Highly efficient visible-light-assisted photocatalytic hydrogen generation from water splitting catalyzed by Zn0.5Cd0.5S/Ni2P heterostructures

Development of heterostructured photocatalysts which can facilitate spatial separation of photo-generated charge carriers is crucial for achieving improved photocatalytic H₂ production. Consequently, herein, we report the synthesis of Zn_0.5Cd_0.5S/Ni₂P heterojunction photocatalysts with varying amount of Ni₂P, 0.5 (S1), 1 (S2), 3 (S3), 5 (S4) and 10wt% (S5) for the efficient visible-light-assisted H₂ generation by water splitting. The heterostructures were characterized thoroughly by PXRD, FE-SEM, EDS, HR-TEM and XPS studies. FE-SEM and HR-TEM analyses of the samples unveiled the presence of Zn_0.5Cd_0.5S microspheres composed of smaller nanocrystals with the surface of the microspheres covered with Ni₂P nanosheets and the intimate contact between the Zn_0.5Cd_0.5S and the Ni₂P. Further, visible-light-assisted photocatalytic investigation of the samples showed excellent water splitting activity of the heterostructure, Zn_0.5Cd_0.5S/1wt%Ni₂P (S2) with very high H₂ generation rate of 21.19 mmol h^?1g^?1 and the AQY of 21.16% at 450 nm with turnover number (TON) and turnover frequency (TOF) of 251,516 and 62,879 h^?1 respectively. Interestingly, H₂ generation activity of S2 was found to be about four times higher than that of pure Zn_0.5Cd_0.5S (5.0 mmol h^?1g^?1) and about 240 times higher than that of CdS/1wt%Ni₂P. The enhanced H₂ generation activity of S2 has been attributed to efficient spatial separation of photogenerated charge carriers and the presence of highly reactive Ni₂P sites on the surface of Zn_0.5Cd_0.5S microspheres. A possible mechanism for the enhanced photocatalytic H₂ generation activity of Zn_0.5Cd_0.5S/1wt%Ni₂P (S2) has been proposed and is further supported by photoluminescence and photocurrent measurements. Furthermore, the catalyst, S2 can be recycled for several cycles without significant loss of catalytic activity and photostability. Remarkably, the H₂ generation activity of S2 was found to be even higher than the reported examples of Zn_xCd_1-xS doped with noble metal cocatalysts. Hence, the present study highlights the importance of Zn_0.5Cd_0.5S/Ni₂P heterostructures based on non-noble metal co-catalyst for efficient visible-light-driven H₂ production from water splitting.     

The prognostic significance of sialyl-Tn antigen in women treated with breast carcinoma treated with adjuvant chemotherapy

BACKGROUND: Sialyl-Tn (STn) represents an aberrantly glycosylated mucin epitope that is expressed in breast carcinoma and other adenocarcinomas and is an important factor in the development of novel immunotherapeutic approaches. The primary aim of the current study was to investigate the influence of STn expression on the prognoses of patients with breast carcinoma. METHODS: A cohort of 207 women diagnosed with invasive breast carcinoma who were treated with anthracycline-containing adjuvant chemotherapy and were enrolled in a randomized clinical trial were studied. Expression of STn was determined by an immunohistochemical procedure in which the B72.3 monoclonal antibody was used. Kaplan-Meier and Cox proportional regression survival analyses were used to compare low STn and high STn patients. RESULTS: Forty-eight (23%) of the 207 specimens demonstrated high STn staining (>25% cells were immunoreactive). During a median follow-up of 5 years, high STn patients had worse disease free survival than low STn patients (55% vs. 74%, respectively; P = 0.03). High STn expression was significantly associated with age (P = 0.04) but not with other conventional prognostic markers. In multivariate analysis using the Cox regression model, high STn emerged as an independent prognostic indicator for disease free survival (hazard ratio [HR], 2.02; 95% confidence interval [CI], 1.09-3.73) and for overall survival (HR, 2.16; 95% CI, 0.95-4.92). CONCLUSIONS: The results of this study suggest that STn may be a valuable marker for identifying women at high risk of developing recurrent breast carcinoma who may be candidates for trials investigating new therapies in combination with standard adjuvant therapy.     

Multiobjective design of actively controlled structures using a hybrid optimization method

A multiobjective approach to the combined structure and control optimization problem for flexible space structures is presented. The proposed formulation addresses robustness considerations for controller design, as well as a simultaneous determination of optimum actuator locations. The structural weight, controlled system energy, stability robustness index and damping augmentation provided by the active controller are considered as objective functions of the multiobjective problem which is solved using a cooperative game-theoretic approach. The actuator locations and the cross-sectional areas of structural members are treated as design variables. Since the actuator locations are spatially discrete, whereas the cross-sectional areas are continuous, the optimization problem has mixed discrete-continuous design variables. A solution approach to this problem based on a hybrid optimization scheme is presented. The hybrid optimizer is a synergetic blend of artificial genetic search and gradient-based search techniques. The computational procedure is demonstrated through the design of an ACOSS-FOUR space structure. The optimum solutions obtained using the hybrid optimizer are shown to outperform the optimum results obtained using gradient-based search techniques.     

