A combined experimental and theoretical study on p‐sulfonatocalix[4]arene encapsulated 7‐methoxycoumarin

Host‐guest interactions are essential in chemistry, biology, medicine and environmental science. In this combined experimental and theoretical contribution, the encapsulation of 7‐methoxycoumarin (herniarin, 7MC) with p‐sulfonatocalix[4]arene (p‐SC4) is studied using absorption and fluorescence spectroscopy, cyclic voltammetry and computational approaches. The 1:1 stoichiometry is confirmed using Job's plot. Our results show that the keto group of 7MC is the main source for electrochemical conversion of this complex. The excited state 7MC radiative decay is studied using time‐correlated single photon counting technique. The computed UV‐Vis absorption spectra for this complex at gas phase and solvent are online with the experimental spectra. Moreover, we determined the binding energy and the binding constant of the 7MC‐p‐SC4 complex. Density functional theory computations revealed that stabilization of the complex formed by p‐SC4 and 7MC is due to weak noncovalent and dispersive types of interactions. A comparison with encapsulation of amino acids by p‐SC4 is also conducted. Finally, we show that the flexibility of p‐SC4 and the weak nature of its interaction with 7MC are on the origin of the reversibility of encapsulation, which is mandatory for applications such as drug delivery.     

Cluster synchronization,switching and spatiotemporal coding in a phase oscillator network

A network of five globally-coupled identical phase oscillators is considered. Cluster states consisting of two synchronized pairs of oscillators and one singleton are investigated. Forcing the system with non-uniform constant inputs results in regular switches between cluster states. The resultant cyclic sequences of switches (spatiotemporal codes) are studied for different initial conditions and input configurations. Implications on information coding in neural systems are briefly discussed. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Asymmetric synthesis of alkaloids using polyfunctionalized chiral building blocks

Enantiopure N‐sulfinyl‐δ‐amino‐β‐ketoesters and isoquinolones, prepared from sulfinimines (N‐sulfinyl imines) are a new class of polyfunctionalized chiral building blocks. These building blocks provide easy access to enantiomerically pure, functionalized piperidines and tetrahydroisoquinolines with a minimum of chemical manipulation and protecting‐group chemistry. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:486–492, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10090     

Effect of A Sun Protection Intervention on the Immune Response to Measles Booster Vaccination in Infants in Rural South Africa

The incidence of many serious childhood infections can be reduced by vaccination. High sun exposure at the time of vaccination has been associated with a reduced antigen‐specific immune response. We hypothesized that providing sun protection advice and equipment to mothers of children who were waiting to be vaccinated would result in a more robust immunization response. We conducted a pilot study in 2015/2016 (data analyzed in 2017–2018) among 98 Black African children (~18 months of age) receiving the booster measles vaccination at two clinics in South Africa. Clinics were randomized to receive (or not) sun protection advice and equipment. We recorded demographic information on children and mothers and data on the child's usual sun exposure. At approximately 4 weeks’ postmeasles vaccination, we measured measles immunoglobulin G levels in children. All children with blood results (n = 87, 89%) across both groups had antibody titers higher than 200 mIU mL^?1 which was considered the protective antibody concentration. There was no statistically significant difference in titers between groups: geometric difference in mean titers 1.13 mIU mL^?1 (95% CI 0.85, 1.51; P = 0.39) and 1.38 mIU mL^?1 (95% CI 0.90, 2.11, P = 0.14) for unadjusted and adjusted analyses, respectively. This study demonstrated that a sun protection intervention study could be performed in a developing‐world pediatric vaccination setting. Although the sun protection intervention around the time of vaccination was not associated with a higher antibody level, given the potential importance of such an effect, a larger study should be considered.     

Effect of Particle Size on the Kinetics of Enzymatic Hydrolysis of Microcrystalline Cotton Cellulose: a Modeling and Simulation Study

Applied Biochemistry and Biotechnology - As the bioconversion of cellulosic substrate to fuels is essential to suppress the dependence on conventional fossil fuels, development of new improved...     

