Hydrogen-bonded supramolecular polymers as self-healing hydrogels: Effect of a bulky adamantyl substituent in the ureido-pyrimidinone monomer

In an attempt to generate supramolecular assemblies able to function as self-healing hydrogels, a novel ureido-pyrimidinone (UPy) monomer, 2-(N ′-methacryloyloxyethylureido)-6-(1-adamantyl)-4[1H]-pyrimidinone, was synthesized and then copolymerized with N,N-dimethylacrylamide at four different feed compositions, using a solution of lithium chloride in N,N-dimethylacetamide as the polymerization medium. The assembling process in the resulting copolymers is based on crosslinking through the reversible quadruple hydrogen bonding between side-chain UPy modules. The adamantyl substituent was introduced in order to create a “hydrophobic pocket” that may protect the hydrogen bonds against the disruptive effect of water molecules. Upon hydration to equilibrium, all copolymers generated typical hydrogels when their concentration in the hydrated system was at least 15%. The small-deformation rheometry showed that all hydrated copolymers were hydrogels that maintained a solid-like behavior, and that their extrusion through a syringe needle did not affect significantly this behavior, suggesting a self-healing capacity in these materials. An application as injectable substitutes for the eye's vitreous humor was proposed

A compliant, banded outflow cannula for decreased afterload sensitivity of rotary right ventricular assist devices

Biventricular support with dual rotary ventricular assist devices (VADs) has been implemented clinically with restriction of the right VAD (RVAD) outflow cannula to artificially increase afterload and, therefore, operate within recommended design speed ranges. However, the low preload and high afterload sensitivity of these devices increase the susceptibility of suction events. Active control systems are prone to sensor drift or inaccurate inferred (sensor-less) data, therefore an alternative solution may be of benefit. This study presents the in vitro evaluation of a compliant outflow cannula designed to passively decrease the afterload sensitivity of rotary RVADs and minimize left-sided suction events. A one-way fluid-structure interaction model was initially used to produce a design with suitable flow dynamics and radial deformation. The resultant geometry was cast with different initial cross-sectional restrictions and concentrations of a softening diluent before evaluation in a mock circulation loop. Pulmonary vascular resistance (PVR) was increased from 50 dyne s/cm5 until left-sided suction events occurred with each compliant cannula and a rigid, 4.5 mm diameter outflow cannula for comparison. Early suction events (PVR ∼ 300 dyne s/cm5) were observed with the rigid outflow cannula. Addition of the compliant section with an initial 3 mm diameter restriction and 10% diluent expanded the outflow restriction as PVR increased, thus increasing RVAD flow rate and preventing left-sided suction events at PVR levels beyond 1000 dyne s/cm5. Therefore, the compliant, restricted outflow cannula provided a passive control system to assist in the prevention of suction events with rotary biventricular support while maintaining pump speeds within normal ranges of operation.

Click functionalization of methacrylate-based hydrogels and their cellular response

Methacrylate-based hydrogels, such as homo- and copolymers of 2-hydroxyethyl methacrylate (HEMA), have demonstrated significant potential for use in biomedical applications. However, many of these hydrogels tend to resist cell attachment and growth at their surfaces, which can be detrimental for certain applications. In this article, glycidyl methacrylate (GMA) was copolymerized with HEMA to generate gels functionalized with epoxide groups. The epoxides were then functionalized by two sequential click reactions, namely, nucleophilic ring opening of epoxides with sodium azide and then coupling of small molecules and peptides via Huisgen's copper catalyzed 1,3-dipolar cycloaddition of azides with alkynes. Using this strategy it was possible to control the degree of functionalization by controlling the feed ratio of monomers during polymerization. In vitro cell culture of human retinal pigment epithelial cell line (ARPE-19) with the hydrogels showed improved cell adhesion, growth and proliferation for hydrogels that were functionalized with a peptide containing the RGD sequence. In addition, the cell attachment progressively decreased with increasing densities of the RGD containing peptide. In summary, a facile methodology has been presented that gives rise to hydrogels with controlled degrees of functionality, such that the cell response is directly related to the levels and nature of that functionality.

