Hybrid nanocomposites of 2D black phosphorus nanosheets encapsulated in PMMA polymer material: new platforms for advanced device fabrication.

Hybrid materials, containing a 2D filler embedded in a polymeric matrix, are an interesting platform for several applications, because of the variety of properties that the filler can impart to the polymer matrix when dispersed at the nanoscale. Moreover, novel properties could arise from the interaction between the two. Mostly the bulk properties of these materials have been studied so far, especially focusing on how the filler changes the polymeric matrix properties. Here we propose a complete change of perspective by using the hybrid nanocomposite material as a platform suitable to engineer the properties of the filler and to exploit its potential in the fabrication of devices. As a proof of concept of the versatility and the potential of the new method, we applied this approach to prepare black phosphorus (bP) nanocomposites through its dispersion in poly (methyl methacrylate). bP is a very interesting 2D material, whose application have so far been limited by its high reactivity to oxygen and water. In this respect, we show that electronic-grade bP flakes, already embedded in a protecting matrix since their exfoliation from the bulk material, are endowed with significantly increased stability and can be further processed into devices without degrading their properties.

A Bipolar CdS/Pd Photocatalytic Membrane for Selective Segregation of Reduction and Oxidation Processes.

A photocatalytically active bipolar membrane consisting of a CdS photocatalyst and Pd electrocatalyst has been constructed to carry out environmentally relevant oxidation and reduction processes. The ion exchange property of a bipolar membrane (BPM) has allowed us to load the CdS photocatalyst on one side and Pd electrocatalyst on the other side. By inserting the photocatalytic BPM-CdS/Pd membrane between the two compartments of an H-cell, we can separate the reduction and oxidation processes. Following visible light excitation of CdS in the BPM-CdS/Pd membrane, we can induce vectorial electron transfer from CdS to Pd and to an electron acceptor (4-nitrophenol). The holes generated at CdS are scavenged by ethanol or 4-chlorophenol. The photocatalytic reduction rate dependence on the Pd loading in the membrane as well as its effect on modulating the rates of electron and hole transfer processes are discussed. The design of a semiconductor and metal loaded membrane paves the way for improving selectivity and efficiency of photocatalytic processes.

3D Photothermal Cryogels for Solar-Driven Desalination.

This paper reports the fabrication of photothermal cryogels for freshwater production via the solar-driven evaporation of seawater. Photothermal cryogels were prepared via in situ oxidative polymerization of pyrrole with ammonium persulfate on preformed poly(sodium acrylate) (PSA) cryogels. We found that the pyrrole concentration used in the fabrication process has a significant effect on the final PSA/PPy cryogels (PPCs), causing the as-formed polypyrrole (PPy) layer on the PPC to evolve from nanoparticles to lamellar sheets and to consolidated thin films. PPC fabricated using the lowest pyrrole concentration (i.e., PPC10) displays the best solar-evaporation efficiency compared to the other samples, which is further improved by switching the operative mode from floating to standing. Specifically, in the latter case, the apparent solar evaporation rate and solar-to-vapor conversion efficiency reach 1.41 kg m-2 h-1 and 96.9%, respectively, due to the contribution of evaporation from the exposed lateral surfaces. The distillate obtained from the condensed vapor, generated via solar evaporation of a synthetic seawater through PPC10, shows an at least 99.99% reduction of Na while all the other elements are reduced to a subppm level. We attribute the superior solar evaporation and desalination performance of PPC10 to its (i) higher photoabsorption efficiency, (ii) higher heat localization effect, (iii) open porous structure that facilitates vapor removal, (iv) rough pore surface that increases the surface area for light absorption and water evaporation, and (v) higher water-absorption capacity to ensure efficient water replenishment to the evaporative sites. It is anticipated that the gained know-how from this study would offer insightful guidelines to better designs of polymer-based 3D photothermal materials for solar evaporation as well as for other emerging solar-related applications.

Photocatalytic Activity of Cellulose Acetate Nanoceria/Pt Hybrid Mats Driven by Visible Light Irradiation.