A comparative computational study of diesel steam reforming in a catalytic plate heat‐exchange reactor

A two‐dimensional steady‐state model of a catalytic plate reactor for diesel steam reforming is developed. Heat is provided indirectly to endothermic reforming sites by flue gas from a SOFC tail‐gas burner. Two experimentally validated kinetic models on diesel reforming on platinum (Pt) catalyst were implemented for a comparative study; the model of Parmar et al., Fuel. 2010;89(6):1212–1220 for a Pt/Al₂O₃ and the model of Shi et al., International Journal of Hydrogen Energy. 2009;34(18):7666–7675 for a Pt/Gd‐CeO₂ (GDC). The kinetic models were compared for: species concentration, approach to equilibrium, gas hourly space velocity and effectiveness factor. Cocurrent flow arrangement between the reforming and the flue gas channels showed better heat transfer compared to counter‐current flow arrangement. The comparison between the two kinetic models showed that different supports play significant role in the final design of a reactor. The study also determined that initial 20% of the plate reactor has high diffusion limitation suggesting to use graded catalyst to optimize the plate reactor performance. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1102–1113, 2017     

Quality of maize grains treated with allyl isothiocyanate stored in hermetic bags

This purpose of this study was to evaluate the quality of maize grain treated with allyl isothiocyanate (AITC) and stored under hermetic conditions. Maize grains with moisture contents of 14.8 or 17.9% wet basis (w.b.) initial moisture content were packaged in high density polyethylene bags and submitted to treatment with AITC at a concentration of 300 μL kg⁻¹. The bags were stored in controlled temperature chambers at 15, 25 or 35 °C. At 30-day intervals, for a period of 150 days, three bags were removed from the chambers and the grains were submitted to commercial classification, moisture content, bulk density, germination potential and electrical conductivity analyses. It was verified that AITC at 300 μL kg⁻¹ has no significant effect on the physiological quality of maize grains stored in hermetic bags. The microbiological analyses indicate the control of fungi and yeasts on the grains stored with 17.9% w.b. and treated with AITC. The maize grains stored with 14.8% w.b. moisture content in hermetic systems suffered no deterioration and retained their quality for a longer period than grains stored with 17.9% w.b. moisture content, independent of AITC treatment.     

Reduced Granule Cell Proliferation and Molecular Dysregulation in the Cerebellum of Lysosomal Acid Phosphatase 2 (ACP2) Mutant Mice

Lysosomal acid phosphatase 2 (Acp2) mutant mice (naked-ataxia, nax) have a severe cerebellar cortex defect with a striking reduction in the number of granule cells. Using a combination of in vivo and in vitro immunohistochemistry, Western blotting, BrdU assays, and RT-qPCR, we show downregulation of MYCN and dysregulation of the SHH signaling pathway in the nax cerebellum. MYCN protein expression is significantly reduced at P10, but not at the peak of proliferation at around P6 when the number of granule cells is strikingly reduced in the nax cerebellum. Despite the significant role of the SHH–MycN pathway in granule cell proliferation, our study suggests that a broader molecular pathway and additional mechanisms regulating granule cell development during the clonal expansion period are impaired in the nax cerebellum. In particular, our results indicate that downregulation of the protein synthesis machinery may contribute to the reduced number of granule cells in the nax cerebellum.     

A Polymath Approach for the Prediction of Optimized Transesterification Process Variables of Polanga Biodiesel

An attempt has been made to employ an artificial neural network (ANN) combined with a genetic algorithm (GA) in MATLAB 7.0 for predicting the optimized reaction variables for maximum biodiesel production of polanga oil by the transesterification process. The developed ANN is a multilayer feed-forward back-propagation network (5-10-1) with five input, ten hidden and one output layers. The input variables are the molar ratio of ethanol to oil (X ₁ in % v/v), the catalyst concentration (X ₂ in % w/v), the reaction temperature (X ₃ in °C), the reaction time (X ₄ in min), the agitation speed (X ₅ in rpm) and the output parameter is biodiesel yield (% by weight) of polanga oil. The experimental data used in the developed ANN were obtained from response surface methodology (RSM) based on a central composite design. The trained ANN was tested using different training functions from the MATLAB to predict the best correlation coefficients of training, testing and validation. The data generated by trained ANN is used by GA with regards to the best response (for predicting biodiesel yield greater than predicted by RSM) for different combinations of variables (X ₁, X ₂, X ₃, X ₄, and X ₅) to attain optimization. The average biodiesel yield (by performing experiments under optimized conditions) of 92 % by weight was produced against the proposed value of 91.08 % by weight.     

