Hydrogen-bonded complexes and blends of poly(acrylic acid) and methylcellulose: nanoparticles and mucoadhesive films for Ocular Delivery of Riboflavin

Poly(acrylic acid) (PAA) and methylcellulose (MC) are able to form hydrogen-bonded interpolymer complexes (IPCs) in aqueous solutions. In this study, the complexation between PAA andMC is explored in dilute aqueous solutions under acidic conditions. The formation of stable nanoparticles is established,whose size and colloidal stability are greatly dependent on solution pH and polymers ratio in the mixture. Poly(acrylic acid) and methylcellulose are also used to prepare polymeric films by casting from aqueous solutions. It is established that uniform films can be prepared by casting from polymer mixture solutions at pH 3.4–4.5. At lower pHs (pH<3.0) the films have inhomogeneous morphology resulting from strong interpolymer complexation and precipitation of polycomplexes, whereas at higher pHs (pH 8.3) the polymers form fully immiscible blends because of the lack of interpolymer hydrogen-bonding. The PAA/MC films cast at pH 4 are shown to be non-irritant to mucosal surfaces. These films provide a platform for ocular formulation of riboflavin, a drug used for corneal crosslinking in the treatment of keratoconus. An in vitro release of riboflavin as well as an in vivo retention of the films on corneal surfaces can be controlled by adjusting PAA/MC ratio in the formulations.

Effective LAI and CHP of a single tree from small-footprint full-waveform LiDAR

This letter has tested the canopy height profile (CHP) methodology as a way of effective leaf area index (LAIe) and vertical vegetation profile retrieval at a single-tree level. Waveform and discrete airborne LiDAR data from six swaths, as well as from the combined data of six swaths, were used to extract the LAIe of a single live Callitris glaucophylla tree. LAIe was extracted from raw waveform as an intermediate step in the CHP methodology, with two different vegetation-ground reflectance ratios. Discrete point LAIe estimates were derived from the gap probability using the following: 1) single ground returns and 2) all ground returns. LiDAR LAIe retrievals were subsequently compared to hemispherical photography estimates, yielding mean values within ±7% of the latter, depending on the method used. The CHP of a single dead Callitris glaucophylla tree, representing the distribution of vegetation material, was verified with a field profile manually reconstructed from convergent photographs taken with a fixed-focal-length camera. A binwise comparison of the two profiles showed very high correlation between the data reaching R2 of 0.86 for the CHP from combined swaths. Using a study-area-adjusted reflectance ratio improved the correlation between the profiles, but only marginally in comparison to using an arbitrary ratio of 0.5 for the laser wavelength of 1550 nm.

Instantaneous gelation in Smoluchowski’s coagulation equation revisited

We study the solutions of the Smoluchowski coagulation equation with a regularization term which removes clusters from the system when their mass exceeds a specified cutoff size, M. We focus primarily on collision kernels which would exhibit an instantaneous gelation transition in the absence of any regularization. Numerical simulations demonstrate that for such kernels with monodisperse initial data, the regularized gelation time decreasesas M increases, consistent with the expectation that the gelation time is zero in the unregularized system. This decrease appears to be a logarithmically slow function of M, indicating that instantaneously gelling kernels may still be justifiable as physical models despite the fact that they are highly singular in the absence of a cutoff. We also study the case when a source of monomers is introduced in the regularized system. In this case a stationary state is reached. We present a complete analytic description of this regularized stationary state for the model kernel, K(m1,m2)=max{m1,m2}ν, which gels instantaneously when M→∞ if ν>1. The stationary cluster size distribution decays as a stretched exponential for small cluster sizes and crosses over to a power law decay with exponent ν for large cluster sizes. The total particle density in the stationary state slowly vanishes as [(ν−1)logM]−1/2 when M→∞. The approach to the stationary state is nontrivial: Oscillations about the stationary state emerge from the interplay between the monomer injection and the cutoff, M, which decay very slowly when M is large. A quantitative analysis of these oscillations is provided for the addition model which describes the situation in which clusters can only grow by absorbing monomers.

Hybrid proton and electron transport in peptide fibrils

Protons and electrons are being exploited in different natural charge transfer processes. Both types of charge carriers could be, therefore, responsible for charge transport in biomimetic self-assembled peptide nanostructures. The relative contribution of each type of charge carrier is studied in the present work for fi brils self-assembled from amyloid- β derived peptide molecules, in which two non-natural thiophene-based amino acids are included. It is shown that under low humidity conditions both electrons and protons contribute to the conduction, with current ratio of 1:2 respectively, while at higher relative humidity proton transport dominates the conductance. This hybrid conduction behavior leads to a bimodal exponential dependence of the conductance on the relative humidity. Furthermore, in both cases the conductance is shown to be affected by the peptide folding state under the entire relative humidity range. This unique hybrid conductivity behavior makes self-assembled peptide nanostructures powerful building blocks for the construction of electric devices that could use either or both types of charge carriers for their function.