A photocatalytic system for the degradation of aqueous organic pollutants under visible light irradiation is obtained by an innovative approach based on ceria/platinum (Pt) hybrid nanoclusters on cellulose acetate fibrous membranes. The catalytic materials are fabricated by supersonic beam deposition of Pt nanoclusters directly on the surface of electrospun cellulose acetate fibrous mats, pre-loaded with a cerium salt precursor that is transformed into ceria nanoparticles directly in the solid mats by a simple thermal treatment. The presence of Pt enhances the oxygen vacancies on the surface of the formed ceria nanoparticles and reduces their band gap, resulting in a significant improvement of the photocatalytic performance of the composite mats under visible light irradiation. Upon the appropriate pretreatment and visible light irradiation, we prove that the most efficient mats, with both ceria nanoparticles and Pt nanoclusters, present a degradation efficiency of methylene blue of 70% and a photodegradation rate improved by about five times compared to the ceria loaded samples, without Pt. The present results bring a significant improvement of the photocatalytic performance of polymeric nanocomposite fibrous systems under visible light irradiation, for efficient wastewater treatment applications.

Polymer-Based Black Phosphorus (bP) Hybrid Materials by in Situ Radical Polymerization: An Effective Tool To Exfoliate bP and Stabilize bP Nanoflakes.

Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) toward both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes (bPn) exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: (i) the mixing of conventionally liquid-phase exfoliated bP (in dimethyl sulfoxide, DMSO) with poly(methyl methacrylate) (PMMA) solution; (ii) the direct exfoliation of bP in a polymeric solution; (iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn-MMA by sonication-assisted liquid-phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of the bPn is particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-solid state NMR studies) and are particularly stable to air and UV light exposure. The feasibility of this approach, capable of efficiently exfoliating bP while protecting the bPn, has been then verified by using different vinyl monomers (styrene and N-vinylpyrrolidone), thus obtaining hybrids where the nanoflakes are embedded in polymer matrices with a variety of intriguing thermal, mechanical, and solubility characteristics.

Postabsorptive and insulin-stimulated energy homeostasis and leucine turnover in offspring of type 2 diabetic patients.

OBJECTIVE: This study was performed to ascertain whether insulin resistance with respect to protein metabolism is an additional primary metabolic abnormality affecting insulin-resistant offspring of type 2 diabetic parents, along with insulin resistance with respect to glucose and lipid metabolism. RESEARCH DESIGN AND METHODS: We studied 18 young, nonobese offspring of type 2 diabetic parents and 27 healthy matched (by means of dual-energy X-ray absorption) individuals with the bolus plus continuous infusion of [6,6-(2)H(2)]glucose and [1-(13)C]leucine in combination with the insulin clamp (40 mU x m(-2) x min(-1)). RESULTS: Fasting plasma leucine, phenylalanine, alanine, and glutamine concentrations, as well as the glucose and leucine turnover (reciprocal pool model: 155 +/- 10 vs. 165 +/- 5 micromol x kg lean body mass(-1) x h(-1) in offspring of type 2 diabetic patients and healthy matched individuals, respectively), were also not different. During the clamp, glucose turnover rates were significantly reduced in offspring of type 2 diabetic patients (7.1 +/- 0.5) in comparison with healthy matched individuals (9.9 +/- 0.6 mg x kg lean body mass(-1) x min(-1); P < 0.01). Also, the suppression of leucine turnover was impaired in offspring of type 2 diabetic patients (12 +/- 1%) in comparison with healthy matched individuals (17 +/- 1%; P = 0.04) and correlated with the degree of the impairment of insulin-stimulated glucose metabolism (R(2) = 0.13; P = 0.02). CONCLUSIONS: Nonobese, nondiabetic, insulin-resistant offspring of type 2 diabetic patients were characterized by an impairment of insulin-dependent suppression of protein breakdown, which was proportional to the impairment of glucose metabolism. These results demonstrate that in humans, a primary in vivo impairment of insulin action affects glucose and fatty acid metabolism as previously shown and also protein/amino acid metabolism.

Fasting plasma leptin, tumor necrosis factor-alpha receptor 2, and monocyte chemoattracting protein 1 concentration in a population of glucose-tolerant and glucose-intolerant women: impact on cardiovascular mortality.

