Topology sorting: Separating linear/star polymer blend components by imbibition in nanopores.

We report the imbibition and adsorption kinetics of a series of symmetric linear/star cis-1,4-polyisoprene blends within the long channels of self-ordered nanoporous anodic aluminum oxide (abbreviated: AAO). Using in situ nanodielectric spectroscopy, we followed the evolution of the longest chain modes in the blends with a judicious selection of molar masses for the constituent components. We demonstrated differences in the imbibition kinetics of linear and star components based on the relative viscosities (e.g., polymers with lower zero-shear viscosity penetrated first the nanopores). Following the complete imbibition of the pores, the adsorption time, τads, of each component was evaluated from the reduction in the dielectric strength of the respective chain modes. In the majority of blends, both components exhibited slower adsorption kinetics with respect to the homopolymers. The only exception was the case of entangled stars mixed with shorter linear chains, the latter acting as a diluent for the star component. This gives rise to what is known as topology sorting, e.g., the separation of linear/star blend components in the absence of solvent. Moreover, a simple relation (τads ∼ 10 × tpeak; tpeak is the time needed for the complete filling of pores) was found for linear polymers and stars. This suggested that the characteristic timescale of imbibition (tpeak) governs the adsorption process of polymers. It further implied the possibility of predicting the adsorption times of high molar mass polymers of various architectures by the shorter imbibition times.

Electrolysis on a Chip with Tunable Thin Film Nanostructured PGM Electrocatalysts Generated from Self-Assembled Block Copolymer Templates.

Self-assembled block copolymers are promising templates for fabricating thin film materials with tuned periodic feature sizes and geometry at the nanoscale. Here, a series of nanostructured platinum and iridium oxide electrocatalysts templated from poly(styrene)-block-poly(vinyl pyridine) (PSbPVP) block copolymers via an incipient wetness impregnation (IWI) pathway is reported. Both nanowire and nanocylinder electrocatalysts of varying feature sizes are assessed and higher catalyst loadings are achieved by the alkylation of the pyridine moieties in the PVP block prior to IWI. Electrocatalyst evaluations featuring hydrogen pump and water electrolysis demonstrations are carried out on interdigitated electrode (IDE) chips flexible with liquid supporting electrolytes and thin film polymer electrolytes. Notably, the mass activities of the nanostructured electrocatalysts from alkylated block copolymer templates are 35%-94% higher than electrocatalysts from non-alkylated block copolymer templates. Standing cylinder nanostructures lead to higher mass activities than lamellar variants despite their not having the largest surface area per unit catalyst loading demonstrating that mesostructure architectures have a profound impact on reactivity. Overall, IDE chips with model thin film electrocatalysts prepared from self-assembled block copolymers offer a high-throughput experimental method for correlating electrocatalyst nanostructure and composition to electrochemical reactivity.

Ceftazidime/avibactam and eravacycline susceptibility of carbapenem-resistant Klebsiella pneumoniae in two Greek tertiary teaching hospitals.

The present study evaluated the carbapenem resistance mechanisms of Klebsiella pneumoniae strains isolated in two Greek tertiary teaching hospitals and their susceptibility to currently used and novel antimicrobial agents.Forty-seven carbapenem resistant K. pneumoniae strains were collected in G. Papanikolaou and Ippokrateio hospital of Thessaloniki between 2016 and 2018. Strain identification and antimicrobial susceptibility was conducted by Vitek 2 system (Biomérieux France). Susceptibility against new antimicrobial agents was examined by disk diffusion method. Polymerase chain reaction (PCR) was used to detect blaKPC, blaVIM, blaNDM and blaOXA-48 genes.The meropenem-EDTA and meropenem-boronic acid synergy test performed on the 24 K. pneumoniae strains demonstrated that 8 (33.3%) yielded positive for metallo-beta-lactamases (MBL) and 16 (66.6%) for K. pneumonia carbapenemases (KPC) production. Colistin demonstrated the highest in vitro activity (87.7%) among the 47 K. pneumoniae strains followed by gentamicin (76.5%) and tigecycline (51%). Among new antibiotics ceftazidime/avibactam showed the highest sensitivity (76.6%) in all strains followed by eravacycline (66.6%). The blaKPC gene was present in 30 strains (63.8%), the blaNDM in 11 (23.4%) and the blaVIM in 6 (12.8%). The blaOXA-48 gene was not detected.Well established antimicrobial agents such as colistin, gentamicin and tigecycline and novel antibiotics like ceftazidime/avibactam and eravacycline can be reliable options for the treatment of invasive infections caused by carbapenem-resistant K. pneumoniae.

