coated FPSE media was created using short-chain poly(ethylene glycol) (PEG) and the applicability of this novel microextraction device to extract highly polar amphenicol antibiotics from raw milk was investigated. Due to the intense affinity of amphenicols towards the strongly polar sol–gel PEG-coated FPSE device, absolute recovery of the selected antibiotics residues were found to be 44% for thiamphenicol, 66.4% for florfenicol, and 81.4% for chloramphenicol. The developed method was validated in terms of sensitivity, linearity, accuracy, precision, and selectivity according to European Decision 657/2002/EC. Decision limit (CCα) values were 52.49μgkg−1 for thiamphenicol, 55.23μgkg−1 for florfenicol, and 53.8μgkg−1 for chloramphenicol, while the corresponding results for detection capability (CCβ) were 56.8μgkg−1, 58.99μgkg−1, and 55.9μgkg−1, respectively.

Pegylation effect of chitosan based polyplex on DNA transfection.

The aim of this study was to develop hepatocyte-targeting non-viral polymeric nono-carriers for gene delivery. Chitosan was selected as the main polymer. An asialoglycoprotein receptor recognized sugar, galactose, was introduced. The methoxy poly(ethylene glycol) (mPEG) or short chain poly(ethylene glycol) diacid (PEGd) was further grafted onto galactosylated chitosan. All polyplex possessed positive charge character. The compaction of DNA by grafted chitosan was in order of chitosan-galactose-mPEG>chitosan-galactose-PEGd>chitosan-galactose where the chitosan-galactose-mPEG and pDNA formed the most stable polyplex. The polyplex prominently enhanced DNA cellular transfection as compared to naked DNA in HepG2 cells in order of chitosan-galactose/pDNA (11.6±0.6-33.0±4.4%)>chitosan-galactose-PEGd/pDNA (12.7±2.5-15.5±3.0%)>chitosan-galactose-mPEG/pDNA (9.0±1.1-12.9±2.4%).

Degradable glycine-based photo-polymerizable polyphosphazenes for use as scaffolds for tissue regeneration.

Photo-polymerizable scaffolds are designed and prepared via short chain poly(organo)phosphazene building blocks bearing glycine allylester moieties. The polyphosphazene was combined with a trifunctional thiol and divinylester in various ratios, followed by thiol-ene photo-polymerization to obtain porous matrices. Degradation studies under aqueous conditions showed increasing rates in correlation with the polyphosphazene content. Preliminary cell studies show the non-cytotoxic nature of the polymers and their degradation products, as well as the cell adhesion and proliferation of adipose-derived stem cells.

Synthesis of poly(ethylene oxide) approaching monodispersity.

Polydispersity in polymers hinders fundamental understanding of their structure-property relationships and prevents them from being used in fields like medicine, where polydispersity affects biological activity. The polydispersity of relatively short-chain poly(ethylene oxide) [(CH2CH2O2)n; PEO] affects its biological activity, for example, the toxicity and efficacy of PEOylated drugs. As a result, there have been intensive efforts to reduce the dispersity as much as possible (truly monodispersed materials are not possible). Here we report a synthetic procedure that leads to an unprecedented low level of dispersity. We also show for the first time that it is possible to discriminate between PEOs differing in only 1 ethylene oxide (EO) unit, essential in order to verify the exceptionally low levels of dispersity achieved here. It is anticipated that the synthesis of poly(ethylene oxide) approaching monodispersity will be of value in many fields where the applications are sensitive to the distribution of molar mass.

Effects of Oxidized Lipid Species on Permeability of Giant Unilamellar Vesicle Membranes

Oxidation of unsaturated lipids in cellular membranes has been shown to cause severe membrane damage and potentially cell death. Even in low concentrations, oxidized lipid species are known to cause changes in the membrane structure, such as decreased fluidity. Vesicles containing concentrations of oxidized species as low as 20mol% total lipid concentration can display the spontaneous formation of pores. Below this poration limit, the effects of oxidation on membrane permeability have not been quantified. Here, we use giant unilamellar vesicles (GUVs) as a system to measure passive transport across membranes containing defined concentrations of oxidized lipid species. GUVs consisting of a saturated phospholipid, an unsaturated phospholipid, and cholesterol were used as a model membranes. By replacing defined amounts of the unsaturated lipid with a corresponding oxidized product, the oxidation process could be mimicked, yielding vesicles of varying oxidized lipid concentration. Oxidized lipid concentration was varied from 0mol% to 15mol% of the total lipid concentration. We measured passive transport across the membrane using a microfluidic trap to capture the vesicles and spinning disk confocal microscopy to track the transport of a fluorescent species in the equatorial plane of each GUV analyzed. We used fluorescently labeled short-chain poly(ethylene glycol) species of various molecular weights to track the diffusion of a representative small molecule. Membrane permeability was determined by fitting the resulting concentration profiles to a finite element model of diffusion and permeation around and through the membrane. Experiments showed that an increase in oxidized concentration increases membrane permeability. As passive transport is an important mechanism for drug delivery, understanding the relationship between oxidation and permeation could provide insight into the pharmaceutical characteristics of oxidized cells.