OBJECTIVE: Leptin and tumor necrosis factor (TNF)-alpha are associated with insulin resistance and cardiovascular disease. In vitro studies suggested that these effects may be mediated via overproduction of monocyte chemoattracting protein (MCP)-1/CCL2, which is a chemokine involved in the pathogenesis of atherosclerosis. RESEARCH DESIGN AND METHODS: In this study, fasting plasma leptin, soluble TNF-alpha receptor 2 (TNF-alpha-R2), and MCP-1/CCL2 concentrations were measured in 207 middle-aged women (age 61 +/- 12 years, BMI 30.1 +/- 6.6 kg/m(2)), including 53 patients with type 2 diabetes, 42 with impaired glucose tolerance, and 112 with normal glucose tolerance, to assess cross-sectionally their relationship with markers of atherosclerosis and, longitudinally over 7 years, whether their circulating levels were associated with cardiovascular disease (CVD) mortality. RESULTS: At baseline, leptin and TNF-alpha-R2 were not different among groups; meanwhile, MCP-1/CCL2 was increased in type 2 diabetes (P < 0.05). All showed significant associations with biochemical risk markers of atherosclerosis. In a univariate analysis, age, fasting insulin, leptin, and MCP-1/CCL2 were associated with CVD mortality at 7 years. When a multivariate analysis was performed, only age, leptin, and insulin retained an independent association with CVD mortality, with leptin showing a protective effect (hazard ratio 0.88; P < 0.02). CONCLUSIONS: In middle-aged women, MCP-1/CCL2, leptin, and TNF-alpha-R2 were all related to biochemical risk markers of atherosclerosis. MCP-1/CCL2 concentration was the only one to be increased in type 2 diabetes with respect to nondiabetic women and the only one to be associated with increased risk of CVD mortality after a 7-year follow-up period in the univariate analysis. In the multivariate analysis, neither MCP-1/CCL2 nor TNF-alpha-R2 was associated with CVD mortality, and inspection of the data showed that leptin, in both the univariate and multivariate analysis, was associated with a protective effect.

Postabsorptive and insulin-stimulated energy and protein metabolism in patients with myotonic dystrophy type 1.

BACKGROUND: Exaggerated insulin resistance was described as the major metabolic abnormality in myotonic dystrophy type 1 (DM1). We reported recently that the severity of the impairment in insulin-stimulated glucose metabolism in these patients was overestimated. OBJECTIVE: The aim was to dissect out insulin action with respect to whole-body energy homeostasis and glucose, protein, and lipid metabolism in patients with DM1 to assess the relevance of insulin resistance to the heterogeneous clinical manifestations of this syndrome. DESIGN: Ten nondiabetic patients with DM1 and 10 matched healthy control subjects were studied by means of 1) dual-energy X-ray absorptiometry; 2) a euglycemic-hyperinsulinemic clamp (40 mU. m(-2). min(-1)) combined with a primed, continuous infusion of [6,6-d(2)]glucose and [1-(13)C]leucine; 3) indirect calorimetry; and 4) localized (1)H magnetic resonance spectroscopy of the calf muscles. RESULTS: Patients with DM1 had less lean body mass, greater fat mass, and greater intramyocellular lipid contents than did healthy control subjects. Energy expenditure and glucose and lipid metabolism did not differ significantly between the groups. In contrast, markers of proteolysis were higher in DM1 patients in the postabsorptive and insulin-stimulated conditions and were associated with lower plasma concentrations of insulin-like growth factor 1 (P < 0.03) and higher plasma concentrations of tumor necrosis factor alpha receptor 2 (P = 0.04). CONCLUSIONS: Despite greater body fat and intramyocellular lipid contents in patients with DM1, insulin sensitivity was not significantly different between patients and control subjects. In contrast, the loss of lean body mass in patients with DM1 was associated with abnormal postabsorptive and insulin-stimulated regulation of protein breakdown. Lower plasma insulin-like growth factor 1 concentrations and higher tumor necrosis factor system activity might be involved in the muscle wasting of DM1.

Assessment of insulin sensitivity based on a fasting blood sample in men with liver cirrhosis before and after liver transplantation.