Free Surface Relaxations of Star-Shaped Polymer Films.

The surface relaxation dynamics of supported star-shaped polymer thin films are shown to be slower than the bulk, persisting up to temperatures at least 50 K above the bulk glass transition temperature T_{g}^{bulk}. This behavior, exhibited by star-shaped polystyrenes with functionality f=8 arms and molecular weights per arm M_{arm}

Phase behavior of diblock copolymer/star-shaped polymer thin film mixtures.

We investigated the phase behavior of thin film, thickness h≈ 100 nm, mixtures of a polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP) diblock copolymer with star-shaped polystyrene (SPS) molecules of varying functionalities f, where 4 ≤f≤ 64, and molecular weights per arm Marm. The miscibility of the system and the surface composition varied appreciably with Marm and f. For large values of Marm, regardless of f, the miscibility of the system was qualitatively similar to that of linear chain PS/PS-b-P2VP mixtures - the copolymer chains aggregate to form micelles, each composed of an inner P2VP core and PS corona, which preferentially segregate to the free surface. On the other hand, for large f and small Marm, SPS molecules preferentially resided at the free surface. Moreover, blends containing SPS molecules with the highest values of f and lowest values of Marm were phase separated. These observations are rationalized in terms of competing entropic interactions and the dependence of the surface tension of the star-shaped molecules on Marm and f.

A computational and experimental study of the linear and nonlinear response of a star polymer melt with a moderate number of unentangled arms.

We present from simulations and experiments results on the linear and nonlinear rheology of a moderate functionality, low molecular weight unentangled polystyrene (PS) star melt. The PS samples were anionically synthesized and close to monodisperse while their moderate functionality ensures that they do not display a pronounced core effect. We employ a highly coarse-grained model known as Responsive Particle Dynamics where each star polymer is approximated as a point particle. The eliminated degrees of freedom are used in the definition of an appropriate free energy as well as describing the transient pair-wise potential between particles that accounts for the viscoelastic response. First we reproduce very satisfactorily the experimental moduli using simulation. We then consider the nonlinear response of the same polymer melts by implementing a start-up shear protocol for a wide range of shear rates. As in experiments, we observe the development of a stress overshoot with increasing shear rate followed by a steady-state shear stress. We also recover the shear-thinning nature of the melt, although we slightly overestimate the extent of shear-thinning with simulations. In addition, we study relaxations upon the removal of shear where we find encouraging agreement between experiments and simulations, a finding that corroborates our agreement for the linear rheology.

Surface-initiated polymerization from carbon nanotubes: strategies and perspectives.

Carbon nanotubes (CNTs) represent one of the most promising materials in nanoscience today, with their unique electronic, chemical and mechanical properties. Strong van der Waals interactions and poor solubility greatly affect their potential for applications in various fields. In the past decade, great efforts have been undertaken to modify CNTs into organophilic material via covalent and non-covalent grafting strategies. This review focuses on advances in various strategies used for the surface initiated polymerization and provides perspectives on grafting polymers covalently from CNTs.

Nonmonotonic Composition Dependence of Viscosity upon Adding Single-Chain Nanoparticles to Entangled Polymers.

