Survey of arsenic and its speciation in rice products such as breakfast cereals, rice crackers and Japanese rice condiments

Rice has been demonstrated to be one of the major contributors to arsenic (As) in human diets in addition to drinking water, but little is known about rice products as an additional source of As exposure. Rice products were analyzed for total As and a subset of samples were measured for arsenic speciation using high performance liquid chromatography interfaced with inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). A wide range of rice products had total and inorganic arsenic levels that typified those found in rice grain including, crisped rice, puffed rice, rice crackers, rice noodles and a range of Japanese rice condiments as well as rice products targeted at the macrobiotic, vegan, lactose intolerant and gluten intolerance food market. Most As in rice products are inorganic As (75.2-90.1%). This study provides a wider appreciation of how inorganic arsenic derived from rice products enters the human diet. (C) 2008 Elsevier Ltd. All rights reserved.

Changing climate, changing process: implications for salt transportation and weathering within building sandstones in the UK

Salt weathering is a crucial process that brings about a change in stone, from the scale of landscapes to stone outcrops and natural building stone facades. It is acknowledged that salt weathering is controlled by fluctuations in temperature and moisture, where repeated oscillations in these parameters can cause re-crystallisation, hydration/de-hydration of salts, bringing about stone surface loss in the form of, for example, granular disaggregation, scaling, and multiple flaking. However, this ‘traditional’ view of how salt weathering proceeds may need to be re-evaluated in the light of current and future climatic trends. Indeed, there is considerable scope for the investigation of consequences of climate change on geomorphological processes in general. Building on contemporary research on the ‘deep wetting’ of natural building stones, it is proposed that (as stone may be wetter for longer), ion diffusion may become a more prominent mechanism for the mixing of molecular constituents, and a shift in focus from physical damage to chemical change is suggested. Data from ion diffusion cell experiments are presented for three different sandstone types, demonstrating that salts may diffuse through porous stone relatively rapidly (in comparison to, for example, dense concrete). Pore water from stones undergoing diffusion experiments was extracted and analysed. Factors controlling ion diffusion
relating to ‘time of wetness’ within stones are discussed, (continued saturation, connectivity of pores, mineralogy, behaviour of salts, sedimentary structure), and potential changes in system dynamics as a result of climate change are addressed. System inputs may change in terms of increased moisture input, translating into a greater depth of wetting front. Salts are likely to be ‘stored’ differently in stones, with salt being in solution for longer periods (during prolonged winter wetness). This has myriad implications in terms of the movement of ions by diffusion and the potential for chemical change in the stone (especially in more mobile constituents), leading to a weakening of the stone matrix/grain boundary cementing. The ‘output’ may be mobilisation and precipitation of elements leading to, for example, uneven cementing in the stone. This reduced strength of the stone, or compromised ability of the stone to absorb stress, is likely to make crystallisation a more efficacious mechanism of decay when it does occur. Thus, a delay in the onset of crystallisation while stonework is wet does not preclude exaggerated or accelerated material loss when it finally happens.

Moisture and temperature dependence of the dielectric properties of pharmaceutical powders

The dielectric properties of pharmaceutical powder-(paracetamol, aspirin, lactose, maize starch, adipic acid) solvent (water) mixtures were measured at 2,450 MHz at a range of moisture contents (0-1.0 kg kg(-1), dry basis) and temperatures (20-70 A degrees C). The dielectric constant (epsilon'), loss factor (epsilon aEuro(3)) and penetration depth (d (p)) were found to be dependent on frequency, moisture content, temperature and powder type. For powder-water mixtures, a linear increase in the dielectric properties with moisture content was observed, whilst the temperature dependence was of quadratic form. The penetration depth was also significantly affected by temperature and moisture content. Although, epsilon aEuro(3) also increased with increasing temperature, variation with moisture content was temperature dependent. This information on dielectric properties is essential for mathematical description of the pharmaceutical product temperature history during microwave heating and for the design of microwave drying equipment.

The use and meanings of 'time of wetness' in understanding stone decay

Moisture is a well documented, and crucial, control on the nature of stone decay. The term time of wetness has frequently been adopted to describe how long a stone block is wet, with a view to understanding the impact of this on decay processes. Although this term has proved conceptually useful, it has been used in different ways, by different groups to mean mean quite different things. For example, the time of wetness for a stone block surface (the traditional understanding) may be quite different from that of a block interior, controlled by the different dynamics of wetting and drying in those zones. Thus, surface wetting will occur regularly (sometimes swiftly followed by drying, depending on the time of year), with block interior wetting requiring the accumulation of surface moisture to penetrate to depth (more likely in autumn and winter months), and drying out much more slowly. This relatively new but important perspective, framed in the context of climate change, is crucial to understanding the length of time stone may remain damp at depth following a period of prolonged precipitation. The nature and speed of drying is also relevant in quantifying time of wetness of both surfaces and the interior of building stones.
These ideas related to time of wetness have implications for decay processes, specifically how a prolonged time of deep wetness may re-focus the emphasis of salt weathering in natural building stones toward chemical action. Literature on chemical change is discussed, suggesting that chemical change occurring during periods of prolonged wetness is likely to be significant in itself, with implications for weakening the stone (in terms of, for example, cement dissolution or grain boundary weakening) and exacerbating physical damage from salt crystallisation when blocks finally dry out.