Ultrasonic Degradation of Poly(acrylic acid)

The ultrasonic degradation of poly(acrylic acid), a water-soluble polymer, was studied in the presence of persulfates at different temperatures in binary solvent Mixtures of methanol and water. The degraded samples were analyzed by gel permeation chromatography for the time evolution of the molecular weight distributions. A continuous distribution kinetics model based on midpoint chain scission was developed, and the degradation rate coefficients were determined. The decline in the rate of degradation of poly(acrylic acid) with increasing temperature and with an increment in the methanol content in the binary solvent mixture of methanol and water was attributed to the increased vapor pressure of the solutions. The experimental data showed an augmentation of the degradation rate of the polymer with increasing oxidizing agent (persulfate) concentrations. Different concentrations of three persulfates-potassium persulfate, ammonium persulfate, and sodium persulfate-were used. It was found that the ratio of the polymer degradation rate coefficient to the dissociation rate constant of the persulfate was constant. This implies that the ultrasonic degradation rate of poly(acrylic acid) can be determined a priori in the presence of any initiator.

Feasibility of autologous bone marrow mesenchymal stem cell-derived extracellular matrix scaffold for cartilage tissue engineering

Extracellular matrix (ECM) materials are widely used in cartilage tissue engineering. However, the current ECM materials are unsatisfactory for clinical practice as most of them are derived from allogenous or xenogenous tissue. This study was designed to develop a novel autologous ECM scaffold for cartilage tissue engineering. The autologous bone marrow mesenchymal stem cell-derived ECM (aBMSC-dECM) membrane was collected and fabricated into a three-dimensional porous scaffold via cross-linking and freeze-drying techniques. Articular chondrocytes were seeded into the aBMSC-dECM scaffold and atelocollagen scaffold, respectively. An in vitro culture and an in vivo implantation in nude mice model were performed to evaluate the influence on engineered cartilage. The current results showed that the aBMSC-dECM scaffold had a good microstructure and biocompatibility. After 4 weeks in vitro culture, the engineered cartilage in the aBMSC-dECM scaffold group formed thicker cartilage tissue with more homogeneous structure and higher expressions of cartilaginous gene and protein compared with the atelocollagen scaffold group. Furthermore, the engineered cartilage based on the aBMSC-dECM scaffold showed better cartilage formation in terms of volume and homogeneity, cartilage matrix content, and compressive modulus after 3 weeks in vivo implantation. These results indicated that the aBMSC-dECM scaffold could be a successful novel candidate scaffold for cartilage tissue engineering.

Approaches to selecting native plant replacements for fleshy-fruited invasive species

Invasive plants are a serious threat to biodiversity. Yet, in some cases, they may play an important ecological role in heavily modified landscapes, such as where fleshy-fruited invasive plants support populations of native frugivores. How can such conservation conflicts be managed? We advocate an approach in which native fleshy-fruited plants are ranked on their ability to provide the fruit food resources for native frugivores currently being provided by invasive plants. If these native taxa are preferentially used, where ecologically appropriate, in plantings for restoration and in park and garden settings, they could help support native frugivore populations in the event of extensive invasive plant control. We develop and critically examine six approaches to selecting candidate native plant taxa: a multivariate approach based on the frugivore assemblage, a scoring model, and several multivariate approaches (including trait combinations having the greatest correlation with the diet of the native frugivore assemblage) based on the functional traits of fruit morphology, phenology, conspicuousness, and accessibility. To illustrate these approaches, we use a case study with Bitou bush (Chrysanthemoides monilifera subsp. rotundata) (Asteraceae), an Australian Weed of National Significance. The model using a dissimilarity value generated from all available traits identified a set of species used by the frugivores of C. monilifera more than null models. A replacement approach using species ranked by either all traits available or the frugivore community appears best suited to guide selection of plants in restoration practice.

