811 research outputs found

    Probing structural relaxation in complex fluids by critical fluctuations

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    Complex fluids, such as polymer solutions and blends, colloids and gels, are of growing interest in fundamental and applied soft-condensed-matter science. A common feature of all such systems is the presence of a mesoscopic structural length scale intermediate between atomic and macroscopic scales. This mesoscopic structure of complex fluids is often fragile and sensitive to external perturbations. Complex fluids are frequently viscoelastic (showing a combination of viscous and elastic behaviour) with their dynamic response depending on the time and length scales. Recently, non-invasive methods to infer the rheological response of complex fluids have gained popularity through the technique of microrheology, where the diffusion of probe spheres in a viscoelastic fluid is monitored with the aid of light scattering or microscopy. Here we propose an alternative to traditional microrheology that does not require doping of probe particles in the fluid (which can sometimes drastically alter the molecular environment). Instead, our proposed method makes use of the phenomenon of "avoided crossing" between modes associated with the structural relaxation and critical fluctuations that are spontaneously generated in the system.Comment: 4 pages, 4 figure

    Unraveling Substituent Effects on the Glass Transition Temperatures of Biorenewable Polyesters

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    Converting biomass-based feedstocks into polymers not only reduces our reliance on fossil fuels, but also furnishes multiple opportunities to design biorenewable polymers with targeted properties and functionalities. Here we report a series of high glass transition temperature (Tg up to 184 °C) polyesters derived from sugar-based furan derivatives as well as a joint experimental and theoretical study of substituent effects on their thermal properties. Surprisingly, we find that polymers with moderate steric hindrance exhibit the highest Tg values. Through a detailed Ramachandran-type analysis of the rotational flexibility of the polymer backbone, we find that additional steric hindrance does not necessarily increase chain stiffness in these polyesters. We attribute this interesting structure-property relationship to a complex interplay between methylinduced steric strain and the concerted rotations along the polymer backbone. We believe that our findings provide key insight into the relationship between structure and thermal properties across a range of synthetic polymers

    A Comprehensive Examination of the Immediate Recovery of Children Following Tonsillectomy and Adenoidectomy

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    Objectives Using multiple well-validated measures and a large sample size, the goal of this paper was to describe the immediate clinical and behavioral recovery of children following tonsillectomy with or without an adenoidectomy (T&A) during the first two weeks following surgery. Study design Observational, longitudinal study. Setting Four major pediatric hospitals in the U.S. consisting of Children\u27s Hospital of Orange County, Children\u27s Hospital of Los Angeles, Lucile Packard Children\u27s Hospital, and Children\u27s Hospital Colorado. Subjects and Methods: Participants included 827 patients between 2 and 15 years of age who underwent tonsillectomy with or without adenoidectomy surgery. Baseline and demographic information were gathered prior to surgery, and measures of clinical, behavioral, and physical recovery were recorded immediately following and up through two weeks after surgery. Results Pain following T&A was clinically significant through the first post-operative week and nearly resolved by the end of the second week. Negative behavioral changes were highly prevalent after surgery (75.6% of children at Day 0) through the first week (63.9% at Week 1), and over 20% of children continued to evidence new onset negative behavioral changes at two weeks post-operatively. Children were rated as experiencing significant functional impairment in the immediate three days following surgery and most children returned to baseline functioning by the end of the second week. Conclusions Results of this study suggest that children show immediate impairment in functioning and experience clinically significant pain throughout the first week following T&A, and new onset maladaptive behavioral changes persisting even up to the two-week assessment period

    Reflecting diffusions and hyperbolic Brownian motions in multidimensional spheres

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    Diffusion processes (Xd(t))t0(\underline{\bf X}_d(t))_{t\geq 0} moving inside spheres SRdRdS_R^d \subset\mathbb{R}^d and reflecting orthogonally on their surfaces SRd\partial S_R^d are considered. The stochastic differential equations governing the reflecting diffusions are presented and their kernels and distributions explicitly derived. Reflection is obtained by means of the inversion with respect to the sphere SRdS_R^d. The particular cases of Ornstein-Uhlenbeck process and Brownian motion are examined in detail. The hyperbolic Brownian motion on the Poincar\`e half-space Hd\mathbb{H}_d is examined in the last part of the paper and its reflecting counterpart within hyperbolic spheres is studied. Finally a section is devoted to reflecting hyperbolic Brownian motion in the Poincar\`e disc DD within spheres concentric with DD

