Conformation of poly(L-lysine)-graft-poly(ethylene glycol) molecular brushes in aqueous solution studied by small-angle neutron scattering

Small-angle neutron scattering (SANS) has been employed for the analysis of conformations of poly(L-lysine)-graft-poly(ethylene glycol) (PLL-g -PEG) molecular bottle brushes in aqueous solutions. The degree of polymerisation of the PEG chains was systematically varied in order to unravel dependence of the conformational properties of the bottle brushes on the molecular weight of the grafted chains. The grafting density was kept constant and high enough to ensure strong overlap of the PEG chains. The scattering spectra were fitted on the basis of the model of an effective worm-like chain with the account of average radial distribution and local fluctuations of the PEG density in the bottle brush. The results of the fits indicate that molecular brushes retain weakly bent configuration on the length scale of the order of (or larger than) the brush thickness. This finding is in agreement with earlier simulation and recent theoretical results.     

Methoxycarbonyl-terminated hyperbranched poly(amine-ester) as templates for synthesis of silver nanoparticles

Highly stable and spherical silver nanoparticles, stabilized by methoxycarbonyl-terminated hyperbranched poly(amine-ester) (HPAE-COOCH₃), were synthesized in water with reducing AgNO₃/HPAE-COOCH₃ using two methods, viz. NaBH₄ and ultraviolet irradiation. HPAE-COOCH₃ was found to play a key role in the formation of nanoparticles. UV–visible absorption, Transmission electron microscopic (TEM), and Fourier transform infrared spectroscopy (FT-IR) had been used to study the structure and characterization of the silver nanoparticles. The absorption peaks of the silver nanoparticles appear at ~420 nm in UV–visible absorption spectra; average particle size reduced by NaBH₄ is ~30 nm, which is ~10 and ~15 nm, respectively, when ultraviolet irradiation time is 12 and 24 h. FT-IR spectra confirm that there is strong interaction between silver nanoparticles and HPAE-COOCH₃. And silver nanoparticles/HPAE-COOCH₃ aqueous solution can keep stable for more than 3 months.     

One-step synthesis of silver nanoparticles in an aqueous solution and their antibacterial activities

A one-step simple synthesis of silver colloid nanoparticles with controllable sizes is presented in this research. In the synthesis, an amino-terminated hyperbranched polymer (HBP-NH₂) was applied as a stabilizer and a reductant. The syntheses, performed at various initial AgNO₃ concentrations (0.28–0.56 g/l) in a 2 g/l HBP-NH₂ aqueous solution, produced silver colloid nanoparticles having average sizes from 3 to 30 nm with narrow size distributions. The formation of silver colloid nanoparticles was characterized by Fourier Transform Infrared Spectrophotometry (FTIR), Dynamic Light Scattering (DLS), Transmission Electron Microscopy (TEM), UV/Visible Absorption Spectrophotometry, and X-ray Diffraction (XRD) measurements. The results indicated that both particle size and the UV absorption are strongly dependent on the initial AgNO₃ concentrations. The silver colloid nanoparticles, prepared with a 0.35 g/l AgNO₃ aqueous solution in the presences of 2 g/l HBP-NH₂, showed good antibacterial activities against Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus). A very low concentration of nano-silver (as low as 3.0 ug/ml Ag) also gave excellent antibacterial performance.     

Ferrocenyl branched poly (ethylene imine) micelles as reductive templates for the preparation of silver nanoparticles

Journal of Nanoparticle Research - Polymeric micelles with a branched poly (ethylene imine) shell and a reductive ferrocene core were prepared via self-assembly of ferrocene modified branched poly...     

