Co-Fermentation of Cheese Whey and Crude Glycerol in EGSB Reactor as a Strategy to Enhance Continuous Hydrogen and Propionic Acid Production

This study evaluated the production of hydrogen and propionic acid in an expanded granular sludge bed (EGSB) reactor by co-fermentation of cheese whey (CW) and crude glycerol (CG). The reactor was operated at hydraulic retention time (HRT) of 8 h by changing the CW/CG ratio from 5:1 to 5:2, 5:3, 5:4, and 5:5. At the ratio of 5:5, HRT was reduced from 8 to 0.5 h. The maximum hydrogen yield of 0.120 mmol H₂ g COD^?1 was observed at the CW/CG ratio of 5:1. Increasing the CG concentration repressed hydrogen production in favor of propionic acid, with a maximum yield of 6.19 mmol HPr g COD^?1 at the CW/CG ratio of 5:3. Moreover, by reducing HRT of 8 to 0.5 h, the hydrogen production rate was increased to a maximum value of 42.5 mL H₂ h^?1 L^?1at HRT of 0.5 h. The major metabolites were propionate, 1,3-propanediol, acetate, butyrate, and lactate.     

Multivariate control charts based on NAS and mid‐infrared spectroscopy for quality control of B5 blends of methyl soybean biodiesel in diesel

In this work, mid‐infrared spectroscopy and multivariate control charts based on net analyte signal were applied for quality control of B5 blends of biodiesel/diesel (5% biodiesel/95% diesel). Control charts were constructed using instrumental signal decomposition, generating three charts: the net analyte signal chart for monitoring the analyte of interest (methyl soybean biodiesel); the interference chart, which corresponds to the contribution of all other compounds in the diesel sample (diesel); and the residual chart, which corresponds to non‐systematic variations. Statistical limits were established for each developed chart, using samples inside quality specifications (normal operation conditions). To validate multivariate control charts, new samples were analyzed. The new samples represented samples in‐control and samples out‐of‐control in relation to the content of biodiesel, adulterated biodiesel with severe vegetable oils and adulterated diesel with residual automotive lubricant oil, kerosene, and gasoline. The results obtained show an excellent distinction between the samples inside and out of the quality specifications, with 91% and 100% correctly classified, respectively, which demonstrates that the methodology developed is a viable alternative for quality monitoring of this type of fuel. Copyright © 2015 John Wiley & Sons, Ltd.     

Investigation of thermal stability, spectral, magnetic, and antimicrobial behavior for new complexes of Ni(II), Cu(II), and Zn(II) with a bismacrocyclic ligand

Novel complexes of type M₂LCl₄·nH₂O (M: Ni, n = 4; M: Cu, n = 2.5 and M: Zn, n = 1.5; L: ligand resulted from 1,3-phenylenediamine, 3,6-diazaoctane-1,8-diamine, and formaldehyde one-pot condensation) were synthesized and characterized. The ligand was also isolated and characterized. The complexes features have been assigned from microanalytical, electrospray ionization tandem mass spectrometry, IR, UV–vis, ¹H NMR, and EPR spectra as well as magnetic data at room temperature. Simultaneous thermogravimetric/dynamic scanning calorimetry/evolved gas analysis measurements were performed to evidence the nature of the gaseous products formed in each step. Processes as water elimination, fragmentation, and oxidative degradation of the organic ligand as well as chloride elimination were observed during the thermal decomposition. The final product of decomposition was metal(II) oxide except for copper complex where CuCl remained also in the oxide network. The complexes exhibited an improved antibacterial activity in comparison with the ligand concerning both planktonic as well as biofilm-embedded cells.     

Electrochemical DNA biosensor for human papillomavirus 16 detection in real samples

An electrochemical DNA biosensor for human papillomavirus (HPV) 16 detection has been developed. For this proposed biosensor, l-cysteine was first electrodeposited on the gold electrode surface to form l-cysteine film (CYSFILM). Subsequently, HPV16-specific probe was immobilized on the electrode surface with CYSFILM. Electrochemistry measurement was studied by differential pulse voltammetry method (DPV). The measurement was based on the reduction signals of methylene blue (MB) before and after hybridization either between probe and synthetic target or extracted DNA from clinical samples. The effect of probe concentration was analyzed and the best results were seen at 1000 nM. The hybridization detection presented high sensitivity and broad linear response to the synthetic-target concentration comprised between 18.75 nM and 250 nM as well as to a detection limit of 18.13 nM. The performance of this biosensor was also investigated by checking probe-modified electrode hybridization with extracted DNA from samples. The results showed that the biosensor was successfully developed and exhibited high sensitivity and satisfactory selectivity to HPV16. These results allow for the possibility of developing a new portable detection system for HPVs and for providing help in making an effective diagnosis in the early stages of infection.     