    Constructal blade shape in nanofluids

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    Blade configuration of nanofluids has been proven to perform much better than dispersed configuration for some heat conduction systems. The analytical analysis and numerical calculation are made for the cylinder--shaped and regular-rectangular-prism--shaped building blocks of the blade-configured heat conduction systems (using nanofluids as the heat conduction media) to find the optimal cross-sectional shape for the nanoparticle blade under the same composing materials, composition ratio, volumetric heat generation rate, and total building block volume. The regular-triangular-prism--shaped blade has been proven to perform better than all the other three kinds of blades, namely, the regular-rectangular-prism--shaped blade, the regular-hexagonal-prism--shaped blade, and the cylinder--shaped blade. Thus, the regular-triangular-prism--shaped blade is selected as the optimally shaped blade for the two kinds of building blocks that are considered in this study. It is also proven that the constructal cylinder--regular-triangular-prism building block performs better than the constructal regular-rectangular-prism--regular-triangular-prism building block

    Essential and checkpoint functions of budding yeast ATM and ATR during meiotic prophase are facilitated by differential phosphorylation of a meiotic adaptor protein, Hop1

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    A hallmark of the conserved ATM/ATR signalling is its ability to mediate a wide range of functions utilizing only a limited number of adaptors and effector kinases. During meiosis, Tel1 and Mec1, the budding yeast ATM and ATR, respectively, rely on a meiotic adaptor protein Hop1, a 53BP1/Rad9 functional analog, and its associated kinase Mek1, a CHK2/Rad53-paralog, to mediate multiple functions: control of the formation and repair of programmed meiotic DNA double strand breaks, enforcement of inter-homolog bias, regulation of meiotic progression, and implementation of checkpoint responses. Here, we present evidence that the multi-functionality of the Tel1/Mec1-to-Hop1/Mek1 signalling depends on stepwise activation of Mek1 that is mediated by Tel1/Mec1 phosphorylation of two specific residues within Hop1: phosphorylation at the threonine 318 (T318) ensures the transient basal level Mek1 activation required for viable spore formation during unperturbed meiosis. Phosphorylation at the serine 298 (S298) promotes stable Hop1-Mek1 interaction on chromosomes following the initial phospho-T318 mediated Mek1 recruitment. In the absence of Dmc1, the phospho-S298 also promotes Mek1 hyper-activation necessary for implementing meiotic checkpoint arrest. Taking these observations together, we propose that the Hop1 phospho-T318 and phospho-S298 constitute key components of the Tel1/Mec1- based meiotic recombination surveillance (MRS) network and facilitate effective coupling of meiotic recombination and progression during both unperturbed and challenged meiosis

    DRAM-3 modulates autophagy and promotes cell survival in the absence of glucose

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    Macroautophagy is a membrane-trafficking process that delivers cytoplasmic constituents to lysosomes for degradation. The process operates under basal conditions as a mechanism to turnover damaged or misfolded proteins and organelles. As a result, it has a major role in preserving cellular integrity and viability. In addition to this basal function, macroautophagy can also be modulated in response to various forms of cellular stress, and the rate and cargoes of macroautophagy can be tailored to facilitate appropriate cellular responses in particular situations. The macroautophagy machinery is regulated by a group of evolutionarily conserved autophagy-related (ATG) proteins and by several other autophagy regulators, which either have tissue-restricted expression or operate in specific contexts. We report here the characterization of a novel autophagy regulator that we have termed DRAM-3 due to its significant homology to damage-regulated autophagy modulator (DRAM-1). DRAM-3 is expressed in a broad spectrum of normal tissues and tumor cells, but different from DRAM-1, DRAM-3 is not induced by p53 or DNA-damaging agents. Immunofluorescence studies revealed that DRAM-3 localizes to lysosomes/autolysosomes, endosomes and the plasma membrane, but not the endoplasmic reticulum, phagophores, autophagosomes or Golgi, indicating significant overlap with DRAM-1 localization and with organelles associated with macroautophagy. In this regard, we further proceed to show that DRAM-3 expression causes accumulation of autophagosomes under basal conditions and enhances autophagic flux. Reciprocally, CRISPR/Cas9-mediated disruption of DRAM-3 impairs autophagic flux confirming that DRAM-3 is a modulator of macroautophagy. As macroautophagy can be cytoprotective under starvation conditions, we also tested whether DRAM-3 could promote survival on nutrient deprivation. This revealed that DRAM-3 can repress cell death and promote long-term clonogenic survival of cells grown in the absence of glucose. Interestingly, however, this effect is macroautophagy-independent. In summary, these findings constitute the primary characterization of DRAM-3 as a modulator of both macroautophagy and cell survival under starvation conditions
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