Well-characterized single-chain nanoparticles (SCNPs), synthesized from a linear polystyrene precursor through an intramolecular [4 + 4] thermal cycloaddition cross-linking reaction in dilute conditions, were added to entangled polystyrene melts at different concentrations. Starting from the pure linear melt, which is much more viscous than the melt of SCNPs, the zero-shear viscosity increased upon the addition of nanoparticles and reached a maximum before eventually dropping to the value of the SCNP melt. Molecular simulations reveal the origin of this unexpected behavior, which is the interplay of the very different compositional dependences of the dynamics of the two components. The SCNPs become much slower than the linear chains as their concentration decreases because they are threaded by the linear chains, reaching a maximum viscosity which is higher than that of the linear chains at a fraction of about 20%. This behavior is akin to that of single-loop ring polymers when added to linear matrices. This finding provides insights into the design and use of SCNPs as effective entropic viscosity modifiers of polymers and contributes to the discussion of the physics of loopy structures.

Nanostructured Single-ion Polymer Blend Electrolytes Composed of Polyanionic Particles and Low Molecular Weight PEO.

The development of single-ion solid polymer electrolytes with high ion conductivity holds the key to the realization of safe, long-lasting, high-energy batteries. Here we introduce the use of core-shell nanostructured polyanionic particles, composed of polyanion asymmetric miktoarm stars with a large number of glassy polystyrene-based polyanion arms that complement longer poly(ethylene oxide), PEO, arms, as additives to low molecular weight, liquid PEO. Due to the proposed macromolecular design approach, the polyanion particles are well dispersed for wt % ≤ 55 that enables the formation of a nanostructured single-ion electrolyte with highly interconnected channels composed of liquid PEO that promotes fast ion transport. Noticeably, while the ion conductivity remains fairly unaffected and close to 10-5 S/cm at room temperature with nanoparticle loading, the shear modulus monotonically increases by several order of magnitudes indicating a very strong decoupling between the antagonistic properties of mechanical modulus and ion conductivity.

Non-equilibrium Effects of Polymer Dynamics under Nanometer Confinement: Effects of Architecture and Molar Mass.

The non-equilibrium dynamics of linear and star-shaped cis-1,4 polyisoprenes confined within nanoporous alumina is explored as a function of pore size, d, molar mass, and functionality (f = 2, 6, and 64). Two thermal protocols are tested: one resembling a quasi-static process (I) and another involving fast cooling followed by annealing (II). Although both protocols give identical equilibrium times, it is through protocol I that it is easier to extract the equilibrium times, teq, by the linear relationships of the characteristic peak frequencies with time and rate, respectively, as log(fmax) = C1 - k log(t) and log(fmax) = C2 + λ log(ß). Both thermal protocols establish the existence of a critical temperature (at Tc, where k → 0 and λ → 0) below which non-equilibrium effects set-in. The critical temperature depends on the degree of confinement, 2Rg/d, and on molecular architecture. Strikingly, establishing equilibrium dynamics at all temperatures above the bulk, Tg, requires 2Rg/d ∼ 0.02, i.e., pore diameters that are much larger than the chain dimensions. This reflects non-equilibrium configurations of the adsorbed layer that extent away from the pore walls. The equilibrium times depend strongly on temperature, pore size, and functionality. In general, star-shaped polymers require longer times to reach equilibrium because of the higher tendency for adsorption. Both thermal protocols produced an increasing dielectric strength for the segmental and chain modes. The increase was beyond any densification, suggesting enhanced orientation correlations of subchain dipoles.

Functionalization of Single-Walled Carbon Nanotubes with End-Capped Polystyrene via a Single-Step Diels-Alder Cycloaddition.

A facile, single-step, [4+2] Diels-Alder cycloaddition reaction for the surface functionalization of single-walled carbon nanotubes (SWNTs) with end-capped polystyrene chains is presented. The thermal cycloaddition reaction took place at high temperature (~230 °C) without any catalyst between the sp2 network of carbon nanotubes, which acted as dienophile, and the diphenylethylene cyclobutene (DPE-CB) terminal group of the polystyrene chain. Anionic polymerization was employed for the synthesis of the polystyrene macromolecule, and successful and quantitative end-capping reaction with the DPE-CB molecule was confirmed by matrix-assisted laser desorption/ionization time of flight mass spectroscopy. Thermogravimetric analysis revealed the wt % of the grafted macromolecule on the CNT surface as well as the grafting density of the polymer chains on the SWNTs (0.027 chains nm-2). Direct evidence for the surface functionalization and the presence of thin polystyrene film was obtained by transmission electron microscopy (TEM) and by atomic force microscopy (AFM).

