Biodegradable and Biocompatible PDLLA-PEG1k-PDLLA Diacrylate Macromers:Synthesis, Characterisation and Preparation of Soluble Hyperbranched Polymers and Crosslinked Hydrogels

A series of PDLLA-PEG1k-PDLLA tri-block co-polymers with various compositions, i.e., containing 2–10 lactoyl units, were prepared via ring opening polymerisation of d,l-lactide in the presence of poly (ethylene glycol) (PEG) (Mn = 1000 g·mol−1) as the initiator and stannous 2-ethylhexanoate as the catalyst at different feed ratios. PDLLA-PEG1k-PDLLA co-polymers were then functionalised with acrylate groups using acryloyl chloride under various reaction conditions. The diacrylated PDLLA-PEG1k-PDLLA (diacryl-PDLLA-PEG1k-PDLLA) were further polymerised to synthesize soluble hyperbranched polymers by either homo-polymerisation or co-polymerisation with poly(ethylene glycol) methyl ether methylacrylate (PEGMEMA) via free radical polymerisation. The polymer samples obtained were characterised by 1H NMR (proton Nuclear Magnetic Resonance), FTIR (Fourier Transform Infra-red spectroscopy), and GPC (Gel Permeation Chromatography). Moreover, the diacryl-PDLLA-PEG1k-PDLLA macromers were used for the preparation of biodegradable crosslinked hydrogels through the Michael addition reaction and radical photo-polymerisation with or without poly(ethylene glycol) methyl ether methylacrylate (PEGMEMA, Mn = 475 g·mol−1) as the co-monomer. It was found that fine tuning of the diacryl-PDLLA-PEG1k-PDLLA constituents and its combination with co-monomers resulted in hydrogels with tailored swelling properties. It is envisioned that soluble hyperbranched polymers and crosslinked hydrogels prepared from diacryl-PDLLA-PEG1k-PDLLA macromers can have promising applications in the fields of nano-medicines and regenerative medicines

Magnetic fluctuations and superconducting properties of CaKFe4As4 studied by 75As NMR

We report $^{75}$As nuclear magnetic resonance (NMR) studies on a new iron-based superconductor CaKFe$_4$As$_4$ with $T_{\rm c}$ = 35 K. $^{75}$As NMR spectra show two distinct lines corresponding to the As(1) and As(2) sites close to the K and Ca layers, respectively, revealing that K and Ca layers are well ordered without site inversions. We found that nuclear quadrupole frequencies $\nu_{\rm Q}$ of the As(1) and As(2) sites show an opposite temperature ($T$) dependence. Nearly $T$ independent behavior of the Knight shifts $K$ are observed in the normal state, and a sudden decrease in $K$ in the superconducting (SC) state clearly evidences spin-singlet Cooper pairs. $^{75}$As spin-lattice relaxation rates 1/$T_1$ show a power law $T$ dependence with different exponents for the two As sites. The isotropic antiferromagnetic spin fluctuations characterized by the wavevector ${\bf q}$ = ($\pi$, 0) or (0, $\pi$) in the single-iron Brillouin zone notation are revealed by 1/$T_1T$ and $K$ measurements. Such magnetic fluctuations are necessary to explain the observed temperature dependence of the $^{75}$As quadrupole frequencies, as evidenced by our first-principles calculations. In the SC state, 1/$T_1$ shows a rapid decrease below $T_{\rm c}$ without a Hebel-Slichter peak and decreases exponentially at low $T$, consistent with an $s^{\pm}$ nodeless two-gap superconductor.Comment: 9 pages, 6 figures, accepted for publication in Phys.Rev.