Mammalian-microbial cometabolism of L-Carnitine in the context of atherosclerosis

g-butyrobetaine has long been known as the precursor of endogenous L-carnitine synthesis. In this issue, Koeth et al. (2014) demonstrate that it is also a major metabolite of L-carnitine degradation by gut bacteria that precedes the enteric production of trimethylamine and trimethylamine-N-oxide.

First-principles study of the inversion thermodynamics and electronic structure of FeM2X4 (thio)spinels (M = Cr, Mn, Co, Ni; X = O, S)

FeM2X4 spinels, where M is a transition metal and X is oxygen or sulfur, are candidate materials for spin filters, one of the key devices in spintronics. We present here a computational study of the inversion thermodynamics and the electronic structure of these (thio)spinels for M = Cr, Mn, Co, Ni, using calculations based on the density functional theory with on-site Hubbard corrections (DFT+U). The analysis of the configurational free energies shows that different behaviour is expected for the equilibrium cation distributions in these structures: FeCr2X4 and FeMn2S4 are fully normal, FeNi2X4 and FeCo2S4 are intermediate, and FeCo2O4 and FeMn2O4 are fully inverted. We have analyzed the role played by the size of the ions and by the crystal field stabilization effects in determining the equilibrium inversion degree. We also discuss how the electronic and magnetic structure of these spinels is modified by the degree of inversion, assuming that this could be varied from the equilibrium value. We have obtained electronic densities of states for the completely normal and completely inverse cation distribution of each compound. FeCr2X4, FeMn2X4, FeCo2O4 and FeNi2O4 are half-metals in the ferrimagnetic state when Fe is in tetrahedral positions. When M is filling the tetrahedral positions, the Cr-containing compounds and FeMn2O4 are half-metallic systems, while the Co and Ni spinels are insulators. The Co and Ni sulfide counterparts are metallic for any inversion degree together with the inverse FeMn2S4. Our calculations suggest that the spin filtering properties of the FeM2X4 (thio)spinels could be modified via the control of the cation distribution through variations in the synthesis conditions.

Freshwater transport in the coupled ocean-atmosphere system: a passive ocean

Conservation of water demands that meridional ocean and atmosphere freshwater transports (FWT) are of equal magnitude but opposite in direction. This suggests that the atmospheric FWT and its associated latent heat (LH) transport could be thought of as a \textquotedblleft coupled ocean/atmosphere mode\textquotedblright. But what is the true nature of this coupling? Is the ocean passive or active? Here we analyze a series of simulations with a coupled ocean-atmosphere-sea ice model employing highly idealized geometries but with markedly different coupled climates and patterns of ocean circulation. Exploiting streamfunctions in specific humidity coordinates for the atmosphere and salt coordinates for the ocean to represent FWT in their respective medium, we find that atmospheric FWT/LH transport is essentially independent of the ocean state. Ocean circulation and salinity distribution adjust to achieve a return freshwater pathway demanded of them by the atmosphere. So, although ocean and atmosphere FWTs are indeed coupled by mass conservation, the ocean is a passive component acting as a reservoir of freshwater.

Multiple schools, languages, experiences and affiliations: ideological becomings and positionings

This article focuses on the identity accounts of a group of Chinese children who attend a heritage language school. Bakhtin’s concepts of ideological becoming, and authoritative and internally persuasive discourse, frame our exploration. Taking a dialogic view of language and learning raises questions about schools as socializing spaces and ideological environments. The children in this inquiry articulate their own ideological patterns of alignment. Those patterns, and the children's code switching, seem mostly determined by their socialization, language affiliations, friendship patterns, family situations, and legal access to particular schools. Five patterns of ideological becoming are presented. The children’s articulated preferences indicate that they assert their own ideological stances towards prevailing authoritative discourses, give voice to their own sense of agency and internally persuasive discourses, and respond to the ideological resources that mediate their linguistic repertoires.