Fabrication and characterization of silver/titanium dioxide composite nanoparticles in ethylene glycol with alkaline solution through sonochemical process

This paper aims to study fabrication and characterization of silver/titanium oxide composite nanoparticle through sonochemical process in the presence of ethylene glycol with alkaline solution. By using ultrasonic irradiation of a mixture of silver nitrate, the dispersed TiO₂ nanoparticle in ethylene glycol associated with aqueous solution of sodium oxide yields Ag/TiO₂ composite nanoparticle with shell/core-type geometry. The powder X-ray diffraction (XRD) of the Ag/TiO₂ composites showed additional diffraction peaks corresponding to the face-centered cubic (fcc) structure of silver crystallization phase, apart from the signals from the cores of TiO₂. Transmission electron microscopy (TEM) images of Ag/TiO₂ composites, which average particle size is roughly 80 nm, reveal that the titanium oxide coated by Ag nanoparticle with a grain size of about 2–5 nm. Additionally, the formation of silver nanoparticles on TiO₂ was monitored by ultraviolet visible light spectrophotometer (UV–Vis). As measured the optical absorption spectra of as-synthesized Ag nanoparticle varying with time, the mechanism of surface formatting silver shell on the cores of TiO₂ could be explored by autocatalytic reaction; the conversion of Ag particle from silver ion is 98% for the reaction time of 1000 s; and the activity energy of synthesizing Ag nanoparticles on TiO₂ is 40 kJ/mol at temperature ranging from 5 to 25 °C. Hopefully, this preliminary investigation could be used for mass production of composite nanoparticles assisted by ultrasonic chemistry in the future.     

Magnetic fluid poly(ethylene glycol) with moderate anticancer activity

Poly(ethylene glycol) (PEG)-containing magnetic fluids - magnetite (Fe₃O₄) stabilized by sodium oleate - were prepared. Magnetic measurements confirmed superparamagnetic behaviour at room temperature. The structure of that kind of magnetic fluid was characterized using different techniques, including electron microscopy, photon cross correlation spectroscopy and small-angle neutron scattering, while the adsorption of PEG on magnetic particles was analyzed by differential scanning calorimetry and Fourier transform infrared spectroscopy. From the in vitro toxicity tests it was found that a magnetic fluid containing PEG (MFPEG) partially inhibited the growth of cancerous B16 cells at the highest tested dose (2.1 mg/ml of Fe₃O₄ in MFPEG).     

Polymer electrolytes based on poly(vinylidene fluoride-co-hexafluoropropylene) with crosslinked poly(ethylene glycol) for lithium batteries

The combination of a poly(ethylene glycol) (PEG) network and poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) copolymer chains is one of the most efficient means for modifying PVDF-HFP gel electrolytes. Previous preparations tend to introduce contamination into the polymer gel electrolyte because of irradiation, high temperature or the initiator needed for crosslinking which might result in the electrochemical degradation. In order to overcome the above disadvantages, a new method has been developed to successfully prepare the semi-interpenetrating polymer networks of PVDF-HFP based electrolytes with crosslinked diepoxy polyethylene glycol (DIEPEG). In this process, impurities are avoided because of a moderate reaction temperature at 50 °C and poly(ethylenimine) (PEI) as the crosslinking agent. Microporous films with various compositions are prepared and characterized. Thermal, mechanical, swelling and electrochemical properties, as well as microstructures of the prepared polymer electrolytes have been investigated using thermogravimetric analysis, electrochemical impedance spectroscopy, linear sweep voltammetry, and scanning electron microscopy. The results show that the blend polymer electrolyte with PVDF-HFP/PEI + DIEPEG (60:40 w/w) has an ionic conductivity of 2.3 mS cm^? 1 at room temperature in the presence of 1 M LiPF₆ in EC and DMC (1:1 w/w). All the blend electrolytes are electrochemically stable up to 4.8 V versus Li/Li⁺. The results reveal that this new method may be very promising for improving PVDF-HFP based electrolytes.     

Covalent attachment of poly(ethylene glycol) on multi-walled carbon nanotubes

A new 'graft-onto' method to attach poly(ethylene glycol) (PEG) onto multi-walled carbon nanotubes (MWNTs) has been developed. The method is based on the coupling reaction of radicals formed at the chain end of PEG onto the surface of MWNTs. The polymeric radicals are generated by atom (halogen) transfer reaction between chloroacetyl-terminated PEG and transition metal catalysts. The method allows direct covalent attachment of PEG to pristine MWNTs without pretreatment that could alter their original structure. The resulting PEG-grafted MWNTs showed improved dispersion stability in isopropanol and methanol.     