Understanding the ionic activity and conductivity value differences between random copolymer electrolytes and block copolymer electrolytes of the same chemistry.

Herein, a systematic study where the macromolecular architectures of poly(styrene-block-2-vinyl pyridine) block copolymer electrolytes (BCE) are varied and their activity coefficients and ionic conductivities are compared and rationalized versus a random copolymer electrolyte (RCE) of the same repeat unit chemistry. By performing quartz crystal microbalance, ion-sorption, and ionic conductivity measurements of the thin film copolymer electrolytes, it is found that the RCE has higher ionic activity coefficients. This observation is ascribed to the fact that the ionic groups in the RCE are more spaced out, reducing the overall chain charge density. However, the ionic conductivity of the BCE is 50% higher and 17% higher after the conductivity is normalized by their ion exchange capacity values on a volumetric basis. This is attributed to the presence of percolated pathways in the BCE. To complement the experimental findings, molecular dynamics (MD) simulations showed that the BCE has larger water cluster sizes, rotational dynamics, and diffusion coefficients, which are contributing factors to the higher ionic conductivity of the BCE variant. The findings herein motivate the design of new polymer electrolyte chemistries that exploit the advantages of both RCEs and BCEs.

Designing All-Polymer Nanostructured Solid Electrolytes: Advances and Prospects.

Multi-phase nanostructured polymer electrolytes, where the one phase conducts ions while the other imparts the desired mechanical properties, are currently the most promising candidates for solid-state electrolytes in high-density lithium metal batteries. In contrast to homogeneous polymer electrolytes, where ion transport is coupled with polymer segmental dynamics and any attempt to improve conductivity via faster polymer motions results in a decrease in stiffness, nanostructured materials efficiently decouple these two antagonistic parameters. Nevertheless, for reasons discussed herein the synthesis of a polymer electrolyte that simultaneously has a shear modulus of G' ≈ GPa and an ion conductivity of σ > 10-4 S/cm (in the case dual ion conductor) or of σ > 10-5 S/cm (in the case of single-ion conductor) remains a challenge. This review focuses on recent designing strategies for the synthesis of all-polymer nanostructured electrolytes, and protocols for introducing a single-ion character in such materials.

Grafting reactions of living macroanions with multi-walled carbon nanotubes.

Grafting reactions of living polystyryllithium (PSLi) with acid chloride containing multi-walled carbon nanotubes (MWNTs-COCI) were performed under vacuum in benzene at room temperature. Covalent grafting of polystyrene (PS) was characterized using spectroscopic, microscopic, and thermogravimetric analyses. Grafting at different ratios of macroanion to acylchloride of the carbon nanotubes showed that the grafting efficiency was not dependent on the concentration of the macroanions. The mole percent of PS present in the MWNTs-g-PS samples was inversely proportional to the precursor molecular weight of PSLi. Direct reactions of PSLi, polybutadienyllithium and n-butyllithium with pristine MWNTs without any functional groups were also performed in the presence and in the absence of tetrahydrofuran in benzene. The grafting reactions of living macroanions either with MWNTs-COCl or with pristine MWNTs indicated a partial grafting of polymer on the carbon nanotubes in benzene at room temperature.

Initial dosing of paricalcitol based on PTH levels in hemodialysis patients with secondary hyperparathyroidism.

