Biocomposites Based on Electrospun Fibers of Poly(3-hydroxybutyrate) and Nanoplatelets of Graphene Oxide: Thermal Characteristics and Segmental Dynamics at Hydrothermal and Ozonation Impact.

In order to create new biodegradable nanocomposites for biomedicine, packaging, and environmentally effective adsorbents, ultra-thin composite fibers consisting of poly(3-hydroxybutyrate) (PHB) and graphene oxide (GO) were obtained by electrospinning. Comprehensive studies of ultrathin fibers combining thermal characteristics, dynamic electron paramagnetic resonance (ESR) probe measurements, and scanning electron microscopy (SEM) were carried out. It is shown that at the addition of 0.05, 0.1, 0.3, and 1% OG, the morphology and geometry of the fibers and their thermal and dynamic characteristics depend on the composite content. The features of the crystalline and amorphous structure of the PHB fibers were investigated by the ESR and DSC methods. For all compositions of PHB/GO, a nonlinear dependence of the correlation time of molecular mobility TEMPO probe (τ) and enthalpy of biopolyether melting (ΔH) is observed. The influence of external factors on the structural-dynamic properties of the composite fiber, such as hydrothermal exposure of samples in aqueous medium at 70 °C and ozonolysis, leads to extreme dependencies of τ and ΔH, which reflect two processes affecting the structure in opposite ways. The plasticizing effect of water leads to thermal destruction of the orientation of the pass-through chains in the amorphous regions of PHB and a subsequent decrease in the crystalline phase, and the aggregation of GO nanoplates into associates, reducing the number of GO-macromolecule contacts, thus increasing segmental mobility, as confirmed by decreasing τ values. The obtained PHB/GO fibrillar composites should find application in the future for the creation of new therapeutic and packaging systems with improved biocompatibility and high-barrier properties.

Improving Access to Kidney Transplantation: Perspectives From Dialysis and Transplant Staff in the Southeastern United States.

RATIONALE & OBJECTIVE: There are many barriers to meeting the goal of increasing kidney transplants in the United States. It is important to understand dialysis and transplant center providers' existing practices and identified barriers to increasing the number of dialysis patients who are evaluated for and get wait-listed for a transplant. STUDY DESIGN: Cross-sectional survey of dialysis unit and transplant center staff in End Stage Renal Disease Network 6 (Georgia, North Carolina, South Carolina). SETTING & PARTICIPANTS: Ninety-one transplant staff from all 9 transplant centers in the region and 421 dialysis staff from 421 facilities responded to the survey. PREDICTORS: N/A. OUTCOME: Provider perceptions of barriers faced by patients in the kidney transplant evaluation process and suggestions for improving care. ANALYTICAL APPROACH: Mixed methods. Descriptive analyses of responses to multiple-choice questions and qualitative analysis of open-ended survey responses. RESULTS: The top 5 barriers to kidney transplantation as reported by transplant staff were transportation (63.7%), low health literacy (50.5%), lack of understanding about the transplant process (37.4%), distance to transplant center (29.7%), and low socioeconomic status (28.6%). When asked how dialysis units can help patients complete the evaluation process, the most common responses from transplant center staff were educating patients about transplant (54%), helping patients through steps in the process (35%), and better communication with transplant centers (15%). When dialysis unit staff were asked what could be done to help the facility improve its transplant wait-list rate, the most common responses were educational materials for patients and staff (55%), better communication with transplant centers (12%), and transportation and financial assistance (9%). LIMITATIONS: Survey responses are from 1 end stage renal disease network. CONCLUSIONS: Dialysis units, transplant centers, and ESRD networks can work together to help patients address key barriers to transplantation to improve the country's transplantation rate.

Aggressive Impacts Affecting the Biodegradable Ultrathin Fibers Based on Poly(3-Hydroxybutyrate), Polylactide and Their Blends: Water Sorption, Hydrolysis and Ozonolysis.

Ultrathin electrospun fibers of pristine biopolyesters, poly(3-hydroxybutyrate) (PHB) and polylactic acid (PLA), as well as their blends, have been obtained and then explored after exposure to hydrolytic (phosphate buffer) and oxidative (ozone) media. All the fibers were obtained from a co-solvent, chloroform, by solution-mode electrospinning. The structure, morphology, and segmental dynamic behavior of the fibers have been determined by optical microscopy, SEM, ESR, and others. The isotherms of water absorption have been obtained and the deviation from linearity (the Henry low) was analyzed by the simplified model. For PHB-PLA fibers, the loss weight increments as the reaction on hydrolysis are symbate to water absorption capacity. It was shown that the ozonolysis of blend fibrils has a two-stage character which is typical for O3 consumption, namely, the pendant group's oxidation and the autodegradation of polymer molecules with chain rupturing. The first stage of ozonolysis has a quasi-zero-order reaction. A subsequent second reaction stage comprising the back-bone destruction has a reaction order that differs from the zero order. The fibrous blend PLA/PHB ratio affects the rate of hydrolysis and ozonolysis so that the fibers with prevalent content of PLA display poor resistance to degradation in aqueous and gaseous media.