Choosing a model of maternity care: decision support needs of Australian women

- BACKGROUND Access to information on the features and outcomes associated with the various models of maternity care available in Australia is vital for women's informed decision-making. This study sought to identify women's preferences for information access and decision-making involvement, as well as their priority information needs, for model of care decision-making. - METHODS A convenience sample of adult women of childbearing age in Queensland, Australia were recruited to complete an online survey assessing their model of care decision support needs. Knowledge on models of care and socio-demographic characteristics were also assessed. - RESULTS Altogether, 641 women provided usable survey data. Of these women, 26.7 percent had heard of all available models of care before starting the survey. Most women wanted access to information on models of care (90.4%) and an active role in decision-making (99.0%). Nine priority information needs were identified: cost, access to choice of mode of birth and care provider, after hours provider contact, continuity of carer in labor/birth, mobility during labor, discussion of the pros/cons of medical procedures, rates of skin-to-skin contact after birth, and availability at a preferred birth location. This information encompassed the priority needs of women across age, birth history, and insurance status subgroups. - CONCLUSIONS This study demonstrates Australian women's unmet needs for information that supports them to effectively compare available options for model of maternity care. Findings provide clear direction on what information should be prioritized and ideal channels for information access to support quality decision-making in practice.

Electrical conduction in plasma polymerized thin films of γ-terpinene

Plasma polymerized c-terpinene (pp2GT) thin films are fabricated using RF plasma polymerization. MIM structures are fabricated and using the capacitive structures dielectric properties of the material is studied. The dielectric constant values are found to be in good agreement with those determined from ellipsometric data. At a frequency of 100 kHz, the dielectric constant varies with RF deposition power, from 3.69 (10 W) to 3.24 (75 W). The current density–voltage (J2V) characteristics of pp–GT thin films are investigated as a function of RF deposition power at room temperature to determine the resistivity and DC conduction mechanism of the films. At higher applied voltage region, Schottky conduction is the dominant DC conduction mechanism. The capacitance and the loss tangent are found to be frequency dependent. The conductivity of the pp2GT thin films is found to decrease from 1.39 3 10212 S/cm (10 W) to 1.02 3 10213 S/cm (75 W) and attributed to the change in the chemical composition and structure of the polymer. The breakdown field for pp–GT thin films increases from 1.48 MV/cm (10 W) to 2 MV/cm (75 W). A single broad relaxation peak is observed indicating the contribution of multiple relaxations to the dielectric response for temperature dependent J2V. The distribution of these relaxation times is determined through regularization methods. VC 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42318.

Nonparametric traversability estimation in partially occluded and deformable terrain

Terrain traversability estimation is a fundamental requirement to ensure the safety of autonomous planetary rovers and their ability to conduct long-term missions. This paper addresses two fundamental challenges for terrain traversability estimation techniques. First, representations of terrain data, which are typically built by the rover’s onboard exteroceptive sensors, are often incomplete due to occlusions and sensor limitations. Second, during terrain traversal, the rover-terrain interaction can cause terrain deformation, which may significantly alter the difficulty of traversal. We propose a novel approach built on Gaussian process (GP) regression to learn, and consequently to predict, the rover’s attitude and chassis configuration on unstructured terrain using terrain geometry information only. First, given incomplete terrain data, we make an initial prediction under the assumption that the terrain is rigid, using a learnt kernel function. Then, we refine this initial estimate to account for the effects of potential terrain deformation, using a near-to-far learning approach based on multitask GP regression. We present an extensive experimental validation of the proposed approach on terrain that is mostly rocky and whose geometry changes as a result of loads from rover traversals. This demonstrates the ability of the proposed approach to accurately predict the rover’s attitude and configuration in partially occluded and deformable terrain.

Information flow, trading activity and commodity futures volatility

Based on unique news data relating to gold and crude oil, we investigate how news volume and sentiment, shocks in trading activity, market depth and trader positions unrelated to information flow covary with realized volatility. Positive shocks to the rate of news arrival, and negative shocks to news sentiment exhibit the largest effects. After controlling for the level of news flow and cross-correlations, net trader positions play only a minor role. These findings are at odds with those of [Wang (2002a). The Journal of Futures Markets, 22, 427–450; Wang (2002b). The Financial Review, 37, 295–316], but are consistent with the previous literature which doesn't find a strong link between volatility and trader positions.