BACKGROUND: Adjustment of the initial dose of paricalcitol in hemodialysis patients with secondary hyperparathyroidism (SHPT) on the basis of severity of SHPT generally is preferred in current practice. Whether the proposed dose, based on the formula baseline intact parathyroid hormone (iPTH [picograms per milliliter]) divided by 80, is the most appropriate has not been assessed adequately. METHODS: A double-blind randomized trial comparing iPTH/80 dose with the immediately lower iPTH/120 dose was undertaken. Forty-three hemodialysis patients with iPTH levels between 300 and 900 pg/mL (300 and 900 ng/L) were followed up for 12 weeks. The primary outcome was control of iPTH levels within a target range between 150 and 300 pg/mL (150 and 300 ng/L). RESULTS: No difference between the 2 dose groups was noted in time to achieve target iPTH levels of 150 to 300 pg/mL (150 to 300 ng/L). More episodes of excessive decrease in iPTH levels occurred in the iPTH/80 group compared with the iPTH/120 group (P = 0.003). Nine patients in the iPTH/80 group (45%) versus 2 patients in the iPTH/120 group (10%) had iPTH levels less than 150 pg/mL (<150 ng/L) in at least half the measurements performed during the second half of the study (P = 0.034). Increases in calcium levels were greater in the iPTH/80 group at all times during the study (P < 0.05 at weeks 4 and 10). The number of required dose reductions was significantly greater in the iPTH/80 group compared with the iPTH/120 group (P = 0.008). CONCLUSION: In hemodialysis patients with SHPT, a lower initial dose of iPTH/120 shows efficacy similar to that of the already widely used iPTH/80 scheme in reaching target iPTH levels (150 to 300 pg/mL [150 to 300 ng/L]), with less required dose adjustments, lower increase in calcium levels, and lower cost. In addition, the initial dose of paricalcitol based on the iPTH/80 formula leads significantly more patients to excessive suppression of iPTH (<150 pg/mL [<150 ng/L]) than the iPTH/120 dose.

Do serum and red blood cell folate levels indicate iron response in hemodialysis patients?

The relationship among iron status, ferritin, and folate levels, and the possible contribution of folate measurement in the prediction of iron response in hemodialysis patients, have not been assessed. In addition to serum ferritin and transferrin saturation (TSAT), serum and red blood cell (RBC) folate levels were evaluated as indices for intravenous iron therapy responsiveness in 60 hemodialysis patients. Patients were classified as iron responders or nonresponders depending on whether they exhibited a rise in hemoglobin above 1 g/dl after administration of 1 g of iron sucrose. An inverse relation between serum ferritin concentration and RBC folate levels was found in iron responders (n=26, r=-0.62, p<0.001) but not in nonresponders (n=34, r=0.07, p=nonsignificant). Only serum and RBC folate levels could predict iron response in patients with ferritin levels above 150 microg/l (n=25), with a sensitivity of 83.3% and a specificity of 94.7%. Our findings suggest that RBC folate concentration is inversely related with ferritin levels in iron-responsive but not in non-responsive hemodialysis patients. Serum and RBC folate concentration seems to predict response to iron administration better than serum ferritin or TSAT in patients with ferritin levels above 150 microg/l; therefore, in these patients, it might be used to guide iron management.

Elastic Mechanical Response of Thin Supported Star-Shaped Polymer Films.

We show evidence of thickness-dependent elastic mechanical moduli that are associated largely with the effects of architecture (topology) and the overall shape of the macromolecule. Atomic force microscopy (AFM) based nanoindentation experiments were performed on linear chain polystyrene (LPS) and star-shaped polystyrene (SPS) macromolecules of varying functionalities (number of arms, f) and molecular weights per arm Mwarm. The out-of-plane elastic moduli E(h) increased with decreasing film thickness, h, for h less than a threshold film thickness, hth. For SPS with f ≤ 64 and Mwarm > 9 kg/mol, the dependencies of E(h) on h were virtually identical for the linear chains. Notably, however, for SPS with f = 64 and Mwarm = 9 kg/mol (SPS-9k-64), the hth was over 50% larger than that of the other polymers. These observations are rationalized in terms of the structure of the polymer for high f and sufficiently small Mwarm and not in terms of the influence of interfacial interactions.