Pinning down the solid-state polymorphism of the ionic liquid [bmim][PF6]

The solid-state polymorphism of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6], has been investigated via low-temperature and high-pressure crystallisation experiments. The samples have been characterised by single-crystal X-ray diffraction, optical microscopy and Raman spectroscopy. The solid-state phase behaviour of the compound is confirmed and clarified with respect to previous phase diagrams. The structures of the previously reported gamma-form, which essentially exhibits a G'T cation conformation, as well as those of the elusive beta- and alpha-forms, are reported. Crystals of the beta-phase are twinned and the structure is heavily disordered; the cation conformation in this form is predominantly TT, though significant contributions from other less frequently encountered conformers are also observed at low temperature and high pressure. The cation conformation in the alpha-form is GT; the presence of the G'T conformer at 193 K in this phase can be eliminated on cooling to 100 K. Whilst X-ray structural data are overall in good agreement with previous interpretations based on Raman and NMR studies, they also reveal a more subtle interplay of intermolecular interactions, which give rise to a wider range of conformers than previously considered.

EFFECT OF IMPELLER DESIGN ON PRODUCT HOMOGENIETY IN HIGH SHEAR WET GRANULATION

Design of small mixer impellers is not tailored for granulation as they are designed for a wide range of processes. The Kenwood KM070 was employed as a standard apparatus to undertake this investigation. Five different impeller designs were used, possessing different shapes and surface areas. The aim of this research was to evaluate the performances of these impellers to provide
guidance on the selection and design for the purposes of granulation. Lactose granules were produced using wet granulation with water as the binder.
The efficacy of respective granulates was measured by adding an optically
sensitive tracer.This was used to determine powder concentrations
within various regions of the granulator. It was found that impeller design influenced the homogeneity of the granules; and therefore can affect final product performance.

Lovastatin biosynthesis depends on the carbon-nitrogen proportion: model development and controller design

Lovastatin biosynthesis depends on the relative concentrations of dissolved oxygen and the carbon and nitrogen resources. An elucidation of the underlying relationship would facilitate the derivation of a controller for the improvement of lovastatin yield in bioprocesses. To achieve this goal, batch submerged cultivation experiments of lovastatin production by Aspergillus flavipus BICC 5174, using both lactose and glucose as carbon sources, were performed in a 7 liter bioreactor and the data used to determine how the relative concentrations of lactose, glucose, glutamine and oxygen affected lovastatin yield. A model was developed based on these results and its prediction was validated using an independent set of batch data obtained from a 15-liter bioreactor using five statistical measures, including the Willmott index of agreement. A nonlinear controller was designed considering that dissolved oxygen and lactose concentrations could be measured online, and using the lactose feed rate and airflow rate as process inputs. Simulation experiments were performed to demonstrate that a practical implementation of the nonlinear controller would result in satisfactory outcomes. This is the first model that correlates lovastatin biosynthesis to carbon-nitrogen proportion and possesses a structure suitable for implementing a strategy for controlling lovastatin production.

Cultural and Genetic Influences on the “Biological Standard of Living”

This study suggests an improvement of a popular measure of living standards, namely the biological standard of living. One influence on it is a population's consumption pattern. Since there are different dietary patterns all over the world, researchers estimate the influences of national diets on final average male height. These habits are predominantly related to income, but also to genetics, cultural history, and decisions regarding whether to trade or consume high-quality foodstuffs. Systematic differences are found when analyzing protein-consumption habits among 51 countries between the 1960s and the 1980s. The author calculates metric correction values which can facilitate international comparisons of male average height. While the proposed correction values make a little difference on average, they can be valuable in a comparison of countries with markedly different dietary patterns.

