Stereochemistry and thermal stability of tartaric acid on the intrinsically chiral Cu{531} surface

Intrinsically chiral metal surfaces provide enantiospecific reaction environments without the need of coadsorbed modifiers. Amongst the intrinsically chiral copper surfaces, Cu{531} has the smallest unit cell and the highest density of chiral sites. XPS, NEXAFS and TPD were employed to investigate the adsorption and decomposition behaviour of the two chiral enantiomers of tartaric acid on this surface. The results obtained from XPS and NEXAFS show that at saturation coverage both enantiomers of tartaric acid adsorb in a μ4 configuration through the two carboxylic groups,which are rotatedwith respect to each other by 90°±≈15°within the surface plane. At intermediate coverage the R,R enantiomer adopts a similar configuration, but the S,S enantiomer is different and shows a high degree of dissociation. Growth of multilayers is observed at high exposures when the sample is kept at below 370 K. TPD experiments show that multilayers desorb between 390 K and 470 K and decomposition of the chemisorbed layer occurs between 470 K and 600 K. The desorption spectra support a two-step decomposition mechanism with a O_C_C_O or HO–HC_CH–OH intermediate that leads to production of CO2 and CO. Enantiomeric differences are observed in the desorption features related to the decomposition of the chemisorbed layer.

Seasonal surface urban energy balance and wintertime stability simulated using three land-surface models in the high-latitude city Helsinki

The performance of three urban land surface models, run in offline mode, with their default external parameters, is evaluated for two distinctly different sites in Helsinki: Torni and Kumpula. The former is a dense city centre site with 22% vegetation, while the latter is a suburban site with over 50% vegetation. At both locations the models are compared against sensible and latent heat fluxes measured using the eddy covariance technique, along with snow depth observations. The cold climate experienced by the city causes strong seasonal variations that include snow cover and stable atmospheric conditions. Most of the time the three models are able to account for the differences between the study areas as well as the seasonal and diurnal variability of the energy balance components. However, the performances are not systematic across the modelled components, season and surface type. The net all-wave radiation is well simulated, with the greatest uncertainties related to snowmelt timing, when the fraction of snow cover has a key role, particularly in determining the surface albedo. For the turbulent fluxes, more variation between the models is seen which can partly be explained by the different methods in their calculation and partly by surface parameter values. For the sensible heat flux, simulation of wintertime values was the main problem, which also leads to issues in predicting near-surface stabilities particularly at the dense city centre site. All models have the most difficulties in simulating latent heat flux. This study particularly emphasizes that improvements are needed in the parameterization of anthropogenic heat flux and thermal parameters in winter, snow cover in spring and evapotranspiration in order to improve the surface energy balance modelling in cold climate cities.

New insights into the compressibility and high-pressure stability of Ni(CN)2: a combined study of neutron diffraction, Raman spectroscopy, and inelastic neutron scattering

Nickel cyanide is a layered material showing markedly anisotropic behaviour. High-pressure neutron diffraction measurements show that at pressures up to 20.1 kbar, compressibility is much higher in the direction perpendicular to the layers, c, than in the plane of the strongly chemically bonded metal-cyanide sheets. Detailed examination of the behaviour of the tetragonal lattice parameters, a and c, as a function of pressure reveal regions in which large changes in slope occur, for example, in c(P) at 1 kbar. The experimental pressure dependence of the volume data is fitted to a bulk modulus, B0, of 1050 (20) kbar over the pressure range 0–1 kbar, and to 124 (2) kbar over the range 1–20.1 kbar. Raman spectroscopy measurements yield additional information on how the structure and bonding in the Ni(CN)2 layers change with pressure and show that a phase change occurs at about 1 kbar. The new high-pressure phase, (Phase PII), has ordered cyanide groups with sheets of D4h symmetry containing Ni(CN)4 and Ni(NC)4 groups. The Raman spectrum of phase PII closely resembles that of the related layered compound, Cu1/2Ni1/2(CN)2, which has previously been shown to contain ordered C≡N groups. The phase change, PI to PII, is also observed in inelastic neutron scattering studies which show significant changes occurring in the phonon spectra as the pressure is raised from 0.3 to 1.5 kbar. These changes reflect the large reduction in the interlayer spacing which occurs as Phase PI transforms to Phase PII and the consequent increase in difficulty for out-of-plane atomic motions. Unlike other cyanide materials e.g. Zn(CN)2 and Ag3Co(CN)6, which show an amorphization and/or a decomposition at much lower pressures (~100 kbar), Ni(CN)2 can be recovered after pressurising to 200 kbar, albeit in a more ordered form.