BACKGROUND: Insulin resistance is a key factor in the pathogenesis of hepatogenous diabetes and influences the prognosis of chronic liver diseases. In vivo assessment of insulin resistance in humans is expensive; therefore, surrogate indices based on a fasting plasma glucose and insulin concentrations (HOMA-IS, QUICKI) were proposed. This study aimed to test whether these simple indices are reliable measures of insulin sensitivity in patients with liver cirrhosis before and after liver transplantation (LTx). METHODS: HOMA-IS and QUICKI were compared with insulin sensitivity as assessed with the gold standard technique (insulin clamp) in 20 patients with liver cirrhosis, in 36 patients after LTx, and in 25 matched healthy subjects (predominantly men). To test whether these indices may be applied also in prospective studies, 10 patients with liver cirrhosis were studied longitudinally before and 2 years after LTx. RESULTS: Both HOMA-IS and QUICKI were associated with insulin sensitivity in patients with liver cirrhosis (r=0.63, P=0.005 and r=0.60, P=0.009) and in LTx patients (r=0.41, P=0.02 and r=0.46, P=0.05). Both were able to detect the improvement of insulin sensitivity after LTx in the patients studied prospectively. CONCLUSIONS: HOMA-IS and QUICKI are simple reliable tools to assess insulin sensitivity in clinical and epidemiologic investigations of chronic liver disease before and after LTx.

Abnormal left ventricular energy metabolism in obese men with preserved systolic and diastolic functions is associated with insulin resistance.

OBJECTIVE: Perturbations in cardiac energy metabolism might represent early alterations in diabetes preceding functional and pathological changes. We evaluated left ventricular (LV) structure/geometry and function in relation to energy metabolism and cardiovascular risk factors in overweight/obese men using magnetic resonance techniques. RESEARCH DESIGN AND METHODS: We studied 81 healthy men (aged 22-55 years, with BMI between 19 and 35 kg/m2) by means of cardiac magnetic resonance imaging and 31P-magnetic resonance spectroscopy in the resting and fasted conditions and stratified them in quartiles of BMI (cut offs: 23.2, 25.5 and 29.0 kg/m2). RESULTS: LV mass increased across quartiles of BMI; meanwhile, the volumes did not differ. Parameters of LV systolic and diastolic function were not different among quartiles. The phosphocreatine-to-ATP ratio was reduced across increasing quartiles of mean +/- SD BMI (2.25 +/- 0.52, 1.89 +/- 0.26, 1.99 +/- 0.38, and 1.79 +/- 0.29; P < 0.006) in association with insulin sensitivity (computer homeostasis model assessment 2 model); this relation was independent of age, BMI, blood pressure, wall mass, HDL cholesterol, triglycerides, smoking habits, and metabolic syndrome. CONCLUSIONS: Abnormal LV energy metabolism was detectable in obese men in the presence of normal function, supporting the hypothesis that metabolic remodeling in insulin resistant states precedes functional and structural/geometrical remodeling of the heart regardless of the onset of overt hyperglycemia.

Insulin resistance and whole body energy homeostasis in obese adolescents with fatty liver disease.

Obese adolescents are at risk of developing NAFLD and type 2 diabetes. We measured noninvasively the IHF content of obese adolescents to ascertain whether it is associated with insulin resistance and abnormal energy homeostasis. IHF content, whole body energy homeostasis, insulin sensitivity, and body composition were measured using localized hepatic (1)H-MRS, indirect calorimetry, fasting-derived and 3-h-OGTT-derived surrogate indexes (HOMA2 and WBISI), and DEXA, respectively, in 54 obese adolescents (24 female and 30 male, age 13 +/- 2 yr, BMI >99th percentile for their age and sex). NAFLD (defined as IHF content >5% wet weight) was found in 16 individuals (30%) in association with higher ALT (P < 0.006), Hb A(1c) (P = 0.021), trunk fat content (P < 0.03), and lower HDL cholesterol (P < 0.05). Individuals with NAFLD had higher fasting plasma glucose (89 +/- 8 vs. 83 +/- 9 mg/dl, P = 0.01) and impaired insulin sensitivity (HOMA2 and WBISI, P < 0.05). Meanwhile, parameters of insulin secretion were unaffected. Their reliance on fat oxidation in the fasting state was lower (RQ 0.83 +/- 0.08 vs. 0.77 +/- 0.05, P < 0.01), and their ability to suppress it during the oral glucose challenge was impaired (P < 0.05) vs. those with normal IHF content. When controlling for trunk fat content, the correlation between IHF content and insulin sensitivity was weakened, whereas the correlation with fasting lipid oxidation was maintained. In conclusion, NAFLD is common in childhood obesity, and insulin resistance is present in association with increased trunk fat content. In contrast, the rearrangement of whole body substrate oxidation in these youngsters appeared to be an independent feature.