Cross-Linkable Polyimide Membranes for Improved Plasticization Resistance and Permselectivity in Sour Gas Separations

A series of cross-linkable membrane materials based on the 6FDA-DAM:DABA (3:2) polyimide backbone were synthesized for improved sour gas separation performance, in terms of both membrane stability and permselectivity. Short-chain poly(ethylene glycol) (PEG) molecules were used as cross-linking agents in an esterification-based cross-linking reaction. Pure and mixed gas permeation and pure gas sorption experiments were performed on dense films of these materials. Compared to unmodified 6FDA-DAM:DABA (3:2), higher sour gas permselectivity and membrane stability were achieved under aggressive feed conditions. H2S-induced plasticization was not evident until pure H2S feed pressures greater than approximately 6–8 bar. Pure CO2-induced plasticization only occurred at feed pressures greater than about 25 bar. Under mixed gas feed conditions with 20% H2S, 20% CO2, and 60% CH4 at 35 °C, attractive selectivities above 22 and 27 for H2S/CH4 and CO2/CH4, respectively, were observed for a feed pressure of 62 bar with ...

Supramolecular Functionalities Influence the Thermal Properties, Interactions and Conductivity Behavior of Poly(ethylene glycol)/LiAsF6 Blends

In this study, we tethered terminal uracil groups onto short-chain poly(ethylene glycol) (PEG) to form the polymers, uracil (U)-PEG and U-PEG-U. Through AC impedance measurements, we found that the conductivities of these polymers increased upon increasing the content of the lithium salt, LiAsF6, until the Li-to-PEG ratio reached 1:4, with the conductivities of the LiAsF6/U-PEG blends being greater than those of the LiAsF6/U-PEG-U blends. The ionic conductivity of the LiAsF6/U-PEG system reached as high as 7.81 × 10−4 S/cm at 30 °C. Differential scanning calorimetry, wide-angle X-ray scattering, 7Li nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy revealed that the presence of the uracil groups in the solid state electrolytes had a critical role in tuning the glass transition temperatures and facilitating the transfer of Li+ ions.

Glycerine and levulinic acid: Renewable co-substrates for the fermentative synthesis of short-chain poly(hydroxyalkanoate) biopolymers

Glycerine (a biodiesel co-product) and levulinic acid (a pulp and paper co-product) were used as co-substrates for the fermentative synthesis of short-chain polyhydroxyalkanoate (sc-PHA) biopolymers with tunable monomer and molecular weight characteristics. Pseudomonas oleovorans NRRL B-14682 utilized glycerine alone to produce poly(3-hydroxybutyrate) (PHB). When levulinic acid was added to the media at shake-flask scale in concentrations ⩽0.6wt.%, poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB/V) copolymers were produced with 3-HV contents ranging from 37 to 97mol%; a glycerine:levulinic acid ratio of 0.2%:0.8% (w/v) resulted in poly(3-hydroxyvalerate) (PHV). Ten-liter batch fermentations using glycerine:levulinic acid ratios of 1%:0, 0.75%:0.25%, 0.5%:0.5% and 0.25%:0.75% (w/v) resulted in PHB, P(73%-3HB-co-27%-3HV), P(30%-3HB-co-70%-3HV) and PHV with increasing number average molecular weights (×103g/mol) of 328, 511, 728 and 1330, respectively, owing to glycerine-based chain termination. These results provide a novel means by which glycerine and levulinic acid can be used collectively to produce an array of distinct sc-PHA biopolymers.

Highly emissive PEG-encapsulated conjugated polymer nanoparticles

A novel bioimaging probe based on a conjugated polymer, poly(9,9-dihexylfluorene-alt-2,1,3-benzoxadiazole) (PFBD), is demonstrated. Transfer of the hydrophobic polymer into water using a short chain poly(ethylene glycol) (PEG) resulted in conjugated polymer nanoparticles (PEG-PFBD) with a fluorescence quantum yield of 46%. The PEG-PFBD nanoparticles possessed several desirable structural and photophysical properties, such as colloidal stability in a broad range of pH values, sub-20 nm particle size, the presence of surface chemical functionality, as well as desirable excitation and emission spectra, for bioimaging applications. PEG-PFBD nanoparticles were conjugated with cyclic RGDfK targeting peptide for labeling of membrane α(V)β(3) integrin receptors on live HT-29 adenocarcinoma cells. Single nanoparticle microscopy revealed that the PEG-capped PFBD nanoparticles exhibit at least ten times higher emitted photon counts than single quantum dots (QD655) of comparable size. In addition, Fluorescence Lifetime Imaging Microscopy (FLIM) of single PEG-PFBD nanoparticles revealed that the nanoparticles display a clearly resolvable single nanoparticle fluorescence lifetime.