Kinetics of photochemical reactions of biphotochromic compounds based on spironaphthopyran and enamine--conjugation effect.

A novel biphotochromic compound (BPC) with two photochromic fragments, namely spironaphthopyran and hydroxyazomethine, was synthesized and studied by nanosecond laser flash photolysis using the excitation wavelengths of 337, 430, 470 and 500 nm in methanol and toluene. The photoexcitation of BPC results in the formation of at least two colored transients. The first one is the merocyanine form B (the maximum in the absorption spectrum is near 600 nm and the lifetime is 0.1 and 0.05 s in methanol and toluene, respectively) due to the spiro-bond break followed by isomerization. The second one is the trans-keto form A(Kt) (the maximum in the absorption spectra is near 480 nm and the lifetime is 0.1 and 5 ms in methanol and toluene, respectively) as a result of cis-enol or cis-keto tautomer transformations. The relative yields of B and A(Kt) depends essentially on the wavelength of excitation. The form A(Kt) is the key transient formed under excitation with the visible light, whereas its yield under excitation with UV light is comparable with that of B. The specific solvation by methanol molecules favors the spirocycle opening even under visible light excitation. The results obtained for novel BPC were compared with those for other BPC where the same fragments are combined in such a way that the form B is the major one under excitation with UV light whereas it virtually is not observed under visible light excitation. The difference in both BPC is discussed in terms of conjugation (π-coupling) between photochromic fragments.

Molecular dynamics simulation of thermomechanical properties of montmorillonite crystal. 3. montmorillonite crystals with PEO oligomer intercalates.

We present the results of molecular dynamics (MD) simulation of the structure and thermomechanical behavior of Wyoming-type Na+-montmorillonite (MMT) with poly(ethylene oxide) (PEO) oligomer intercalates. Periodic boundary conditions in all three directions and simulation cells containing two MMT lamellae [Si248Al8][Al112Mg16]O640[OH]128 oriented parallel to the XY-plane were used. The interlamellar space, or gallery, between neighboring MMT lamellae was populated by 24 Na+ counterions and PEO macromolecules of different lengths, ranging from 2 up to 240 repeat units. We considered three different loadings of PEO within the gallery: 80, 160, and 240 repeat units, corresponding to 13, 23, and 31 wt % PEO based on total mass of the nanocomposite, respectively. In the cases of 13 and 23 wt %, the polymer chains formed one or two well-defined amorphous layers with interlayer distances of 1.35 and 1.8 nm, respectively. We have observed also formation of a wider monolayer gallery with interlayer distances of 1.6 nm. Three-layer PEO films formed in the case of 31 wt % loading. The thermal properties were analyzed over the range 300-400 K, and the isothermal linear compressibility, transversal moduli, and shear moduli were calculated at 300 K. These properties are compared with the results of our simulation of thermal and mechanical properties of MMT crystal with galleries filled by one or two water layers as well as with those of an isolated clay nanoplate.

Molecular dynamics simulation of thermomechanical properties of montmorillonite crystal. 1. Isolated clay nanoplate.

The structure and mechanical properties of clay nanoparticles is a subject of growing interest because of their numerous applications in engineering. We present the results of molecular dynamics simulation for a single nanoplate of pyrophyllite - a 2:1 clay mineral consisting of two tetrahedral sheets of SiO4 and an intervening octahedral AlO6 sheet. Simulations were performed in the temperature interval from 5 to 750 K using the ionic-type potentials of Cygan et al. On this basis the temperature dependences of structural parameters, characterizing both tetrahedral and octahedral sheets as well as single lamella, have been studied. Two slightly different structures were observed in this wide temperature interval. The mechanical properties of the nanoplate were calculated from stress-strain diagrams, which have been obtained at relatively slow rates of deformation (for molecular simulations). Using different types of loading, we calculated the full elasticity tensor and estimated the influence of temperature on its components. We estimated also the bending and torsion stiffnesses of the nanoplate as specific characteristics of this type of particle. Because the nanoplate is atomically thin, a reasonable determination of the thickness is a nontrivial problem, both in the modeling of mechanical properties and in physical interpretation of the obtained data. We propose a procedure for its calculation.