Single-molecule elasticity measurements of the onset of excluded volume in poly(ethylene glycol)

A polymer must reach a certain size to exhibit significant excluded-volume interactions and adopt a swollen random-walk configuration. We show that single-molecule measurements can sense the onset of swelling by modulating the effective chain size with force: as the force is reduced from a large value, the polymer is first highly aligned, then a Gaussian coil, then finally a swollen chain, with each regime exhibiting a distinct elasticity. We use this approach to quantify the structural parameters of poly(ethylene glycol) and show that they vary in the expected manner with changes in solvent.     

Ultrasonic degradation of poly(vinyl alcohol) in aqueous solution

Solution of poly(vinyl alcohol) in water with different concentrations (by weight 1%, 1.5%, 2%) and different volumes (50, 75 and 100 ml) were subjected to ultrasonic degradation. A method of viscometry was used to study the degradation behavior and kinetic model was developed to estimate the degradation rate constant. The degradation rate constant was correlated with the power input due to ultrasonic irradiation and reaction volume. It was found that rate constant decreases as the reaction volume and concentration increases. The proportionality index of the relation between rate constant, power input and reaction volume was found to be nearly equal for all concentrations studied. The proportionality constant was found to be approximately equal for 1% and 1.5% solution and for 2% solution it was approximately half the value for that of 1% and 1.5% solutions. The decrease in rate constant and proportionality constant is attributed to the fact that at higher concentration and at higher volume, the intensity of cavitation phenomenon is depressed and therefore the extent of polymer chain breaking decreases. The difference in the values of limiting viscosities (constant solution viscosity which does not decrease by further ultrasonic irradiation) for 50, 75 and 100 ml solutions for each of 1% and 1.5% concentration was negligible. But 2% solution at 100 ml volume showed slightly higher value of limiting viscosity than that for 50 and 75 ml.     

Continuous synthesis of colloidal silver nanoparticles by electrochemical discharge in aqueous solutions

This article presents an electrochemical discharge (ECD) method that consists of a combination of chemical methods and electric arc discharges. In the method, 140 V is applied to an Ag electrode from a DC power supply. The arc-discharge between the electrodes produces metallic silver nanoparticles and silver ions in the aqueous solution. Compared with the original arc discharge, this ECD method creates smaller nanoparticles, prevents clumping of the nanoparticles, and shortens the production time. The citrate ions also reduce the silver ions to silver nanoparticles. In addition, the citrate ions cap the surface of the produced silver nanoparticles and the zeta potential increases. In this article, the weight loss of the electrodes and the reduction of silver ions to silver nanoparticles as a function of citrate concentration and electric conductivity of the medium are discussed. Furthermore, the properties of the colloidal silver prepared with ECD are analyzed by UV–Vis spectroscopy, dynamic light scattering, electrophoresis light scattering, and scanning electron microscopy. Finally, a continuous production apparatus is presented for the continuous production of colloidal silver.     

Ultrasound enhances lipase-catalyzed synthesis of poly (ethylene glutarate)

The present work explores the best conditions for the enzymatic synthesis of poly (ethylene glutarate) for the first time. The start-up materials are the liquids; diethyl glutarate and ethylene glycol diacetate, without the need of addition of extra solvent. The reactions are catalyzed by lipase B from Candida antarctica immobilized on glycidyl methacrylate-ter-divinylbenzene-ter-ethylene glycol dimethacrylate at 40 °C during 18 h in water bath with mechanical stirring or 1 h in ultrasonic bath followed by 6 h in vacuum in both the cases for evaporation of ethyl acetate. The application of ultrasound significantly intensified the polyesterification reaction with reduction of the processing time from 24 h to 7 h. The same degree of polymerization was obtained for the same enzyme loading in less time of reaction when using the ultrasound treatment. The degree of polymerization for long-term polyesterification was improved approximately 8-fold due to the presence of sonication during the reaction. The highest degree of polymerization achieved was 31, with a monomer conversion of 96.77%. The ultrasound treatment demonstrated to be an effective green approach to intensify the polyesterification reaction with enhanced initial kinetics and high degree of polymerization.     

Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via photo-initiated graft polymerization of poly(ethylene glycol)

Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) copolymer biomedical elastomer was covalently grafted with poly(ethylene glycol) methyl ether methacrylate (PEGMA) via a photo-initiated graft polymerization technique. The surface graft polymerization of SEBS with PEGMA was verified by ATR-FTIR and XPS. Effect of graft polymerization parameters, i.e., monomer concentration, UV irradiation time and initiator concentration on the grafting density was investigated. Comparing with the virgin SEBS film, the PEGMA-modified SEBS film presented an enhanced wettability and a larger surface energy. Besides, the surface grafting of PEGMA imparted excellent anti-platelet adhesion and anti-protein adsorption to the SEBS surface.     

Effects of poly(ethylene glycol) on electrical conductivity of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) film

A series of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) composite thin films with prescribed concentrations of poly(ethylene glycol) were prepared. The PEDOT–PSS pristine film and PEDOT–PSS/PEG films were studied using four-probe method, photoelectron spectroscopy and atomic force microscopy. The electrical conductivity of PEDOT–PSS/PEG hybrid films was found to be enhanced compared to the PEDOT–PSS pristine film, depending on the PEG concentration and molecular weight. XPS analysis and AFM results showed that PEG induces the phase separation between the PEDOT–PSS conducting particles and the excessive PSSNa shell. Simultaneously PEG may form hydrogen bond with sulfonic groups of PSSH, and hence weaken the electrostatic interactions between PEDOT cationic chains and PSS anionic chains. These resulted in the creation of a better conduction pathway among PEDOT–PSS particles, attributed to the improvement of conductivity.     

Self-assembly of silanated poly(ethylene glycol) on silicon and glass surfaces for improved haemocompatibility

Surface immobilization of poly(ethylene glycol) (PEG) is an effective method to produce a material surface with protein repulsive property. This property could be made permanent by using covalent grafting of the PEG molecules onto material surfaces. In this study, self-assembled monolayers (SAMs) of PEG on silicon-containing materials (silicon chip and glassplate) were obtained through a one-step coating procedure of one kind of silanated PEG molecules made through the reaction between monomethoxy PEG and 3-isocyanatopropyltriethoxysilane. Atomic force microscopy (AFM) and water static contact angle measurement were employed to investigate the surface topography and wettability of the PEGylated material surfaces. The changes in the topography and the water contact angle of the surfaces with time of incubation in PBS solution were also measured. The results revealed that stable and uniform self-assembled monolayers of PEG could be formed on silicon or glass surfaces by simply soaking the substrates in the solution of silanated PEGs. The covalent coupling of PEGs to the substrates was also confirmed. In order to evaluate the stability of the SAMs, blood compatibility of the modified glassplate surface was evaluated by measuring full blood activated partial thromboplastin time (APTT), prothrombin time (PT), and thrombin time (TT), as well as by scanning electron microscopy (SEM) analysis of the appearance of adherence and denaturation of blood platelets onto the glassplate. The silanated PEGs were shown to have good effect on the protein-repulsion as well as haemocompatibility of the substrates.     

Process variables in biomimetic synthesis of silver nanoparticles by aqueous extract of Azadirachta indica (Neem) leaves

Owing to widespread applications, synthesis and characterization of silver nanoparticles is recently attracting considerable attention. Increasing environmental concerns over chemical synthesis routes have resulted in attempts to develop biomimetic approaches. One of them is synthesis using plant parts, which eliminates the elaborate process of maintaining the microbial culture and often found to be kinetically favourable than other bioprocesses. The present study deals with investigating the effect of process variables like reductant concentrations, reaction pH, mixing ratio of the reactants and interaction time on the morphology and size of silver nanoparticles synthesized using aqueous extract of Azadirachta indica (Neem) leaves. The formation of crystalline silver nanoparticles was confirmed using X-ray diffraction analysis. By means of UV spectroscopy, Scanning and Transmission Electron Microscopy techniques, it was observed that the morphology and size of the nanoparticles were strongly dependent on the process parameters. Within 4 h interaction period, nanoparticles below 20-nm-size with nearly spherical shape were produced. On increasing interaction time (ageing) to 66 days, both aggregation and shape anisotropy (ellipsoidal, polyhedral and capsular) of the particles increased. In alkaline pH range, the stability of cluster distribution increased with a declined tendency for aggregation of the particles. It can be inferred from the study that fine tuning the bioprocess parameters will enhance possibilities of desired nano-product tailor made for particular applications.     