Natural Abundant Solid State NMR Studies in Designed Tripeptides for Differentiation of Multiple Conformers

Solid state NMR (SSNMR) experiments on heteronuclei in natural abundance are described for three synthetically designed tripeptides Piv-(L)Pro_(L)Pro-(L)Phe-OMe (1), Piv-(D)Pro_(L)Pro_(L)Phe-OMe (2), and Piv-(D)Pro_(L)Pro_(L)Phe-NHMe (3). These peptides exist in different conformation as shown by solution state NMR and single crystal X-ray analysis (Chatterjee et al., Chem Eur J 2008, 14, 6192). In this study, SSNMR has been used to probe the conformations of these peptides in their powder form. The C-13 spectrum of peptide (1) showed doubling of resonances corresponding to cis/cis form, unlike in solution where the similar doubling is attributed to cis/trans form. This has been confirmed by the chemical shift differences of C-beta and C-gamma carbon of Proline in peptide (1) both in solution and SSNMR. Peptide (2) and (3) provided single set of resonances which represented all transform across the di-Proline segment. The results are In agreement with the X-ray analysis. Solid state N-15 resonances, especially from Proline residues provided additional information, which is normally not observable in solution state NMR. H-1 chemical shifts are also obtained from a two-dimensional heteronuclear correlation experiment between H-1-C-13. The results confirm the utility of NMR as a useful tool for identifying different conformers in peptides in the solid state. (C) 2009 Wiley Periodicals, Inc. Biopolymers 91: 851-860, 2009.

Three-dimensional reconstruction of black tiger prawn (Penaeus monodon) spermatozoa using serial block-face scanning electron microscopy

Serial Block-Face Scanning Electron Microscopy (SBF-SEM) was used in this study to examine the ultrastructural morphology of Penaeus monodon spermatozoa. SBF-SEM provided a large dataset of sequential electron-microscopic-level images that facilitated comprehensive ultrastructural observations and three-dimensional reconstructions of the sperm cell. Reconstruction divulged a nuclear region of the spermatophoral spermatozoon filled with decondensed chromatin but with two apparent levels of packaging density. In addition, the nuclear region contained, not only numerous filamentous chromatin elements with dense microregions, but also large centrally gathered granular masses. Analysis of the sperm cytoplasm revealed the presence of degenerated mitochondria and membrane-less dense granules. A large electron-lucent vesicle and "arch-like" structures were apparent in the subacrosomal area, and an acrosomal core was found in the acrosomal vesicle. The spermatozoal spike arose from the inner membrane of the acrosomal vesicle, which was slightly bulbous in the middle region of the acrosomal vesicle, but then extended distally into a broad dense plate and to a sharp point proximally. This study has demonstrated that SBF-SEM is a powerful technique for the 3D ultrastructural reconstruction of prawn spermatozoa, that will no doubt be informative for further studies of sperm assessment, reproductive pathology and the spermiocladistics of penaeid prawns, and other decapod crustaceans. J. Morphol., 2016. (c) 2016 Wiley Periodicals, Inc.

