Smart Biopolymer-Based Nanocomposite Materials Containing pH-Sensing Colorimetric Indicators for Food Freshness Monitoring

Nanocomposite biopolymer materials containing colorimetric pH-responsive indicators were prepared from gelatin and chitosan nanofibers. Plant-based extracts from barberry and saffron, which both contained anthocyanins, were used as pH indicators. Incorporation of the anthocyanins into the biopolymer films increased their mechanical, water-barrier, and light-screening properties. Infrared spectroscopy and scanning electron microscopy analysis indicated that a uniform biopolymer matrix was formed, with the anthocyanins distributed evenly throughout them. The anthocyanins in the composite films changed color in response to alterations in pH or ammonia gas levels, which was used to monitor changes in the freshness of packaged fish during storage. The anthocyanins also exhibited antioxidant and antimicrobial activity, which meant that they could also be used to slow down the degradation of the fish. Thus, natural anthocyanins could be used as both freshness indicators and preservatives in biopolymer-based nanocomposite packaging materials. These novel materials may therefore be useful alternatives to synthetic plastics for some food packaging applications, thereby improving the environmental friendliness and sustainability of the food supply.     

Cobalt-promoted MoS2 nanosheets: A promising novel diesel hydrodesulfurization catalyst

MoS₂ has been commonly used as a catalyst in hydrodesulfurization (HDS) of petroleum cuts in crude oil refineries. In this study, the synthesis of unsupported MoS₂ and Co-promoted MoS₂ nanosheets produced from molybdenum oxide and thiourea is reported. The synthesized samples were characterized by using x-ray fluorescence, x-ray diffraction, Brunauer–Emmett–Teller (BET), temperature-programmed reduction, thermal gravimetric analysis, and transmission electron microscopy methods, and then they were utilized for HDS of diesel through a fixed-bed catalytic reactor. Results indicated that a cobalt promoter affected both the number and the performance of active sites of the molybdenum sulfides, and the activity of the promoted MoS₂ catalyst was consistently higher than that of the MoS₂ catalyst. More significantly, the activity of the promoted catalyst was slightly declined during 48 h continuous HDS reaction, which indicated the stability of this catalyst. Additionally, during 12 h of test run, the HDS activity of the promoted catalyst was about 60% higher than MoS₂ one.     

Amalgamation property for the class of basic algebras and some of its natural subclasses

We study Basic algebra, the algebraic structure associated with basic propositional calculus, and some of its natural extensions. Among other things, we prove the amalgamation property for the class of Basic algebras, faithful Basic algebras and linear faithful Basic algebras. We also show that a faithful theory has the interpolation property if and only if its correspondence class of algebras has the amalgamation property.     

On the linear Lindenbaum algebra of Basic Propositional Logic

We study the linear Lindenbaum algebra of Basic Propositional Calculus, called linear basic algebra. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A metal organic framework prepared from benzene-1,3,5-tricarboxylic acid and copper(II), and functionalized with various polysulfides as a sorbent for selective sorption of trace amounts of heavy metal ions

Novel composites were obtained via direct assembly of polysulfides (S_x^2?, X?=?3, 4, 6) on the surface of a metal organic framework (MOF; type benzene-1,3,5-tricarboxylic/Cu(II). They are referred to as S_x-MOFs and were used for highly selective and efficient extraction of ultra-trace amounts of heavy metal ions from aqueous solutions. The structure of the S_x-MOFs was characterized by Raman spectroscopy, FT-IR, X-ray diffraction, and scanning electron microscopy. The Raman spectra of S_x-MOF is similar to the bare MOF and shows the MOFs structure to be well retained after S_x functionalization. The selective interaction of S_x with soft metal ions and the high surface area of MOFs resulted in excellent affinity and selectivity for ions such as Hg(II). The S_x-MOFs of type S₄-MOF had the highest distribution coefficient K_d value (~10⁷) and best extraction recovery (~100%) for Hg(II). The S₄-MOF also has high selectivity in the following order: Hg(II) >?>?Pb(II)?>?Zn(II)?>?Ni(II)?>?Co(II). The binding process of the metals occurs via M–S bonding. The ions were quantified by inductively coupled plasma optical emission spectrometry (ICP-OES). The detection limit for Hg(II) is 0.13 μg L^?1. The S₄-MOF was applied to the extraction of trace metal ions from natural and contaminated waters and data were compared with other sorbets. The results revealed that S₄-MOF is an excellent adsorbent for sorption of heavy metal ions even in the presence of the relatively high concentration of other ions.

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Graphical abstract A composite was synthesized via direct assembly of polysulfides (S_x^2?, X?=?3, 4, 6) on surface of the metal organic framework (S_x-MOF) and was used for selective and efficient extraction of ultra-trace amounts of heavy metal ions from aqueous solutions.

     

A New and Efficient Synthesis of Highly Functionalized (Triphenylphosphoranylidene)cyclopentadienes with Zwitterionic Resonance Structures

Different esters of 2‐aryl‐4‐hydroxy‐3‐nitro‐5‐(triphenylphosphoranylidene)cyclopenta‐1,3‐diene‐1‐carboxylates 1 were prepared in excellent yields from the 1 : 1 : 1 reaction between Ph₃P, dialkyl acetylenedicarboxylates 2 , and (substituted) 2‐(nitroethenyl)benzenes 3 (Scheme 1). The structures of the highly functionalized compounds 1 were corroborated spectroscopically (IR, ¹H‐, ¹³C‐, ³¹P‐NMR, EI‐MS) and by elemental analyses. A plausible mechanism for this type of cyclization is proposed (Scheme 2).     