Peptide based hydrogels for cancer drug release: modulation of stiffness, drug release and proteolytic stability of hydrogels by incorporating D-amino acid residue(s)

Synthetic tripeptide based noncytotoxic hydrogelators have been discovered for releasing an anticancer drug at physiological pH and temparature. Interestingly, gel stiffness, drug release capacity and proteolytic stability of these hydrogels have been successfully modulated by incorporating D-amino acid residues, indicating their potential use for drug delivery in the future.

The effect of an external auditory stimulus on postural stability of participants with cochlear implants

Postural control was evaluated in cochlear implant participants with and without amplification under several auditory paradigms. Speed of sway was recorded in each condition by means of Computerized Dynamic Posturography. Results indicate that an external sound source significantly improves balance in patients with cochlear implants.

COLOR STABILITY OF DENTAL CERAMICS SUBMITTED TO ARTIFICIAL ACCELERATED AGING AFTER REPEATED FIRINGS

Statement of problem. Color stability is an important factor to ensure the long-term clinical success of ceramic restorations. There is a lack of information on how color is affected by fabrication procedures, such as the number of firings. Purpose. The purpose of this study was to evaluate the effects that the number of firings and type of substrate have on the color stability of dental ceramic submitted to artificial accelerated aging. Material and methods. Sixty specimens were fabricated: 30 metal ceramic (Verabond II + IPS d.SIGN) and 30 all-ceramic (IPS d.SIGN). Specimens were divided into 3 groups (n=10), and submitted to 2, 3, or 4 firings (+/- 900 degrees C), respectively, according to the manufacturer`s instructions. Color readings were obtained with a spectro photometer before and after artificial accelerated aging, and L*, a*, and b* coordinates and total color variation (Delta E) were analyzed (2-way ANOVA, Bonferroni, (alpha=05). Results. For metal ceramic specimens, differences for the L* coordinates were significant (P<.05) only for the group submitted to 3 firings. With respect to the all-ceramic specimens, smaller L* coordinates were obtained for greater a* and b* coordinates, indicating that the greater the number of firings, the darker and more reddish/yellowish the specimen. All Delta E values, for all groups, were below 1.0. All-ceramic specimens submitted to 3 and 4 firings presented Delta E means differing statistically (P<.05) from those of the metal ceramic group. Conclusions. The type of substrate and number of firings affected the color stability of the ceramic material tested. Artificial accelerated aging did not produce perceptible color stability changes (Delta E<1.0). (J Prosthet Dent 2009-101:13-18)

Assessment of production efficiency, physicochemical properties and storage stability of spray-dried chlorophyllide, a natural food colourant, using gum Arabic, maltodextrin and soy protein isolate-based carrier systems

P>The aim of this research was to study spray drying as potential action to protect chlorophyllide from environmental conditions for shelf-life extension and characterisation of the powders. Six formulations were prepared with 7.5 and 10 g of carrier agents [gum Arabic (GA), maltodextrin (MA) and soybean protein isolate (SPI)]/100 mL of chlorophyllide solutions. The powders were evaluated for morphological characteristics (SEM), particle size, water activity, moisture, density, hygroscopicity, cold water solubility, sorption isotherms, colour and stability, during 90 days. All the powders were highly soluble, with solubility values around 97%. A significant lower hygroscopicity was observed for GA powders, whilst the lower X(m) values obtained by GAB equation fitting of the sorption isotherms was observed for the 7.5 g MA/100 mL samples. All formulations, but the 1 (7.5 g SPI/100 mL of chlorophyllide), provided excellent stability to the chlorophyllide during 90 days of storage even at room temperature.

The effect of homogenisation on the stability of pineapple pulp

P>Pineapple pulp was homogenised at different pressures, and its stability investigated by way of flow curves, particle size distribution, morphology, cloudiness and sedimentation. The particle size of the homogenised pulp ranged from 400 to 100 mu m for homogenisation pressures of between 0 and 700 bar. The pineapple pulp showed shear thinning behaviour with increasing flow index (n) after processing at higher pressures. In addition, the pulps with smaller particles showed less serum cloudiness, even though the sedimentation tests showed the highest stability for pulp homogenised between 200 and 300 bar. Above 400 bar, the pulp showed phase separation and higher sedimentation indexes, similar to that observed for the untreated samples, which was attributed to the formation of aggregates because of interparticle attraction.

