Size- and orientation-selective Si nanowire growth : thermokinetic effects of naeoscale plasma chemistry

A multiscale, multiphase thermokinetic model is used to show the effective control of the growth orientation of thin Si NWs for nanoelectronic devices enabled by nanoscale plasma chemistry. It is shown that very thin Si NWs with [110] growth direction can nucleate at much lower process temperatures and pressures compared to thermal chemical vapor deposition where [111]-directed Si NWs are predominantly grown. These findings explain a host of experimental results and offer the possibility of energy- and matter-efficient, size- and orientation-controlled growth of [110] Si NWs for next-generation nanodevices.

Nanoscale plasma chemistry enables fast, size-selective nanotube nucleation

The possibility of fast, narrow-size/chirality nucleation of thin single-walled carbon nanotubes (SWCNTs) at low, device-tolerant process temperatures in a plasma-enhanced chemical vapor deposition (CVD) is demonstrated using multiphase, multiscale numerical experiments. These effects are due to the unique nanoscale reactive plasma chemistry (NRPC) on the surfaces and within Au catalyst nanoparticles. The computed three-dimensional process parameter maps link the nanotube incubation times and the relative differences between the incubation times of SWCNTs of different sizes/chiralities to the main plasma- and precursor gas-specific parameters and explain recent experimental observations. It is shown that the unique NRPC leads not only to much faster nucleation of thin nanotubes at much lower process temperatures, but also to better selectivity between the incubation times of SWCNTs with different sizes and chiralities, compared to thermal CVD. These results are used to propose a time-programmed kinetic approach based on fast-responding plasmas which control the size-selective, narrow-chirality nucleation and growth of thin SWCNTs. This approach is generic and can be used for other nanostructure and materials systems.

Colloidal semiconductor nanocrystals : controlled synthesis and surface chemistry in organic media

Colloidal semiconductor nanocrystals (CS-NCs) possess compelling benefits of low-cost, large-scale solution processing, and tunable optoelectronic properties through controlled synthesis and surface chemistry engineering. These merits make them promising candidates for a variety of applications. This review focuses on the general strategies and recent developments of the controlled synthesis of CS-NCs in terms of crystalline structure, particle size, dominant exposed facet, and their surface passivation. Highlighted are the organic-media based synthesis of metal chalcogenide (including cadmium, lead, and copper chalcogenide) and metal oxide (including titanium oxide and zinc oxide) nanocrystals. Current challenges and thus future opportunities are also pointed out in this review.

Genetic susceptibility to environmental toxicants : the interface between human and experimental studies in the development of new toxicological concepts

The growing knowledge of the genetic polymorphisms of enzymes metabolising xenobiotics in humans and their connections with individual susceptibility towards toxicants has created new and important interfaces between human epidemiology and experimental toxicology. The results of molecular epidemiological studies may provide new hypotheses and concepts, which call for experimental verification, and experimental concepts may obtain further proof by molecular epidemiological studies. If applied diligently, these possibilities may be combined to lead to new strategies of human-oriented toxicological research. This overview will present some outstanding examples for such strategies taken from the practically very important field of occupational toxicology. The main focus is placed on the effects of enzyme polymorphisms of the xenobiotic metabolism in association with the induction of bladder cancer and renal cell cancer after exposure to occupational chemicals. Also, smoking and induction of head and neck squamous cell cancer are considered.

Tunable electric field enhancement and redox chemistry on TiO2 island films via covalent attachment to Ag or Au nanostructures

Abstract Ag-TiO2 and Au-TiO2 hybrid electrodes were designed by covalent attachment of TiO2 nanoparticles to Ag or Au electrodes via an organic linker. The optical and electronic properties of these systems were investigated using the cytochrome b5 (Cyt b5) domain of sulfite oxidase, exclusively attached to the TiO2 surface, as a Raman marker and model redox enzyme. Very strong SERR signals of Cyt b 5 were obtained for Ag-supported systems due to plasmonic field enhancement of Ag. Time-resolved surface-enhanced resonance Raman spectroscopic measurements yielded a remarkably fast electron transfer kinetic (k = 60 s -1) of Cyt b5 to Ag. A much lower Raman intensity was observed for Au-supported systems with undefined and slow redox behavior. We explain this phenomenon on the basis of the different potential of zero charge of the two metals that largely influence the electronic properties of the TiO2 island film. © 2013 American Chemical Society.