Activity of newest generation β-lactam/β-lactamase inhibitor combination therapies against multidrug resistant Pseudomonas aeruginosa

Multidrug resistant (MDR) P. aeruginosa accounts for 35 % of all P. aeruginosa isolated from respiratory samples of patients with cystic fibrosis (CF). The usefulness of β-lactam antibiotics for treating CF, such as carbapenems and later generation cephalosporins, is limited by the development of antibacterial resistance. A proven treatment approach is the combination of a β-lactam antibiotic with a β-lactamase inhibitor. New β-lactam/β-lactamase inhibitor combinations are available, but data are lacking regarding the susceptibility of MDR CF-associated P. aeruginosa (CFPA) to these new combination therapies. In this study we determined MIC values for three new combinations; imipenem-relebactam (I-R), ceftazidime-avibactam (CZA), and ceftolozane-tazobactam (C/T) against MDR CFPA (n = 20). The MIC90 of I-R, CZA, and C/T was 64/4, 32/4, and 16/8 (all µg/mL), respectively. The susceptibility of isolates to imipenem was not significantly improved with the addition of relebactam (p = 0.68). However, susceptibility to ceftazidime was significantly improved with the addition of avibactam (p \u3c 0.01), and the susceptibility to C/T was improved compared to piperacillin/tazobactam (p \u3c 0.05) These data provide in vitro evidence that I-R may not be any more effective than imipenem monotherapy against MDR CFPA. The pattern of susceptibility observed for CZA and C/T in the current study was similar to data previously reported for non-CF-associated MDR P. aeruginosa

Thermoresponsive and Reducible Hyperbranched Polymers Synthesized by RAFT Polymerisation

Here, we report the synthesis of new thermoresponsive hyperbranched polymers (HBPs) via one-pot reversible addition-fragmentation chain transfer (RAFT) copolymerisation of poly(ethylene glycol)methyl ether methacrylate (PEGMEMA, Mn = 475 g/mol), poly(propylene glycol)methacrylate (PPGMA, Mn = 375 g/mol), and disulfide diacrylate (DSDA) using 2-cyanoprop-2-yl dithiobenzoate as a RAFT agent. DSDA was used as the branching agent and to afford the HBPs with reducible disulfide groups. The resulting HBPs were characterised by Nuclear Magnetic Resonance Spectroscopy (NMR) and Gel Permeation Chromatography (GPC). Differential Scanning Calorimetry (DSC) was used to determine lower critical solution temperatures (LCSTs) of these copolymers, which are in the range of 17–57 °C. Moreover, the studies on the reducibility of HBPs and swelling behaviours of hydrogels synthesized from these HBPs were conducted. The results demonstrated that we have successfully synthesized hyperbranched polymers with desired dual responsive (thermal and reducible) and crosslinkable (via thiol-ene click chemistry) properties. In addition, these new HBPs carry the multiplicity of reactive functionalities, such as RAFT agent moieties and multivinyl functional groups, which can afford them with the capacity for further bioconjugation and structure modifications

Growth and characterization of BaZnGa

We report the growth, structure and characterization of BaZnGa, identifying it as the sole known ternary compound in the Ba-Zn-Ga system. Single crystals of BaZnGa can be grown out of excess Ba-Zn and adopt a tI36 structure type. There are three unique Ba sites and three M\,=\,Zn/Ga sites. Using DFT calculations we can argue that whereas one of these three M sites is probably solely occupied by Ga, the other two M sites, most likely, have mixed Zn/Ga occupancy. Temperature dependent resistivity and magnetization measurements suggest that BaZnGa is a poor metal with no electronic or magnetic phase transitions between 2\,K and 300\,K

Anisotropic thermodynamic and transport properties of single crystalline CaKFe4_{4}As4_{4}