Electrochemical method for the synthesis of silver nanoparticles

The article deals with a novel electrochemical method of preparing long-lived silver nanoparticles suspended in aqueous solution as well as silver powders. The method does not involve the use of any chemical stabilising agents. The morphology of the silver nanoparticles obtained was studied using transmission electron microscopy, scanning electron microscopy, atomic force microscopy and dynamic light scattering measurements. Silver nanoparticles suspended in water solution that were produced by the present technique are nearly spherical and their size distribution lies in the range of 2 to 20 nm, the average size being about 7 nm. Silver nanoparticles synthesised by the proposed method were sufficiently stable for more than 7 years even under ambient conditions. Silver crystal growth on the surface of the cathode in the electrochemical process used was shown to result in micron-sized structures consisting of agglomerated silver nanoparticles with the sizes below 40 nm.     

Dielectric spectroscopy and viscosity studies of aqueous poly(ethylene oxide) and poly(vinyl pyrrolidone) blend

The complex dielectric function, electric modulus, impedance and ac electrical conductivity behaviour of aqueous solutions of 5 wt% poly(ethylene oxide) (PEO) and poly(vinyl pyrrolidone) (PVP) and their different volume percent blends were investigated in the frequency range 20 Hz to 1 MHz at 15, 30 and 45 °C. It is found that the real part of dielectric function of these blends at 1 MHz decreases with the increase of PEO concentration and their dc electrical conductivity has strong correlation with the electrode polarization relaxation time. The static permittivity, ionic conductivity, electrode polarization relaxation time and apparent viscosity have linear behaviour with temperature variation at fixed volume concentration of the aqueous polymers blend. The viscosity of these aqueous polymeric blends increases with the increase of PEO concentration. The behaviour of hydrogen bond interactions between the polar segments of PEO and PVP were explored from the comparative change in dielectric parameters and viscosity of the two phase aqueous polymeric systems.     

Constructing polyamidoamine dendrons from poly(poly(ethylene glycol) monomethacrylate) brushes grafted from planar silicon hydride surfaces for biomedical applications

A facile approach was established to construct polyamidoamine (PAMAM) dendrons from polymer brushes of poly(poly(ethylene glycol) monomethacrylate) (Si-g-P(PEGMA-OH)) grafted from a planar silicon hydride surface. First the Si-g-P(PEGMA-OH) brushes were grown via surface-initiated atom transfer radical polymerization with robust Si–C links on silicon surfaces. The side-chain hydroxyl groups of Si-g-P(PEGMA-OH) were chlorinated with thionyl chloride and further chlorines were substituted with amino groups of ethylenediamine, giving terminal primary amines. Borrowing the solution synthesis approach, we constructed second and third generations of PAMAM dendrons on-chip by surface-initiated alternative growth of two monomers, methyl acrylate and ethylenediamine. Two applications of silicon-based PAMAM dendrons were shown: the dense amino groups were activated via a cross-linker, N-succinimidyl-6-maleimidylhexanoate, to capture a free-thiol-carrying peptide of oxytocin and the third generation of PAMAM dendrons was used as a platform to on-chip synthesize a three amino acid peptide of Arg-Gly-Asp (RGD). The above conclusions were mainly derived from a home-built multiple transmission-reflection infrared spectroscopy, and complemented by X-ray photoelectron spectroscopy, UV–Vis spectroscopy and matrix-assisted laser desorption/ionization-time of flight-mass spectrometry.