Rapid production of a plasmid DNA encoding a malaria vaccine candidate via amino-functionalized poly(GMA-co-EDMA) monolith

Malaria is a global health problem; an effective vaccine is urgently needed. Due to the relative poverty and lack of infrastructure in malaria endemic areas, DNA-based vaccines that are stable at ambient temperatures and easy to formulate have great potential. While attention has been focused mainly on antigen selection, vector design and efficacy assessment, the development of a rapid and commercially viable process to manufacture DNA is generally overlooked. We report here a continuous purification technique employing an optimized stationary adsorbent to allow high-vaccine recovery, low-processing time, and, hence, high-productivity. A 40.0 mL monolithic stationary phase was synthesized and functionalized with amino groups from 2-Chloro-N,N- diethylethylamine hydrochloride for anion-exchange isolation of a plasmid DNA (pDNA) that encodes a malaria vaccine candidate, VR1020-PyMSP4/5. Physical characterization of the monolithic polymer showed a macroporous material with a modal pore diameter of 750 nm. The final vaccine product isolated after 3 min elution was homogeneous supercoiled plasmid with gDNA, RNA and protein levels in keeping with clinical regulatory standards. Toxicological studies of the pVR1020-PyMSP4/5 showed a minimum endotoxin level of 0.28 EU/m.g pDNA. This cost-effective technique is cGMP compatible and highly scalable for the production of DNA-based vaccines in commercial quantities, when such vaccines prove to be effective against malaria. © 2008 American Institute of Chemical Engineers.

Enhancing methacrylate-monolith-based downstream processes to champion plasmid DNA production

Increasing numbers of preclinical and clinical studies are utilizing pDNA (plasmid DNA) as the vector. In addition, there has been a growing trend towards larger and larger doses of pDNA utilized in human trials. The growing demand on pDNA manufacture leads to pressure to make more in less time. A key intervention has been the use of monoliths as stationary phases in liquid chromatography. Monolithic stationary phases offer fast separation to pDNA owing to their large pore size, making pDNA in the size range from 100 nm to over 300 nm easily accessible. However, the convective transport mechanism of monoliths does not guarantee plasmid purity. The recovery of pure pDNA hinges on a proper balance in the properties of the adsorbent phase, the mobile phase and the feedstock. The effects of pH and ionic strength of binding buffer, temperature of feedstock, active group density and the pore size of the stationary phase were considered as avenues to improve the recovery and purity of pDNA using a methacrylate-based monolithic adsorbent and Escherichia coli DH5α-pUC19 clarified lysate as feedstock. pDNA recovery was found to be critically dependent on the pH and ionic strength of the mobile phase. Up to a maximum of approx. 92% recovery was obtained under optimum conditions of pH and ionic strength. Increasing the feedstock temperature to 80°C increased the purity of pDNA owing to the extra thermal stability associated with pDNA over contaminants such as proteins. Results from toxicological studies of the plasmid samples using endotoxin standard (E. coli 0.55:B5 lipopolysaccharide) show that endotoxin level decreases with increasing salt concentration. It was obvious that large quantities of pure pDNA can be obtained with minimal extra effort simply by optimizing process parameters and conditions for pDNA purification.