Juutalaisvastaisuus suomalaisissa aikakauslehdissä ja kirjallisuudessa 1918-1944

Anti-Semitism existed in Finland during the whole period covered by this study. The immoral acts associated with Jews in the articles were mostly regarded as universal habits, qualities and/or modes of action, that is, unconnected with any particular Finnish Jew. Researchers have tried to explain anti-Semitism in several ways. The theory of Jews as outsiders has been a popular explanation as well as xenophobia, chimerical anti-Semitism and the socio-economic models. The main sources of this study have been over 400 Finnish periodicals and magazines, literature and text books published between 1918 and 1944. This vast number of magazines includes those of the army and the civil guard, religion, humour and the papers of the Finnish extreme right. One can see a distinct foreign and especially German influence in the subjects and phraseology of Finnish anti-Semitic writings between 1918 and 1944. Several known Finnish anti-Semitic writers had some kind of link with Germany. Some Finnish organisations and societies were openly anti-Semitic during this period. There had been cycles in the activity of anti-Semitic writing in Finland, obvious peaks appearing in 1918 1919, 1929 1931, 1933 1938 and 1942 1944. The reason for the 1918 1919 activity was the civil rights which were granted to the Jews in Finland, and the Russian Bolshevik revolution. The worldwide depression from 1929 to 1932 seem to be the reason for new anti-Semitic writing activity. The rise of National Socialism in Germany and the influence this phenomenon had in Finland was the reason for the peak during 1933 1938. During the continuation war 1942 1944 National Socialist Germany was fighting side-by-side with Finland and their anti-Semitic propaganda found easier access to Finland. Of the 433 magazines, journals and newspapers which were used in this study, 71 or 16.4 per cent had at least one article that can be identified as anti-Semitic; especially the magazines of national socialists and other extreme right parties were making anti-Semitic annotations. There were about 50 people known to have written anti-Semitic articles. At least half of these known writers had studied at the university, including as many as 10 priests. Over and above these, there was an even larger number of people who wrote under a pseudonym. The material used suggested that anti-Semitism was not very popular in Finland between 1918 and 1944. Anti-Semitic articles appeared mostly in the magazines of the extreme right, but their circulation was not very large. A proof of the slight influence of these extreme right anti-Semitic ideas is that, beside the tightening of policy towards Jewish immigrants in 1938 and the handing over of eight of these refugees to Germany in 1942, the official policy of Finland never became anti-Semitic. As was stated before, despite the cycles in the number of writings, there does not appear to have been any noticeable change in public opinion. One must also remember that most Finns had not at that period actually met a Jew. The material used suggests that between 1918 and 1944 the so-called Jewish question was seemingly unimportant for most Finns and their attitude to Jews and Jewishness can be described as neutral.

Molecular dynamics simulation of the phosphorylation-induced conformational changes of a tau peptide fragment

Aggregation of the microtubule associated protein tau (MAPT) within neurons of the brain is the leading cause of tauopathies such as Alzheimer's disease. MAPT is a phospho-protein that is selectively phosphorylated by a number of kinases in vivo to perform its biological function. However, it may become pathogenically hyperphosphorylated, causing aggregation into paired helical filaments and neurofibrillary tangles. The phosphorylation induced conformational change on a peptide of MAPT (htau225−250) was investigated by performing molecular dynamics simulations with different phosphorylation patterns of the peptide (pThr231 and/or pSer235) in different simulation conditions to determine the effect of ionic strength and phosphate charge. All phosphorylation patterns were found to disrupt a nascent terminal β-sheet pattern (226VAVVR230 and 244QTAPVP249), replacing it with a range of structures. The double pThr231/pSer235 phosphorylation pattern at experimental ionic strength resulted in the best agreement with NMR structural characterization, with the observation of a transient α-helix (239AKSRLQT245). PPII helical conformations were only found sporadically throughout the simulations. Proteins 2014; 82:1907–1923. © 2014 Wiley Periodicals, Inc.

Free energy calculations of the interactions of c-Jun-based synthetic peptides with the c-Fos protein

The c-Fos–c-Jun complex forms the activator protein 1 transcription factor, a therapeutic target in the treatment of cancer. Various synthetic peptides have been designed to try to selectively disrupt the interaction between c-Fos and c-Jun at its leucine zipper domain. To evaluate the binding affinity between these synthetic peptides and c-Fos, polarizable and nonpolarizable molecular dynamics (MD) simulations were conducted, and the resulting conformations were analyzed using the molecular mechanics generalized Born surface area (MM/GBSA) method to compute free energies of binding. In contrast to empirical and semiempirical approaches, the estimation of free energies of binding using a combination of MD simulations and the MM/GBSA approach takes into account dynamical properties such as conformational changes, as well as solvation effects and hydrophobic and hydrophilic interactions. The predicted binding affinities of the series of c-Jun-based peptides targeting the c-Fos peptide show good correlation with experimental melting temperatures. This provides the basis for the rational design of peptides based on internal, van der Waals, and electrostatic interactions.