Determination of pKa values for (E)-2-hydroxy-5-(aryldiazenyl) benzaldehydes in dimethyl sulfoxide: Cyclic voltammetry and density functional theory calculations

The (E)-2-hydroxy-5-(aryldiazenyl) benzaldehydes (azo dyes 1–4 ) were synthesized in high purity. As they are insoluble in water, the usual analytical methods cannot be utilized to determine their pK_a values. Cyclic voltammetry was experimentally used to determine their pKa values in DMSO solvent. In addition, computational methods and a conductor-like screening model (COSMO) were used to calculate the solvent effect. , , K_exchange, and pK_a values were estimated for the azo dyes being studied using the BP86, TPSS, B3LYP, PBE0, TPSSh, and PW6B95 density functionals in def2-TZVP basis sets. The obtained mean absolute deviations (MADs) indicate that the results of BP86, PBE0, and PW6B95 functionals are in good agreement with experimental values.     

Dodecylsulfate-doped polypyrrole film prepared by electrochemical fiber coating technique for headspace solid-phase microextraction of polycyclic aromatic hydrocarbons

The electrochemical fiber coating (EFC) technique was used for the preparation of dodecylsulfate-doped polypyrrole (PPy-DS), and applied as a new fiber for solid-phase microextraction (SPME) procedures. PPy-DS film was directly electrodeposited on the surface of a platinum wire from an aqueous solution containing pyrrole and sodium dodecylsulfate, using cyclic voltammetry (CV). The effect of polymerization conditions and type of dopants on the thermal stability, adhesion and extraction characteristics of the fiber were investigated. The electron microscopy imaging of PPy-DS film suggested that the surface fiber coating was well-distributed with a porous structure. The fiber coating can be prepared easily in a reproducible manner, and it is inexpensive and has a stable performance at high temperatures (up to the 300 degrees C). The extraction properties of the fiber to eight polycyclic aromatic hydrocarbons (PAHs) were examined, using a headspace-SPME (HS-SPME) device coupled with gas chromatography-flame ionization detection (GC-FID) and gas chromatography-mass spectrometry (GC-MS). The results revealed study shows that PPy-DS as a SPME fiber coating is suitable for the successful extraction of PAHs. The effects of the extraction parameters including exposure time, sampling temperature, salt concentration, and stirring rate on the extraction efficiency have been studied. A satisfactory reproducibility for extractions from spiked water samples at PPb-level with R.S.D. < 7.6% (n = 7) was obtained. The calibration graphs were linear in the range of 0.5-100ng ml(-1) and detection limits for the selected PAHs were between 0.05-0.16 ng ml(-1). Comparing the HS-SPME results for extraction and determination of PAHs using PPy-DS fiber with the corresponding literature data using PDMS fiber shows that the proposed fiber has a better detection limit for low molecular weight PAHs. The life span and stability of PPy-DS fiber is good and it can be used more than 50 times at 250 degrees C without any significant change in sorption properties.     

Determination of three antidepressants in urine using simultaneous derivatization and temperature‐assisted dispersive liquid–liquid microextraction followed by gas chromatography–flame ionization detection

This paper presents a fast and simple method for the extraction, preconcentration and determination of fluvoxamine, nortriptyline and maprotiline in urine using simultaneous derivatization and temperature‐assisted dispersive liquid–liquid microextraction (TA‐DLLME) followed by gas chromatography–flame ionization detection (GC‐FID). An appropriate mixture of dimethylformamide (disperser solvent), 1,1,2,2‐tetrachloroethane (extraction solvent) and acetic anhydride (derivatization agent) was rapidly injected into the heated sample. Then the solution was cooled to room temperature and cloudy solution formed was centrifuged. Finally a portion of the sedimented phase was injected into the GC‐FID. The effect of several factors affecting the performance of the method, including the selection of suitable extraction and disperser solvents and their volumes, volume of derivatization agent, temperature, salt addition, pH and centrifugation time and speed were investigated and optimized. Figures of merit of the proposed method, such as linearity (r² > 0.993), enrichment factors (820–1070), limits of detection (2–4 ng mL^?1) and quantification (8–12 ng mL^?1), and relative standard deviations (3–6%) for both intraday and interday precisions (concentration = 50 ng mL^?1) were satisfactory for determination of the selected antidepressants. Finally the method was successfully applied to determine the target pharmaceuticals in urine. Copyright © 2014 John Wiley & Sons, Ltd.     

On the Fitzpatrick transform of a monotone bifunction

A new definition of monotone bifunctions is given, which is a slight generalization of the original definition given by Blum and Oettli, but which is better suited for relating monotone bifunctions to monotone operators. In this new definition, the Fitzpatrick transform of a maximal monotone bifunction is introduced so as to correspond exactly to the Fitzpatrick function of a maximal monotone operator in case the bifunction is constructed starting from the operator. Whenever the monotone bifunction is lower semicontinuous and convex with respect to its second variable, the Fitzpatrick transform permits to obtain results on its maximal monotonicity.