Investigation into chemistry of new particle formation and growth in subtropical urban environment

The role of different chemical compounds, particularly organics, involved in the new particle formation (NPF) and its consequent growth are not fully understood. Therefore, this study was conducted to investigate the chemistry of aerosol particles during NPF events in an urban subtropical environment. Aerosol chemical composition was measured along with particle number size distribution (PNSD) and several other air quality parameters at five sites across an urban subtropical environment. An Aerodyne compact Time-of-Flight Aerosol Mass Spectrometer (c-TOF-AMS) and a TSI Scanning Mobility Particle Sizer (SMPS) measured aerosol chemical composition and PNSD, respectively. Five NPF events, with growth rates in the range 3.3-4.6 nm, were detected at two sites. The NPF events happened on relatively warmer days with lower humidity and higher solar radiation. Temporal percent fractions of nitrate, sulphate, ammonium and organics were modelled using the Generalised Additive Model (GAM), with a basis of penalised spline. Percent fractions of organics increased after the NPF events, while the mass fraction of ammonium and sulphate decreased. This uncovered the important role of organics in the growth of newly formed particles. Three organic markers, factors f43, f44 and f57, were calculated and the f44 vs f43 trends were compared between nucleation and non-nucleation days. f44 vs f43 followed a different pattern on nucleation days compared to non-nucleation days, whereby f43 decreased for vehicle emission generated particles, while both f44 and f43 decreased for NPF generated particles. It was found for the first time that vehicle generated and newly formed particles cluster in different locations on f44 vs f43 plot and this finding can be used as a tool for source apportionment of measured particles.

To sonicate or not to sonicate PM filters: Reactive Oxygen Species generation upon ultrasonic irradiation

In aerosol research, a common approach for the collection of particulate matter (PM) is the use of filters in order to obtain sufficient material to undertake analysis. For subsequent chemical and toxicological analyses, in most of cases the PM needs to be extracted from the filters. Sonication is commonly used to most efficiently extract the PM from the filters. Extraction protocols generally involve 10 - 60 min of sonication. The energy of ultrasonic waves causes the formation and collapse of cavitation bubbles in the solution. Inside the collapsing cavities the localised temperatures and pressures can reach extraordinary values. Although fleeting, such conditions can lead to pyrolysis of the molecules present inside the cavitation bubbles (gases dissolved in the liquid and solvent vapours), which results in the production of free radicals and the generation of new compounds formed by reactions with these free radicals. For example, simple sonication of pure water will result in the formation of detectable levels of hydroxyl radicals. As hydroxyl radicals are recognised as playing key roles as oxidants in the atmosphere the extraction of PM from filters using sonication is therefore problematic. Sonication can result in significant chemical and physical changes to PM through thermal degradation and other reactions. In this article, an overview of sonication technique as used in aerosol research is provided, the capacity for radical generation under these conditions is described and an analysis is given of the impact of sonication-derived free radicals on three molecular probes commonly used by researchers in this field to detect Reactive Oxygen Species in PM.

The effect of graphene oxide and its oxidized debris on the cure chemistry and interphase structure of epoxy nanocomposites

The influence of graphene oxide (GO) and its surface oxidized debris (OD) on the cure chemistry of an amine cured epoxy resin has been investigated by Fourier Transform Infrared Emission Spectroscopy (FT-IES) and Differential Scanning Calorimetry (DSC). Spectral analysis of IR radiation emitted at the cure temperature from thin films of diglycidyl ether of bisphenol A epoxy resin (DGEBA) and 4,4'-diaminodiphenylmethane (DDM) curing agent with and without GO allowed the cure kinetics of the interphase between the bulk resin and GO to be monitored in real time, by measuring both the consumption of primary (1°) amine and epoxy groups, formation of ether groups as well as computing the profiles for formation of secondary (2°) and tertiary (3°) amines. OD was isolated from as-produced GO (aGO) by a simple autoclave method to give OD-free autoclaved GO (acGO). It has been found that the presence of OD on the GO prevents active sites on GO surfaces fully catalysing and participating in the reaction of DGEBA with DDM, which results in slower reaction and a lower crosslink density of the three-dimensional networks in the aGO-resin interphase compared to the acGO-resin interphase. We also determined that OD itself promoted DGEBA homopolymerization. A DSC study further confirmed that the aGO nanocomposite exhibited lower Tg while acGO nanocomposite showed higher Tg compared to neat resin because of the difference in crosslink densities of the matrix around the different GOs.