Effect of flour blending on functional, baking and organoleptic characteristics of bread

Soybean (full‐fat and defatted) and barley flours were incorporated into wheat flour at 5, 10, 15 and 20% substitution levels. The gluten content, sedimentation value and water absorption capacity of the flour blends and the mixing time of the dough decreased with increase in the level of soybean and barley flour separately and in combinations. Protein and glutelin contents increased significantly on blending of soyflour (full‐fat and defatted) to bread wheat flour. The breads prepared from the blends also varied in their loaf weight, loaf volume and sensory characteristics. The bread volume decreased with increasing amount of non‐wheat flour substitution. The crumb colour changed from creamish white to dull brown and a gradual hardening of crumb texture was observed as the addition of soybean (full‐fat and defatted) and barley flours increased. At the higher levels, the acceptability declined because of the compact texture of the crumb and the strong flavour of the product. The addition of 10% of soyflour (full‐fat and defatted) or 15% of barley flour, full‐fat soy + barley or defatted soy + barley flour to bread flour produced acceptable bread.     

Computer simulation and modeling of graded bandgap CuInSe2/CdS based solar cells

This paper proposes the graded bandgap absorber material, Cu_1-xAg_xIn_1-y-zGa_yAl_z Se/sub 2(1-u$/ -/sub w/)S_2uTe_2w (CIS*) multinary system, to improve the low open-circuit voltage (V_OC) seen in CuInSe₂/CdS solar cells, without sacrificing the short-circuit current density (J_sc). It also proposes a p-i-n model for the CuInSe₂/CdS solar cell, where the intrinsic region is the graded bandgap CIS*. Reflecting surfaces are provided at the p-i and n-i interfaces to trap the light in the narrow intrinsic region for maximum generation of electron and hole pairs (EHP's). This optical confinement results in a 25-40% increase in the number of photons absorbed. An extensive numerical simulator was developed, which provides a 1-D self-consistent solution for Poisson's equation and the two continuity equations for electrons and holes. This simulator was used to generate J-V curves to delineate the effect of different grading profiles on cell performance. The effects of a uniform bandgap, normal grading, reverse grading, and a low bandgap notch have been considered. Having established the inherent advantages to these grading profiles an optimal doubly graded structure is proposed with grading between 1.5 eV and 1.3 eV regions which has V_OC=0.86 V, η=17.9%, FF=0.79 and J_sc=26.3 mA/cm² compared to 0.84 V, 14.9%, 0.76, and 23.3 mA/cm², respectively, for the highest efficiency 1.4-eV uniform bandgap cell. Replacing the thick CdS(2.42 ev) layer assumed in our simulations with a wide gap semiconductor such as ZnO(3.35 ev) increases all current densities by about 5 mA/cm², and increases the optimal calculated efficiency from 17.9% to roughly 21% for a doubly graded structure with a thickness of 1 μm and bandgaps ranging from 1.3 eV to 1.5 eV     

Fumigation with essential oil of mustard retards fungal growth and accumulation of ergosterol and free fatty acid in stored shelled groundnuts

Shelled groundnut (Arachis hypogaea) samples with moisture contents (m.c.) between 7.5 and 10.5% and inoculated with conidia of Aspergillus glaucus and A. parasiticus were stored for 15-90 days at 25 ± 2 °C, and fumigated with synthetic food grade essential oil of mustard (100 μl/l space). Deterioration of the samples was assessed by estimating the percentage of kernels colonized by fungi, the number of colony forming units (CFUs)/kernel, and the accumulation of ergosterol and free fatty acids (FFA). The values of these variables increased with the m.c. and storage period, independent of the fumigation treatment; however, the rate of increase was significantly lower in fumigated samples. After 90 days storage, the proportion of kernels yielding A. glaucus was similar in all samples, but the number of CFUs was 300×, ergosterol content 3.6× and FFA 4× higher in non-fumigated than in fumigated samples. In fumigated samples, no molded kernels were visible, while many were seen in non-fumigated samples after 30 or 60 days storage at 10.5 or 9.3% m.c., respectively. The deterioration retardation featured a reduced inoculum on kernel surfaces. Aspergillus parasiticus did not colonize kernels independently of m.c. and fumigation treatments. There was a strong positive correlation between CFUs and ergosterol or FFA content when the data of fumigated and non-fumigated samples were analyzed separately. However, this relationship was absent when data were pooled to disregard the fumigation effect. The correlation between ergosterol and FFA content remained high regardless of the fumigation treatment (r = 0.99). The ergosterol or FFA content of stored groundnuts can be used interchangeably, as a sensitive indicator, to assess deterioration caused by xeric storage fungi. However, the latter was preferable because it was simpler to assess and provided a direct indication of economic losses due to reduced oil yield.