Single crystalline, single phase CaKFe$_{4}$As$_{4}$ has been grown out of a high temperature, quaternary melt. Temperature dependent measurements of x-ray diffraction, anisotropic electrical resistivity, elastoresistivity, thermoelectric power, Hall effect, magnetization and specific heat, combined with field dependent measurements of electrical resistivity and field and pressure dependent measurements of magnetization indicate that CaKFe$_{4}$As$_{4}$ is an ordered, stoichiometric, Fe-based superconductor with a superconducting critical temperature, $T_c$ = 35.0 $\pm$ 0.2 K. Other than superconductivity, there is no indication of any other phase transition for 1.8 K $\leq T \leq$ 300 K. All of these thermodynamic and transport data reveal striking similarities to that found for optimally- or slightly over-doped (Ba$_{1-x}$K$_x$)Fe$_2$As$_2$, suggesting that stoichiometric CaKFe$_4$As$_4$ is intrinsically close to what is referred to as "optimal-doped" on a generalized, Fe-based superconductor, phase diagram. The anisotropic superconducting upper critical field, $H_{c\text{2}}(T)$, of CaKFe$_{4}$As$_{4}$ was determined up to 630 kOe. The anisotropy parameter $\gamma(T)=H_{c\text{2}}^{\perp}/H_{c\text{2}}^{\|}$, for $H$ applied perpendicular and parallel to the c-axis, decreases from $\simeq 2.5$ at $T_c$ to $\simeq 1.5$ at 25 K which can be explained by interplay of paramagnetic pairbreaking and orbital effects. The slopes of $dH_{c\text{2}}^{\|}/dT\simeq-44$ kOe/K and $dH_{c\text{2}}^{\perp}/dT \simeq-109$ kOe/K at $T_c$ yield an electron mass anisotropy of $m_{\perp}/m_{\|}\simeq 1/6$ and short Ginzburg-Landau coherence lengths $\xi_{\|}(0)\simeq 5.8 \text{\AA}$ and $\xi_{\perp}(0)\simeq 14.3 \text{\AA}$. The value of $H_{c\text{2}}^{\perp}(0)$ can be extrapolated to $\simeq 920$ kOe, well above the BCS paramagnetic limit.Comment: 13 pages, 15 figures, part of arXiv:1606.02241 is include

Sustaining Critical Approaches to Translanguaging in Education: A Contextual Framework

Translanguaging remains a timely and important topic in bi/multilingual education. The most recent turn in translanguaging scholarship involves attention to translanguaging in context in response to critiques of translanguaging as a universally empowering educational practice. In this paper, seven early career translanguaging scholars propose a framework for researching translanguaging “in context,” drawing on the Douglas Fir Group\u27s (2016) transdisciplinary framework for language acquisition. Examining translanguaging in context entails paying attention to who in a classroom wields power, as a result of their greater proficiency in societally valued languages, their more “standard” ways of speaking these languages, their greater familiarity with academic literacies valued at school, and/or their more “legitimate” forms of translanguaging. In our framework for researching translanguaging in context, we propose three principles. The first principle is obvious: (1) not to do so apolitically. The other two principles describe a synergy between ethnographic research and teacher-researcher collaborative research: (2) ethnographic research can assess macro-level language ideologies and enacted language hegemonies at the micro- and meso levels, and (3) teacher-researcher collaborations must create and sustain inclusive, equitable classroom social orders and alternative academic norms different from the ones documented to occur in context if left by chance

RAPID: Enabling Fast Online Policy Learning in Dynamic Public Cloud Environments

Resource sharing between multiple workloads has become a prominent practice among cloud service providers, motivated by demand for improved resource utilization and reduced cost of ownership. Effective resource sharing, however, remains an open challenge due to the adverse effects that resource contention can have on high-priority, user-facing workloads with strict Quality of Service (QoS) requirements. Although recent approaches have demonstrated promising results, those works remain largely impractical in public cloud environments since workloads are not known in advance and may only run for a brief period, thus prohibiting offline learning and significantly hindering online learning. In this paper, we propose RAPID, a novel framework for fast, fully-online resource allocation policy learning in highly dynamic operating environments. RAPID leverages lightweight QoS predictions, enabled by domain-knowledge-inspired techniques for sample efficiency and bias reduction, to decouple control from conventional feedback sources and guide policy learning at a rate orders of magnitude faster than prior work. Evaluation on a real-world server platform with representative cloud workloads confirms that RAPID can learn stable resource allocation policies in minutes, as compared with hours in prior state-of-the-art, while improving QoS by 9.0x and increasing best-effort workload performance by 19-43%