Solution chemistry impacts on the seawater neutralisation process: Benefits of nanofiltered seawater and reverse osmosis brine

It is well known that the neutralisation of Bayer liquor with seawater causes the precipitation of stable alkaline products and a reduction in pH and dissolved metal concentrations in the effluent. However, there is limited information available on solution chemistry effects on the stability and reaction kinetics of these precipitates. This investigation shows the influence of reactive species (magnesium and calcium) in seawater on precipitate stabilities and volumetric efficiencies during the neutralisation of bauxite refinery residues. Correlations between synthetic seawater solutions and real samples of seawater (filtered seawater, nanofiltered seawater and reverse osmosis brine) have been made. These investigations have been used to confirm that alternative seawater sources can be used to increase the productivity potential of the neutralisation process with minimal implications on the composition and stability of precipitates formed. The volume efficiency of the neutralisation process using synthetic analogues has been shown to be almost directly proportional with the concentration of magnesium. This was further confirmed in the nanofiltered seawater and reverse osmosis brine that showed increases in the efficiency of neutralisation by factors of 3 and 2 compared to seawater, which corresponds with relatively the same increase in the concentration of magnesium in these alternative seawater sources. An assessment of the chemical stability of the precipitates, volumetric efficiency, and discharge water quality have been determined using numerous techniques that include pH, conductivity, inductively coupled plasma optical emission spectroscopy, infrared spectroscopy, thermogravimetric analysis coupled to mass spectrometry and X-ray diffraction. Correlations between synthetic solution compositions and alternative seawater sources have been used to determine if alternative seawater sources are potential substitutes for seawater based on improvements in productivity, implementation costs, savings to operations and environmental benefits.

Visible-light-induced click chemistry

A rapid and catalyst-free cycloaddition system for visible-light-induced click chemistry is reported. A readily accessible photoreactive 2H-azirine moiety was designed to absorb light at wavelengths above 400 nm. Irradiation with low-energy light sources thus enables efficient small-molecule synthesis with a diverse range of multiple-bond-containing compounds. Moreover, in order to demonstrate the efficiency of the current approach, quantitative ligation of the photoactivatable chromophore with functional polymeric substrates was performed and full conversion with irradiation times of only 1 min at ambient conditions was achieved. The current report thus presents a highly efficient method for applications involving selective cycloaddition to electron-deficient multiple-bond-containing materials.

Photochemical design of stimuli-responsive nanoparticles prepared by supramolecular host–guest chemistry

We introduce the design of a thermoresponsive nanoparticle via sacrificial micelle formation based on supramolecular host–guest chemistry. Reversible addition–fragmentation chain transfer (RAFT) polymerization was employed to synthesize well-defined polymer blocks of poly(N,N-dimethylacrylamide) (poly(DMAAm)) (Mn,SEC = 10 700 g mol–1, Đ = 1.3) and poly(N-isopropylacrylamide) (poly(NiPAAm)) (Mn,SEC = 39 700 g mol–1, Đ = 1.2), carrying supramolecular recognition units at the chain termini. Further, 2-methoxy-6-methylbenzaldehyde moieties (photoenols, PE) were statistically incorporated into the backbone of the poly(NiPAAm) block as photoactive cross-linking units. Host–guest interactions of adamantane (Ada) (at the terminus of the poly(NiPAAm/PE) chain) and β-cyclodextrin (CD) (attached to the poly(DMAAm chain end) result in a supramolecular diblock copolymer. In aqueous solution, the diblock copolymer undergoes micellization when heated above the lower critical solution temperature (LCST) of the thermoresponsive poly(NiPAAm/PE) chain, forming the core of the micelle. Via the addition of a 4-arm maleimide cross-linker and irradiation with UV light, the micelle is cross-linked in its core via the photoinduced Diels–Alder reaction of maleimide and PE units. The adamantyl–cyclodextrin linkage is subsequently cleaved by the destruction of the β-CD, affording narrowly distributed thermoresponsive nanoparticles with a trigger temperature close to 30 °C. Polymer chain analysis was performed via size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) spectroscopy, and dynamic light scattering (DLS). The size and thermoresponsive behavior of the micelles and nanoparticles were investigated via DLS as well as atomic force microscopy (AFM).