Effect of Stabilizer Functionality on the Kinetics of Emulsion Polymerization in Hairy Particles

Two model polystyrene seed-latexes were studied by γ-irradiation dilatometry, with one latex stabilized by short chain poly(acrylic acid) the other stabilized by short chain poly(methacrylic acid),...

Calcium- and polyphosphate-containing acidic granules of sea urchin eggs are similar to acidocalcisomes, but are not the targets for NAADP

Acidocalcisomes are acidic calcium-storage compartments described from bacteria to humans and characterized by their high content in poly P (polyphosphate), a linear polymer of many tens to hundreds of Pi residues linked by high-energy phosphoanhydride bonds. In the present paper we report that millimolar levels of short-chain poly P (in terms of Pi residues) and inorganic PPi are present in sea urchin extracts as detected using 31P-NMR, enzymatic determinations and agarose gel electrophoresis. Poly P was localized to granules randomly distributed in the sea urchin eggs, as shown by labelling with the poly-P-binding domain of Escherichia coli exopolyphosphatase. These granules were enriched using iodixanol centrifugation and shown to be acidic and to contain poly P, as determined by Acridine Orange and DAPI (4′,6′-diamidino-2-phenylindole) staining respectively. These granules also contained large amounts of calcium, sodium, magnesium, potassium and zinc, as detected by X-ray microanalysis, and bafilomycin A1-sensitive ATPase, pyrophosphatase and exopolyphosphatase activities, as well as Ca2+/H+ and Na+/H+ exchange activities, being therefore similar to acidocalcisomes described in other organisms. Calcium release from these granules induced by nigericin was associated with poly P hydrolysis. Although NAADP (nicotinic acid–adenine dinucleotide phosphate) released calcium from the granule fraction, this activity was not significantly enriched as compared with the NAADP-stimulated calcium release from homogenates and was not accompanied by poly P hydrolysis. GPN (glycyl-L-phenylalanine-naphthylamide) released calcium when added to sea urchin homogenates, but was unable to release calcium from acidocalcisome-enriched fractions, suggesting that these acidic stores are not the targets for NAADP.

Activation of the AtoSC two-component system in the absence of the AtoC N-terminal receiver domain in E. coli

The AtoSC two-component system in E. coli consists of the AtoS sensor kinase and the AtoC response regulator. It regulates positively the transcriptional activation of atoDAEB operon, encoding enzymes involved in short-chain fatty acid catabolism upon acetoacetate-mediated induction. AtoSC acting on atoDAEB operon, regulates the biosynthesis and the intracellular distribution of short-chain poly-(R)-3-hydroxybutyrate (cPHB). A phosphorylation-incompetent AtoC form was constructed lacking its N-terminal receiver domain, trAtoC, to study the effects of AtoC domains on cPHB biosynthesis and atoDAEB operon regulation. Both cPHB biosynthesis and atoDAEB gene expression were regulated positively by trAtoC in the absence of any inducer in E. coli of both atoSC (+) and ΔatoSC genotypes. The presence of acetoacetate or spermidine further promoted these trAtoC actions. Competitive regulatory functions between the full length AtoC and trAtoC were observed referring to atoDAEB and cPHB targets as well as growth of trAtoC-overproducing atoSC (+) cells on butyrate as the sole carbon source. trAtoC in contrast to the wild-type AtoC presented different modes of cPHB and atoDAEB regulation in the presence of compounds involved in fatty acid metabolism including CoA-SH, acetyl-CoA, sodium acetate or 3-hydroxybutyryl-CoA. These data provide evidence for a role of the AtoC N-terminal receiver domain in regulating the biological activities of AtoSC as well as additional mechanisms of interactions between the AtoSC constituents including their established inducers or new effectors towards the accomplishment of the AtoSC TCS signal transduction.

