Multifunctional Block Copolymers, Acting as Recycling Aids, by Atom Transfer Radical Polymerization.

Block copolymers utilizing oligomeric poly(pentylene-co-hexylene carbonate)diol modified with 2,4-diisocyanatotoluene and further with 2-bromo-N-(3-hydroxypropyl)-2-methylpropanamide were synthesized and utilized as Activators ReGenerated by Electron Transfer Atom Transfer Radical Polymerization macroinitiators to obtain a first generation of multifunctional recycling additives with poly(glycidyl methacrylate-co-butyl methacrylate-co-methyl methacrylate) side chains, which could act as chain extenders. Then, chosen additive was reacted with a radical scavenger, 3,5-ditertbutyl-4-hydroxybenzoic acid (DHBA), to obtain a second generation of reactive additives. Those copolymers had different numbers of epoxy groups per polymer chain, and different number of epoxides opened with DHBA, hence showed a range of properties, and were utilized as reactive modifiers for polylactide (PLA) extrusion melting. The first-generation modifiers caused an increase in PLA's blends relative melt viscosity, stabilized material properties, and enhanced impact strength, while the second-generation modifiers with more than 8 % of epoxide ring opened showed worse properties. However, they managed to suppress the UV degradation of PLA blend plates.

Influence of the filler distribution on PDMS-graphene based nanocomposites selected properties.

Insufficient homogeneity is one of the pressing problems in nanocomposites' production as it largely impairs the properties of materials with relatively high filler concentration. Within this work, it is demonstrated how selected mixing techniques (magnetic mixer stirring, calendaring and microfluidization) affect filler distribution in poly(dimethylsiloxane)-graphene based nanocomposites and, consequently, their properties. The differences were assessed via imaging and thermal techniques, i.a. Raman spectroscopy, differential scanning calorimetry and thermogravimetry. As microfluidization proved to provide the best homogenization, it was used to prepare nanocomposites of different filler concentration, whose structural and thermal properties were investigated. The results show that the concentration of graphene significantly affects polymer chain mobility, grain sizes, defect density and cross-linking level. Both factors considered in this work considerably influence thermal stability and other features which are crucial for application in electronics, EMI shielding, thermal interface materials etc.

Study of Structural and Optoelectronic Properties of Thin Films Made of a Few Layered WS2 Flakes.

We report a surfactant-free exfoliation method of WS2 flakes combined with a vacuum filtration method to fabricate thin (<50 nm) WS2 films, that can be transferred on any arbitrary substrate. Films are composed of thin (<4 nm) single flakes, forming a large size uniform film, verified by AFM and SEM. Using statistical phonons investigation, we demonstrate structural quality and uniformity of the film sample and we provide first-order temperature coefficient χ, which shows linear dependence over 300-450 K temperature range. Electrical measurements show film sheet resistance RS = 48 MΩ/Υ and also reveal two energy band gaps related to the intrinsic architecture of the thin film. Finally, we show that optical transmission/absorption is rich above the bandgap exhibiting several excitonic resonances, and nearly feature-less below the bandgap.

Thermal properties of thin films made from MoS2 nanoflakes and probed via statistical optothermal Raman method.

A deep understanding of the thermal properties of 2D materials is crucial to their implementation in electronic and optoelectronic devices. In this study, we investigated the macroscopic in-plane thermal conductivity (κ) and thermal interface conductance (g) of large-area (mm2) thin film made from MoS2 nanoflakes via liquid exfoliation and deposited on Si/SiO2 substrate. We found κ and g to be 1.5 W/mK and 0.23 MW/m2K, respectively. These values are much lower than those of single flakes. This difference shows the effects of interconnections between individual flakes on macroscopic thin film parameters. The properties of a Gaussian laser beam and statistical optothermal Raman mapping were used to obtain sample parameters and significantly improve measurement accuracy. This work demonstrates how to address crucial stability issues in light-sensitive materials and can be used to understand heat management in MoS2 and other 2D flake-based thin films.

Graphene-based plastic absorber for total sub-terahertz radiation shielding.

Increasing the requirements on telecommunications systems such as the need for higher data rates and connectivity via the Internet of things results in continuously increasing amounts of electromagnetic radiation in ever-higher telecommunications bands (up to terahertz). This can generate unwanted electromagnetic radiation that can affect the operation of electronic devices and human health. Here, we demonstrate that nonconductive and lightweight, graphene-based composites can shield more than 99.99% of the electromagnetic energy in the sub-THz range mainly via absorption. This contrasts with state-of-the-art electromagnetic radiation shielding materials that simply redirect the energy of the radiation from a protected area via conduction-based reflection mechanisms. This shifts the problem of electromagnetic pollution from one place to another. We have demonstrated that the proposed composites can be fabricated by industrial compatible methods and are characterized by specific shielding efficiency values that exceed 30 dB cm3 g-1, which is more than those for typical metals used today. Therefore these materials might help to solve the problem of electromagnetic environmental pollution.

High accuracy determination of the thermal properties of supported 2D materials.

We present a novel approach for the simultaneous determination of the thermal conductivity κ and the total interface conductance g of supported 2D materials by the enhanced opto-thermal method. We harness the property of the Gaussian laser beam that acts as a heat source, whose size can easily and precisely be controlled. The experimental data for multi-layer graphene and MoS2 flakes are supplemented using numerical simulations of the heat distribution in the Si/SiO2/2D material system. The procedure of κ and g extraction is tested in a statistical approach, demonstrating the high accuracy and repeatability of our method.