Increase in serum magnesium level in haemodialysis patients receiving sevelamer hydrochloride.

BACKGROUND: Clinical studies have shown that sevelamer hydrochloride improves lipid profiles and attenuates the progression of the cardiovascular calcifications in haemodialysis patients. It is known that both of these properties are associated with increased magnesium levels. The effect of sevelamer on serum magnesium level is not well documented. The aim of this study was to determine the effects of sevelamer treatment on serum magnesium in haemodialysis patients and to assess the association of magnesium levels with lipid profiles and intact parathyroid hormone (iPTH). METHODS: Phosphate binders were discontinued during a two week washout period. Forty-seven patients, whose serum phosphate was greater than 6.0 mg/dl at the end of washout, received sevelamer hydrochloride for eight weeks. The patients were then washed off sevelamer for another two weeks. RESULTS: Mean serum phosphorus concentration declined from 7.5 +/- 1.3 to 6.4 +/- 1.2 mg/dl (P < 0.001), mean serum magnesium levels increased from 2.75 +/- 0.35 to 2.90 +/- 0.41 mg/dl (P < 0.001) and median serum iPTH levels decreased from 297 to 213 pg/ml (P=0.001) during the eight weeks of sevelamer treatment. After the two week post-treatment washout phosphorus levels increased to 7.3 +/- 1.3 mg/dl (P < 0.001), magnesium levels were reduced to 2.77 +/- 0.39 mg/dl (P < 0.001) and iPTH levels increased to 240 pg/ml (P=0.012). No change was observed in serum calcium levels during the sevelamer treatment period and the subsequent washout period. The mean decline in total and low density lipoprotein (LDL) cholesterol during sevelamer treatment was 16.3 and 28.3 (P < 0.001), respectively. The mean increase in high density lipoprotein (HDL) cholesterol and in apolipoprotein A1 was 2.9 +/- 5.8 mg/dl (P=0.004) and 6.8 +/- 11.1 mg/dl (P=0.001), respectively. Multivariate analysis showed that the rise in serum magnesium concentration significantly correlated with reductions in iPTH levels (r=-0.40, P=0.016), but did not have any significant correlation with the changes in lipid profiles. CONCLUSIONS: Our findings indicate that patients on haemodialysis receiving sevelamer have a significant increase in serum magnesium concentrations. This increase in serum magnesium is associated with reduction in iPTH levels. The changes in lipid profiles of these patients however are not related to changes in serum magnesium levels.

Immunoadsorption in lupus myocarditis.

Reduction of pathological autoantibodies may be useful in the treatment of systemic lupus erythematosus (SLE). On the other hand clinically manifested myocarditis in SLE, though uncommon, may be life-threatening and its pathogenesis has been ascribed to autoimmunity. The aim of this study is to present a rare case of a patient with severe lupus myocarditis, where immunoadsorption (IA) was evaluated as rescue therapy. A case of SLE with initial manifestation of myocarditis is reported in a 29-year-old male who presented with arthritis, fever, lymphadenopathy, joint swelling and morning stiffness. Laboratory evaluation revealed increased antinuclear antibody (ANA), slightly decreased complement and positive anticoagulant panel. From the above clinical and laboratory features, criteria of SLE seemed applicable. During his hospitalization, the patient developed pericardial effusion and cardiogenic shock. Although pericardiotomy was performed and was treated with immunosuppressive agents, plasmapheresis and supported with current medications, his clinical condition remained critical with an ejection fraction of 20%. At this point it was decided to receive IA onto staphylococcal protein A. After 6 sessions with IA and concomitant immunosuppression, the patient responded well, his condition improved and was dismissed with an ejection fraction of 50%. Fulminant lupus myocarditis is a severe and rare situation lacking a satisfying specific therapy available today. In our presented case, IA in addition to immunosuppressive therapy was beneficial. Considering the benefits of our case and the current knowledge, it might be useful to clarify the open question in scale pilot studies.