Ferromagnetism in DyRh and DyRhX (X = Fe, Ni, Co, Gd) thin films

In an effort to achieve large high-field magnetization and increased Curie temperature, polycrystalline DyRh, (DyRh)95X5 and (DyRh)85X15 (X = Fe, Co, Ni, Gd) thin films have been prepared via ultra-high vacuum DC co-sputtering on SiO2 and Si wafers, using Ta as seed and cap material. A body-centred cubic CsCl-like crystal formation (B2 phase) was achieved for DyRh around the equiatomic equilibrium, known from single crystals. The maximum in-plane spontaneous magnetization at T = 4K in fields of μ0H = 5T of was found to be μ0MS,4K = (1.50 ± 0.09)T with a ferromagnetic transition at TC = (5 ± 1)K and a coercivity of μ0HC,4K[D] = (0.010 ± 0.001)T (at T = 4K) for layers deposited on substrates heated to 350°C. Samples prepared at room temperature exhibited poorer texture, smaller grains and less B2-phase content; this did impact on the Curie temperature which was higher compared to those layers with best crystallisation; however the maximal magnetization stayed unaffected. Ferromagnetic coupling was observed in ternary alloys of DyRhGd and DyRhNi with an increased Curie temperature, larger initial permeability, and
high-field magnetization which was best for (DyRh)85Gd15 with μ0MS,4K[Gd15] = (2.10 ± 0.13)T. DyRhFe and DyRhCo showed antiparallel coupling of the spontaneous magnetic moments.

Investigation of influence of process variables on mechanical strength, size and homogeneity of pharmaceutical granules produced by fluidised hot melt granulation

The overall aim of the project was to study the influence of process variables on the distribution of a model active pharmaceutical ingredient (API) during fluidised melt granulation of pharmaceutical granules with a view of optimising product characteristics. Granules were produced using common pharmaceutical excipients; lactose monohydrate using poly ethylene glycol (PEG1500) as a meltable binder. Methylene blue was used as a model API. Empirical models relating the process variables to the granules properties such as granule mean size, product homogeneity and granule strength were developed using the design of experiment approach. Fluidising air velocity and fluidising air temperature were shown to strongly influence the product properties. Optimisation studies showed that strong granules with homogeneous distribution of the active ingredient can be produced at high fluidising air velocity and at high fluidising air temperatures.

Effect of Impeller Design on Homogeneity, Size and Strength of Pharmaceutical Granules produced by High Shear Wet Granulation

Small mixer impeller design is not tailored for granulation because impellers are intended for a wide range of processes. The aim of this research was to evaluate the performances of several impellers to provide guidance on the selection and design for the purposes of granulation. Lactose granules were produced using wet granulation with water as a binder. A Kenwood KM070 mixer was used as a standard apparatus and five impeller designs with different shapes and surface areas were used. The efficacy of granulate formation was measured by adding an optically sensitive tracer to determine variations in active ingredient content across random samples of granules from the same size classes. It was found that impeller design influenced the homogeneity of the granules and therefore can affect final product performance. The variation in active ingredient content across granules of differing size was also investigated. The results show that small granules were more potent than larger granules.

Release of β-galactosidase from poloxamine/α-cyclodextrin hydrogels

All mammals lose their ability to produce lactase (β-galactosidase), the enzyme that cleaves lactose into galactose and glucose, after weaning. The prevalence of lactase deficiency (LD) spans from 2 to 15% among northern Europeans, to nearly 100% among Asians. Following lactose consumption, people with LD often experience gastrointestinal symptoms such as abdominal pain, bowel distension, cramps and flatulence, or even systemic problems such as headache, loss of concentration and muscle pain. These symptoms vary depending on the amount of lactose ingested, type of food and degree of intolerance. Although those affected can avoid the uptake of dairy products, in doing so, they lose a readily available source of calcium and protein. In this work, gels obtained by complexation of Tetronic 90R4 with α-cyclodextrin loaded with β-galactosidase are proposed as a way to administer the enzyme immediately before or with the lactose-containing meal. Both molecules are biocompatible, can form gels in situ, and show sustained erosion kinetics in aqueous media. The complex was characterized by FTIR that evidenced an inclusion complex between the polyethylene oxide block and α-cyclodextrin. The release profiles of β-galactosidase from two different matrices (gels and tablets) of the in situ hydrogels have been obtained. The influence of the percentage of Tetronic in media of different pH was evaluated. No differences were observed regarding the release rate from the gel matrices at pH 6 (t50 = 105 min). However, in the case of the tablets, the kinetics were faster and they released a greater amount of 90R4 (25%, t50 = 40–50 min). Also, the amount of enzyme released was higher for mixtures with 25% Tetronic. Using suitable mathematical models, the corresponding kinetic parameters have been calculated. In all cases, the release data fit quite well to the Peppas–Sahlin model equation, indicating that the release of β-galactosidase is governed by a combination of diffusion and erosion processes. It has been observed that the diffusion mechanism prevails over erosion during the first 50 minutes, followed by continued release of the enzyme due to the disintegration of the matrix.