Differentially Private Significance Tests for Regression Coefficients

Many data producers seek to provide users access to confidential data without unduly compromising data subjects’ privacy and confidentiality. One general strategy is to require users to do analyses without seeing the confidential data; for example, analysts only get access to synthetic data or query systems that provide disclosure-protected outputs of statistical models. With synthetic data or redacted outputs, the analyst never really knows how much to trust the resulting findings. In particular, if the user did the same analysis on the confidential data, would regression coefficients of interest be statistically significant or not? We present algorithms for assessing this question that satisfy differential privacy. We describe conditions under which the algorithms should give accurate answers about statistical significance. We illustrate the properties of the proposed methods using artificial and genuine data. Supplementary materials for this article are available online.     

Water structure and mobility in acrylamide copolymer glycohydrogels with galactose and siloxane pendant groups

Glycohydrogels containing 2′‐acrylamidoethyl‐β‐d ‐galactopyranoside and varying levels of N,N′ methylene bisacrylamide and 3‐acrylamidopropyltris(trimethylsiloxy)silane were synthesized to determine the effects of crosslinker and amphipathic balance on equilibrium water content (EWC), bound water population, and hydrogen bonding dynamics at the water–polymer interface. Analogous dimethylacrylamide hydrogels were synthesized for comparison with a system containing lower hydrogen bonding propensity. An approach combining experiment (proton nuclear magnetic resonance, thermogravimetric analysis, differential scanning calorimetry, and dynamic vapor sorption analysis) and molecular dynamics simulations was employed to examine the relationship between bulk hydrogel properties, molecular water mobility, and hydrogen bonding characteristics. It was found that copolymer composition (hydrophobic content) and crosslink concentration in high water content glycohydrogels affect EWC, and by extension, structural water population. The organization of water at the polymer interface is greatly impacted by the surrounding environment, where hindered molecular water mobility promotes water–polymer binding and decreases water–water clustering. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 584–597     

SR-FTIR spectroscopy of renal epithelial carcinoma side population cells displaying stem cell-like characteristics

It is hypothesized that cells with stem cell-like properties may be influential in carcinogenesis, possessing the ability to self-renew, produce differentiated daughter cells and resist environmental or therapeutic injury. This has led to a surge in interest in identifying and characterizing the tumour initiating or cancer stem cell (CSC) with the aim of discovering novel diagnostic and prognostic markers and of understanding the basic biology with the ultimate aim of generating new therapeutic approaches and biomarkers. However, a major hurdle to this process has been the lack of a truly specific cancer stem cell biomarker allied to the rarity of these cells. This has led to problems in characterising these CSCs by traditional '-omic' techniques. Using a renal carcinoma cell line model, we show that synchrotron radiation-Fourier transform infrared (SR-FTIR) spectroscopy is a suitable tool to measure discrete differences in the biochemistry of small numbers of single-cells. Using the chemometric techniques of Principal Component and Linear Discriminant Analysis (PCA and LDA) for multivariate reduction, biochemical differences between the cells from different sub-populations were evaluated. Results found lipid and phosphodiester vibrations to be particularly good discriminating markers in the spectra of these stem-like cells, relative to the more differentiated, proliferating cells that make up the majority of the cell population.     

Diffusion tensor imaging in horizontal gaze palsywith progressive scoliosis

Horizontal gaze palsy with progressive scoliosis (HGPPS) is a rare disorder characterized by absence of conjugate horizontal eye movements, preservation of vertical gaze and convergence, progressive scoliosis developing in childhood and adolescence. It is caused by mutations in the ROBO3 gene which are critical for the crossing of long ascending medial lemniscal and descending corticospinal tracts in the medulla. Diffusion tensor imaging on a 14-year-old boy with HGPPS revealed ipsilateral ascending and descending connectivity in the brainstem without any crossing over of the major tracts although normal interhemispheric connections in the corpus callosum was demonstrable. Absent decussation of smaller sized superior cerebellar peduncles but with normal crossing over of the middle cerebellar peduncle was also observed. Tractography is a valuable investigative modality to assess neuronal connections in the brain and is a useful adjunct to the structural magnetic resonance imaging in confirming the diagnosis of HGPPS.