Temperature-dependent thermal properties of supported MoS2 monolayers.

Thermal properties can substantially affect the operation of various electronics and optoelectronics devices based on two-dimensional materials. In this work, we describe our investigation of temperature-dependent thermal conductivity and interfacial thermal conductance of molybdenum disulfide monolayers supported on SiO2/Si substrates, using Raman spectroscopy. We observed that the calculated thermal conductivity (κ) and interfacial thermal conductance (g) decreased with increasing temperature from 62.2 W m(-1) K(-1) and 1.94 MW m(-2) K(-1) at 300 K to 7.45 W m(-1) K(-1) and 1.25 MW m(-2) K(-1) at 450 K, respectively.

Quality indicator set for systemic sclerosis.

BACKGROUND: Systemic sclerosis (SSc) is associated with a marked economic burden, high treatment costs and decreased productivity. Although treatment strategies for SSc can have a substantial effect on patients' outcomes, it is not known whether patients with SSc consistently receive such care. Evaluation of process-of-care quality requires specification of quality indicators (QIs), clinically detailed statements of the eligible patients and the care they should receive to achieve a minimal level of quality of care. Our objective was to develop QIs for patients with SSc. METHODS: We performed a comprehensive literature review of diagnosis and treatment of SSc and proposed QIs that were evaluated by a national Expert Panel (n=9) who were asked to review the supporting literature and individually rank the validity of each QI. These rankings formed the basis of discussion at a face-to-face meeting following the RAND/UCLA method to integrate expert opinion with literature review to identify a set of final QIs. We then presented these QIs to members of the Scleroderma Clinical Trials Consortium (SCTC). RESULTS: Thirty-two QIs for SSc care were judged valid by the Expert Panel. The QI set includes 9 QIs for newly diagnosed with SSc, 12 follow-up QIs for management of SSc, and 11 treatment QIs. The SCTC experts agreed with the validity of each of the 32 QI and agreed that for all but one QI the specified tests, procedures and treatments recommended in the QI were generally available. CONCLUSIONS: We have developed 32 QIs for SSc using a rigorous methodology that can be employed to evaluate and improve care for patients with SSc, as well as inform policy decisions supporting appropriate care for SSc patients.

Increased production of a proliferation-inducing ligand (APRIL) by peripheral blood mononuclear cells is associated with antitopoisomerase I antibody and more severe disease in systemic sclerosis.

OBJECTIVE: A proliferation-inducing ligand (APRIL), a member of the tumor necrosis factor (TNF) family, plays a crucial role in the survival of peripheral B cells, and may contribute to the pathogenesis of systemic sclerosis (SSc) through upregulation of autoantibody production and maintenance of autoimmune phenomena. We evaluated the capacity of peripheral blood mononuclear cells from patients with SSc (SSc-PBMC) to produce APRIL; and investigated correlations between production of APRIL by SSc-PBMC and clinical and laboratory features of the disease. METHODS: PBMC from 20 patients with SSc and 14 healthy subjects were incubated in fetal calf serum-supplemented RPMI medium. APRIL levels were determined in cell culture supernatants by ELISA. RESULTS: PBMC from patients with SSc produced significantly more APRIL (961 ± 151 pg/ml/105 cells) than control PBMC (798 ± 219 pg/ml/105 cells; p < 0.01). In patients with SSc, increased production of APRIL was associated with the presence of diffuse skin involvement, scleroderma lung disease, peripheral vasculopathy, greater capillary damage on capillaroscopy, and presence of anti-topoisomerase I (anti-topo I) antibodies. Multivariate regression analysis revealed anti-topo I antibodies as the only independent predictor of high production of APRIL by PBMC. CONCLUSION: Production of APRIL is increased in SSc-PBMC and is associated with the presence of anti-topo I antibodies and more severe disease. Targeting the APRIL pathway might represent a therapeutic possibility for treatment of patients with SSc, in particular those with anti-topo I antibodies.

Diminished production of TWEAK by the peripheral blood mononuclear cells is associated with vascular involvement in patients with systemic sclerosis.

Widespread vasculopathy and profound fibrosis are key features of the pathogenesis of systemic sclerosis (SSc). We hypothesized that the TNF-like weak inducer of apoptosis (TWEAK), a recently recognized multifunctional cytokine which regulates angiogenesis and tissue remodeling, may play a role in the development of SSc. The production of TWEAK by the peripheral blood mononuclear cells (PBMC) was investigated, by means of ELISA, in 24 SSc patients and 14 healthy subjects. Moreover, production of TWEAK was correlated with clinical features of SSc. PBMC were isolated using density gradient centrifugation on Histopaque and were cultured in FCS supplemented RPMI medium at 37 degrees C under 5% CO2. Production of TWEAK by PBMC was significantly diminished in patients with more severe microvascular damage, as indicated by the presence of "active" capillaroscopic pattern, compared with SSc patients with less pronounced microangiopathy ("slow" pattern), and healthy subjects. Moreover production of TWEAK correlated inversely with duration of Raynaud's phenomenon. PBMC from patients with scleroderma-related interstitial lung disease tended to produce lower amounts of TWEAK compared with SSc patients without lung involvement but the difference was not significant. The results of our study suggest that diminished production of TWEAK might play a role in the pathogenesis of vascular injury in SSc patients. Whether TWEAK may represent a new therapeutic target in SSc requires further studies.