DFT in a nutshell

The purpose of this short essay is to introduce students and other newcomers to the basic ideas and uses of modern electronic density functional theory, including what kinds of approximations are in current use, and how well they work (or not). The complete newcomer should find it orients them well, while even longtime users and aficionados might find something new outside their area. Important questions varying in difficulty and effort are posed in the text, and are answered in the Supporting Information. © 2012 Wiley Periodicals, Inc.     

Sun Exposure over a Lifetime in Australian Adults from Latitudinally Diverse Regions

Spatio‐temporal patterns in sun exposure underlie variations in skin cancer incidence and vitamin D deficiency, indicate effectiveness of sun protection programs and provide insights into future health risks. From 558 adults across four regions of Australia (Brisbane (27°S), Newcastle (33°S), Geelong and the Western Districts of Victoria (37°S) and Tasmania (43°S)), we collected: self‐report data on time‐in‐the‐sun from age 6 years; natural skin color and ethnicity; silicone skin casts (for cumulative skin damage); and serum for vitamin D status. Ambient ultraviolet radiation (UVR) at the location of residence, with time‐in‐the‐sun, was used to calculate a “UVR dose” for each year of life. Individuals maintained their ranking compared to their peers for time‐in‐the‐sun in summer compared to winter and across ages (Spearman rho 0.24–0.84, all P < 0.001). Time‐in‐the‐sun decreased with age in all birth cohorts, and over calendar time. Summer time‐in‐the‐sun increased with increasing latitude (P < 0.001). Seasonal variation in vitamin D status had greater amplitude and vitamin D deficiency increased with increasing latitude. Temporal patterns are consistent with effectiveness of sun protection programs. Higher relative time‐in‐the‐sun persists from childhood through adulthood. Lower summer time‐in‐the‐sun in the warmest location may have implications for predictions of UVR‐related health risks of climate change.     

The Periodate‐Based Double Perovskites M2NaIO6 (M = Ca,Sr, and Ba)

The crystal structures of the M₂NaIO₆ series (M = Ca, Sr, Ba), prepared at 650 °C by ceramic methods, were determined from conventional laboratory X‐ray powder diffraction data. Synthesis and crystal growth were made by oxidizing I^– with O₂^(air) to I⁷⁺ followed by crystal growth in the presence of NaF as mineralizator, or by the reaction of the alkali‐metal periodate with the alkaline‐earth metal hydroxide. All three compounds are insoluble and stable in water. The barium compound crystallizes in the cubic space group Fm3m (no. 225) with lattice parameters of a = 8.3384(1) Å, whereas the strontium and calcium compounds crystallize in the monoclinic space group P2₁/c (no. 14) with a = 5.7600(1) Å, b = 5.7759(1) Å, c = 9.9742(1) Å, β = 125.362(1)° and a = 5.5376(1) Å, b = 5.7911(1) Å, c = 9.6055(1) Å, β = 124.300(1)°, respectively. The crystal structure consists of either symmetric (for Ba) or distorted (for Sr and Ca) perovskite superstructures. Ba₂NaIO₆ contains the first perfectly octahedral [IO₆]^5– unit reported. The compounds of the ortho‐periodates are stable up to 800 °C. Spectroscopic measurements as well as DFT calculations show a reasonable agreement between calculated and observed IR‐ and Raman‐active vibrations.     

Highly sensitive ion preconcentration method based on flow sorbent extraction using multiwall carbon nanotubes

In this work a solid phase on-line uranium ion preconcentration system coupled with spectrophotometry has been developed. The method is based on uranyl ion preconcentration at pH 3.75 onto multiwall carbon nanotubes treated with HNO₃. After preconcentration, the uranyl ions are eluted with 0.32?mol?L^?1HCl followed by reaction with 3,6-bis[(2-arsonophenyl)-azo]-4,5-dihydroxy-2,7-naphthalendisulfonic acid 0.08%[w/v] (Arsenazo III), which had maximum monitored absorbance of 650?nm. Effects of the pertinent experimental parameters on the system were investigated by means of 2^6?2 fractional factorial design, while optimization was carried out using the Doehlert matrix. Under optimized conditions, detection and quantification limits were found to be 0.21 and 0.7?µg?L^?1, respectively. The analytical curve ranged from 5 to 150?µg?L^?1 (r?=?0.998), while the relative standard deviations (RSD) were 3.27 and 2.56% for the respective uranium concentrations of 10 and 100?µg?L^?1 (n?=?10). The features obtained for the on-line preconcentration system were: preconcentration factor of 228, concentration efficiency of 57?min^?1, consumption index of 0.13?mL and sample throughput of 15?h^?1. In order to assess the accuracy of the proposed method, addition and recovery studies were carried out on spring water samples from different sources and synthetic seawater with satisfactory results ranging from 94.85 up to 103.65%.