Automated artifact removal from the electroencephalogram; a comparative study

Contamination of the electroencephalogram (EEG) by artifacts greatly reduces the quality of the recorded signals. There is a need for automated artifact removal methods. However, such methods are rarely evaluated against one another via rigorous criteria, with results often presented based upon visual inspection alone. This work presents a comparative study of automatic methods for removing blink, electrocardiographic, and electromyographic artifacts from the EEG. Three methods are considered; wavelet, blind source separation (BSS), and multivariate singular spectrum analysis (MSSA)-based correction. These are applied to data sets containing mixtures of artifacts. Metrics are devised to measure the performance of each method. The BSS method is seen to be the best approach for artifacts of high signal to noise ratio (SNR). By contrast, MSSA performs well at low SNRs but at the expense of a large number of false positive corrections.

Probing the mucoadhesive interactions between porcine gastric mucin and some water-soluble polymers

This study investigates the structural features of porcine gastric mucin (PGM) in aqueous dispersions and its interactions with water-soluble polymers (poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), poly(ethylene oxide), and poly(ethylene glycol)) using isothermal titration calorimetry, turbidimetric titration, dynamic light scattering, and transmission electron microscopy. It is established that PAA (450 kDa) and PMAA (100 kDa) exhibit strong specific interactions with PGM causing further aggregation of its particles, while PAA (2 kDa), poly(ethylene oxide) (1 000 kDa), and poly(ethylene glycol) (10 kDa) do not show any detectable effects on mucin. Sonication of mucin dispersions prior to their mixing with PAA (450 kDa) and PMAA (100 kDa) leads to more pronounced intensity of interactions.

On the threshold of adulthood: a new approach for the use of maturation indicators to assess puberty in adolescents from medieval England

Objectives: This study provides the first large scale analysis of the age at which adolescents in medieval England entered and completed the pubertal growth spurt. This new method has implications for expanding our knowledge of adolescent maturation across different time periods and regions. Methods: In total, 994 adolescent skeletons (10-25 years) from four urban sites in medieval England (AD 900-1550) were analysed for evidence of pubertal stage using new osteological techniques developed from the clinical literature (i.e. hamate hook development, CVM, canine mineralisation, iliac crest ossification, radial fusion). Results: Adolescents began puberty at a similar age to modern children at around 10-12 years, but the onset of menarche in girls was delayed by up to 3 years, occurring around 15 for most in the study sample and 17 years for females living in London. Modern European males usually complete their maturation by 16-18 years; medieval males took longer with the deceleration stage of the growth spurt extending as late as 21 years. Conclusions: This research provides the first attempt to directly assess the age of pubertal development in adolescents during the tenth to seventeenth centuries. Poor diet, infections, and physical exertion may have contributed to delayed development in the medieval adolescents, particularly for those living in the city of London. This study sheds new light on the nature of adolescence in the medieval period, highlighting an extended period of physical and social transition.

Assessing the performance of dynamical trajectory estimates

Estimating trajectories and parameters of dynamical systems from observations is a problem frequently encountered in various branches of science; geophysicists for example refer to this problem as data assimilation. Unlike as in estimation problems with exchangeable observations, in data assimilation the observations cannot easily be divided into separate sets for estimation and validation; this creates serious problems, since simply using the same observations for estimation and validation might result in overly optimistic performance assessments. To circumvent this problem, a result is presented which allows us to estimate this optimism, thus allowing for a more realistic performance assessment in data assimilation. The presented approach becomes particularly simple for data assimilation methods employing a linear error feedback (such as synchronization schemes, nudging, incremental 3DVAR and 4DVar, and various Kalman filter approaches). Numerical examples considering a high gain observer confirm the theory.

The influence of chronic conditions and the environment on pubertal development. An example from medieval England

Adolescence is a unique period in human development encompassing sexual maturation (puberty) and the physical and psychological transition into adulthood. It is a crucial time for healthy development and any adverse environmental conditions, poor nutrition, or chronic infection can alter the timing of these physical changes; delaying menarche in girls or the age of peak height velocity in boys. This study explores the impact of chronic illness on the tempo of puberty in 607 adolescent skeletons from medieval England (AD 900-1550). A total of 135 (22.2%) adolescents showed some delay in their pubertal development, and this lag increased with age. Of those with a chronic condition, 40.0% (n=24/60) showed delay compared to only 20.3% (n=111/547) of the non-pathology group. This difference was statistically significant. A binary logistic regression model demonstrated a significant association between increasing delay in pubertal stage attainment with age in the pathology group. This is the first time that chronic conditions have been directly associated with a delay in maturation in the osteological record, using a new method to assess stages of puberty in skeletal remains.