PEI–PEG–Chitosan‐Copolymer‐Coated Iron Oxide Nanoparticles for Safe Gene Delivery: Synthesis, Complexation, and Transfection

Gene therapy offers the potential of mediating disease through modification of specific cellular functions of target cells. However, effective transport of nucleic acids to target cells with minimal side effects remains a challenge despite the use of unique viral and non-viral delivery approaches. Here we present a non-viral nanoparticle gene carrier that demonstrates effective gene delivery and transfection both in vitro and in vivo. The nanoparticle system (NP-CP-PEI) is made of a superparamagnetic iron oxide nanoparticle (NP), which enables magnetic resonance imaging, coated with a novel copolymer (CP-PEI) comprised of short chain polyethylenimine (PEI) and poly(ethylene glycol) (PEG) grafted to the natural polysaccharide, chitosan (CP), which allows efficient loading and protection of the nucleic acids. The function of each component material in this nanoparticle system is illustrated by comparative studies of three nanoparticle systems of different surface chemistries, through material property characterization, DNA loading and transfection analyses, and toxicity assessment. Significantly, NP-CP-PEI demonstrates an innocuous toxic profile and a high level of expression of the delivered plasmid DNA in a C6 xenograft mouse model, making it a potential candidate for safe in vivo delivery of DNA for gene therapy.

Hypothesis: Poly-(R)-3-hydroxybutyrate is a major factor in intraocular pressure

Short chain poly-(R)-3-hydroxybutyrate (cPHB) is a ubiquitous molecule that readily adheres to others, that is covalently added to proteins and that forms, with polyphosphate, ion channels. High levels of cPHB have been implicated in atherosclerosis and in diabetes. Here, we propose a hypothesis in which cPHB adheres to filaments in the extracellular matrix and this raises intraocular pressure. In a corollary, we propose that a positive feedback relationship between cPHB adherence to filaments, raised IOP and filament stretching constitutes a switch.

Short-chain polyphosphate in arbuscular mycorrhizal roots colonized by Glomus spp.: A possible phosphate pool for host plants

We investigated the relationship between plant growth and polyphosphate (poly P) content in Allium fistulosum roots colonized by Glomus sp. R10 or Glomus etunicatum with different levels of phosphate addition. Poly P was quantified by two enzymatic assays: long-chain poly P (>∼20 inorganic phosphate [P i] residues) with polyphosphate kinase, and total poly P with polyphosphate exopolyphosphatase. The difference between these values was designated as short-chain poly P (<∼20 P i residues). The content of long-chain poly P in mycorrhizal roots and plant growth was poorly correlated or not, depending in fungal species. However, the content of short-chain poly P and plant growth was highly correlated in both species. This difference suggests that short-chain poly P in mycorrhizal roots colonized by Glomus spp. functions as a pool of P i for the plant.

Effects of Proteins from Culture Medium on Surface Property of Silanes- Functionalized Magnetic Nanoparticles

Monodisperse magnetic nanoparticles (MNPs) were synthesized by thermal decomposition of iron-oleate and functionalized with silanes bearing various functional groups such as amino group (NH2), short-chain poly(ethylene glycol) (PEG), and carboxylic group (COOH). Then, silanes-functionalized magnetic nanoparticles (silanes-MNPs) were incubated in cell culture medium plus fetal calf serum to investigate the effects of proteins from culture medium on surface property of MNPs. Zeta potential measurements showed that although surface charges of silanes-MNPs were different, they exhibited negative charges at neutral pH and approximate isoelectric points after they were incubated in cell culture medium. The reason was that silanes-MNPs could easily adsorb proteins from culture medium via non-covalent binding, resulting in the formation of protein-silanes-MNPs conjugates. Moreover, silanes-MNPs with various functional groups had different adsorption capacity to proteins, as confirmed by Coomassie blue fast staining method. The in vitro cell experiments showed that protein-silanes-MNPs had higher cellular uptake by cancer cells than silanes-MNPs.

Stabilization of chloroperoxidase by polyethylene glycols in aqueous media: kinetic studies and synthetic applications.

Chloroperoxidase (CPO) is one of the most versatile of the heme peroxidase enzymes for synthetic applications. Despite the potential use of CPO, commercial processes have not been developed because of the low water solubility of many organic substrates of synthetic interest and the limited stability due to inactivation by H(2)O(2). CPO catalytic properties have been studied in aqueous solutions in the presence of short-chain poly(ethylene glycol)s (PEGs), and the sulfoxidation of thioanisole, as model substrate, has been investigated. The addition of PEGs allows a better substrate solubilization in the reaction mixture and the enzyme to retain more of its initial activity, with respect to pure buffer. Kinetic studies were performed to optimize the experimental conditions, and complete enantioselective conversion to the (R)-sulfoxide (ee = 99%) was observed in the presence of PEG 200 and tri(ethylene glycol). The relevant stabilization of chloroperoxidase due to the presence of PEGs allows the enzyme to convert the substrate with significant product yields even after 10 days, with a consequent increase in enzyme productivity. This is a promising result in view of industrial application of the enzyme.