EXPRESSION OF COCAINE- AND AMPHETAMINE-REGULATED TRANSCRIPT IN THE RAT FOREBRAIN DURING POSTNATAL DEVELOPMENT

Cocaine- and amphetamine-regulated transcript (CART) is widespread in the rodent brain. CART has been implicated in many different functions including reward, feeding, stress responses, sensory processing, learning and memory formation. Recent studies have suggested that CART may also play a role in neural development. Therefore, in the present study we compared the distribution pattern and levels of CART mRNA expression in the forebrain of male and female rats at different stages of postnatal development: P06, P26 and P66. At 6 days of age (P06), male and female rats showed increased CART expression in the somatosensory and piriform cortices, indusium griseum, dentate gyrus, nucleus accumbens, and ventral premammillary nucleus. Interestingly, we found a striking expression of CART mRNA in the ventral posteromedial and ventral posterolateral thalamic nuclei. This thalamic expression was absent at P26 and P66. Contrastingly, at P06 CART mRNA expression was decreased in the arcuate nucleus. Comparing sexes, we found increased CART mRNA expression in the anteroventral periventricular nucleus of adult females. In other regions including the CA1, the lateral hypothalamic area and the dorsomedial nucleus of the hypothalamus, CART expression was not different comparing postnatal ages and sexes. Our findings indicate that CART gene expression is induced in a distinct temporal and spatial manner in forebrain sites of male and female rats. They also suggest that CART peptide participate in the development of neural pathways related to selective functions including sensory processing, reward and memory formation. (C) 2011 IBRO. Published by Elsevier Ltd. All rights reserved.

Expression Profile and Distribution of Efhc1 Gene Transcript During Rodent Brain Development

One of the putative causative genes for juvenile myoclonic epilepsy (JME) is EFHC1. We report here the expression profile and distribution of Efhc1 messenger RNA (mRNA) during mouse and rat brain development. Real-time polymerase chain reaction revealed that there is no difference in the expression of Efhc1 mRNA between right and left hemispheres in both species. In addition, the highest levels of Efhc1 mRNA were found at intra-uterine stages in mouse and in adulthood in rat. In common, there was a progressive decrease in Efhc1 expression from 1-day-old neonates to 14-day-old animals in both species. In situ hybridization studies showed that rat and mouse Efhc1 mRNAs are expressed in ependymal cells of ventricle walls. Our findings suggest that Efhc1 expression is more important during initial phases of brain development and that at this stage it could be involved in key developmental mechanisms underlying JME.

Stability of gradient semigroups under perturbations

In this paper we prove that gradient-like semigroups (in the sense of Carvalho and Langa (2009 J. Diff. Eqns 246 2646-68)) are gradient semigroups (possess a Lyapunov function). This is primarily done to provide conditions under which gradient semigroups, in a general metric space, are stable under perturbation exploiting the known fact (see Carvalho and Langa (2009 J. Diff. Eqns 246 2646-68)) that gradient-like semigroups are stable under perturbation. The results presented here were motivated by the work carried out in Conley (1978 Isolated Invariant Sets and the Morse Index (CBMS Regional Conference Series in Mathematics vol 38) (RI: American Mathematical Society Providence)) for groups in compact metric spaces (see also Rybakowski (1987 The Homotopy Index and Partial Differential Equations (Universitext) (Berlin: Springer)) for the Morse decomposition of an invariant set for a semigroup on a compact metric space).

Permanence of stability for a class of system of differential equations with two delays

The paper studies a class of a system of linear retarded differential difference equations with several parameters. It presents some sufficient conditions under which no stability changes for an equilibrium point occurs. Application of these results is given. (c) 2007 Elsevier Ltd. All rights reserved.

STABILITY FOR RETARDED FUNCTIONAL DIFFERENTIAL EQUATIONS

It is known that retarded functional differential equations can be regarded as Banach-space-valued generalized ordinary differential equations (GODEs). In this paper, some stability concepts for retarded functional differential equations are introduced and they are discussed using known stability results for GODEs. Then the equivalence of the different concepts of stabilities considered here are proved and converse Lyapunov theorems for a very wide class of retarded functional differential equations are obtained by means of the correspondence of this class of equations with GODEs.

Poisson stability for impulsive semidynamical systems

In this paper, the concept of Poisson stability is investigated for impulsive semidynamical systems. Recursive properties are also investigated. (C) 2009 Elsevier Ltd. All rights reserved.