3-Methylpiperidinium ionic liquids

A wide range of room temperature ionic liquids based on the 3-methylpiperdinium cation core were produced from 3-methylpiperidine, which is a derivative of DYTEK® A amine. First, reaction with 1-bromoalkanes or 1-bromoalkoxyalkanes generated the corresponding tertiary amines (Rmβpip, R = alkyl or alkoxyalkyl); further quaternisation reactions with the appropriate methylating agents yielded the quaternary [Rmmβpip]X salts (X(-) = I(-), [CF3CO2](-) or [OTf](-); Tf = -SO2CF3), and [Rmmβpip][NTf2] were prepared by anion metathesis from the corresponding iodides. All [NTf2](-) salts are liquids at room temperature. [Rmmβpip]X (X(-) = I(-), [CF3CO2](-) or [OTf](-)) are low-melting solids when R = alkyl, but room temperature liquids upon introduction of ether functionalities on R. Neither of the 3-methylpiperdinium ionic liquids showed any signs of crystallisation, even well below 0 °C. Some related non-C-substituted piperidinium and pyrrolidinium analogues were prepared and studied for comparison. Crystal structures of 1-hexyl-1,3-dimethylpiperidinium tetraphenylborate, 1-butyl-3-methylpiperidinium bromide, 1-(2-methoxyethyl)-1-methylpiperidinium chloride and 1-(2-methoxyethyl)-1-methylpyrrolidinium bromide are reported. Extensive structural and physical data are collected and compared to literature data, with special emphasis on the systematic study of the cation ring size and/or asymmetry effects on density, viscosity and ionic conductivity, allowing general trends to be outlined. Cyclic voltammetry shows that 3-methylpiperidinium ionic liquids, similarly to azepanium, piperidinium or pyrrolidinium counterparts, are extremely electrochemically stable; the portfolio of useful alternatives for safe and high-performing electrolytes is thus greatly extended.

Shape stabilised phase change materials based on a high melt viscosity HDPE and paraffin waxes

Shape stabilised phase change materials (SSPCMs) based on a high density poly(ethylene)(hv-HDPE) with high (H-PW, Tm = 56–58 °C) and low (L-PW, Tm = 18–23 °C) melting point paraffin waxes were readily prepared using twin-screw extrusion. The thermo-physical properties of these materials were assessed using a combination of techniques and their suitability for latent heat thermal energy storage (LHTES) assessed. The melt processing temperature (160 °C) of the HDPE used was well below the onset of thermal decomposition of H-PW (220 °C), but above that for L-PW (130 °C), although the decomposition process extended over a range of 120 °C and the residence time of L-PW in the extruder was <30 s. The SSPCMs prepared had latent heats up to 89 J/g and the enthalpy values for H-PW in the respective blends decreased with increasing H-PW loading, as a consequence of co-crystallisation of H-PW and hv-HDPE. Static and dynamic mechanical analysis confirmed both waxes have a plasticisation effect on this HDPE. Irrespective of the mode of deformation (tension, flexural, compression) modulus and stress decreased with increased wax loading in the blend, but the H-PW blends were mechanically superior to those with L-PW.

Sustained release of the candidate antiretroviral peptides T-1249 and JNJ54310516-AFP from a rod insert vaginal ring

Administration of biomacromolecular drugs in effective quantities from conventional vaginal rings is hampered by poor drug permeability in the polymers from which rings are commonly constructed. Here, we report the formulation development and testing of rod insert rings for sustained release of the candidate antiretroviral peptides T-1249 and JNJ54310516-AFP (JNJ peptide), both of which have potential as HIV microbicides. Rod inserts were prepared comprising antiviral peptides T-1249 or JNJ peptide in combination with a hydrophilic excipient (sodium chloride, sodium glutamate, lactose or zinc acetate) dispersed at different loadings within a medical grade silicone elastomer. The inserts were tested for weight change and swelling when immersed in simulated vaginal fluid (SVF). Dye migration into the inserts was also assessed visually over 28 days. In vitro release of T-1249 and JNJ peptide from rings containing various insert types was tested. Weight change and degree of swelling of rods immersed in SVF was dependent on the type and concentration of excipient present. The rods displayed the following rank order in terms of weight change: sodium glutamate > zinc acetate ≈ sodium chloride > lactose. The weight change and degree of swelling of the inserts did not correlate with the level of dye uptake observed. In vitro release of T-1249 was improved through addition of lactose, sodium chloride and sodium glutamate, while release of JNJ peptide was improved through addition of sodium chloride or sodium glutamate. Sustained release of hydrophobic peptides can be achieved using a rod insert ring design formulated to include a hydrophilic excipient. Release rates were dependent upon the type of excipient used. The degree of release improvement with different inserts partially reflects their ability to imbibe surrounding fluid and swell in aqueous environments.