Oxidation State Research Articles

Selenization-induced [001]-oriented Sb2Se3 film formation and its photo-sensing characteristics

Antimony selenide (Sb2Se3) is emerging as a promising material for optoelectronic applications owing to its exceptional properties. Achieving c-axis oriented [001] Sb2Se3 films, which is crucial for optimizing charge carrier transport has consistently been challenging. In this work, a facile route involving reactive selenization of antimony films deposited on glass substrates via thermal evaporation was employed to obtain [001] oriented Sb2Se3 thin films. The resultant films were comprehensively characterized using X-ray diffraction, field emission scanning electron microscopy, and energy-dispersive X-ray spectroscopy to confirm phase purity and compositional homogeneity, elucidating the role of selenization temperature in the formation of Sb2Se3 through this method. XPS analysis was carried out to confirm the oxidation states of Sb and Se. Optical analysis revealed a high absorption coefficient of ∼1.75 × 105 cm−1 with the desired direct band gap values in the range of 1.23 eV–1.20 eV. All these favourable properties, steered to observe a photocurrent of 143 nA at a 5V applied bias in 375°C selenized films under AM1.5 G illumination conditions. An n-Si/Sb2Se3 heterojunction was fabricated and a photocurrent of 2.8 μA was observed with responsivity and detectivity values of 8.18 × 10−5 A/W and 4.26 × 109 Jones respectively at zero applied bias and AM1.5 illumination conditions, showing the favourable prospects of Sb2Se3 thin films prepared via the selenization of antimony films in optoelectronic applications.

Microwave-assisted catalytic gasification of mixed plastics and corn stover for low tar, hydrogen-rich syngas production

The challenge for efficient management of post-consumer plastic and biomass waste has grown over the past few decades due to their dramatic increases. In comparison to conventional gasification, microwave-assisted co-gasification of plastics and corn stover offers many benefits, including increased H2 yield and gas components compared to unfavorable char/tar. Nonetheless, for future commercialization of the process and ease of product separation, further reduction of the undesirable tar is necessary, which can be achieved over the catalytic route. In this work, we studied the catalytic effect of magnetite for microwave-assisted co-gasification of corn stover and plastic to make syngas with higher H2 and lower tar selectivity over non-catalytic conditions. A 1:1:1 ratio of plastic-corn stover-magnetite was used to evaluate the reaction parameters such as temperature, space velocity, heating media, and catalytic cycles under gasification conditions. In comparison with the microwave non-catalytic route, a 100% increase in the total H2 yield with 76% higher H2 production efficiency (mmol/kWh) was achieved in the presence of the magnetite catalyst, while reducing the overall tar formation from 9% to 2%. When magnetite was reduced in situ during the reaction, it coupled with microwave and delivered oxygen radicals that cracked down plastic and corn stover intermediates generated from the synergistic effect under microwave heating. Soon after the oxygen transfer process initiated, magnetite reached its final oxidation state consisting of microwave-active Fe and Fe3C phases that continued coupling with microwaves along with the generated graphitic carbon to maintain the heat necessary to further reduce the generated tar and make additional gaseous products, as confirmed by XRD, Raman, and TGA analyses.

Decomposition and migration behavior of Pt salt on Al2O3 and SiO2 upon calcination studied by XAFS and UV–visible spectroscopy using a laboratory-type spectrometer

Thermal decomposition behavior of two kinds of Pt salts, namely, H2PtCl6 and Pt(NH3)4Cl2, on amorphous SiO2 and γ-Al2O3 under air to prepare supported platinum catalysts up to 773 K was investigated by in-situ laboratory X-ray absorption fine structure (XANES/EXAFS) and UV–Vis spectroscopy. Changing the oxidation state of platinum species and the coordination environment, the migration to vacant sites or aggregation process on the surface were discussed. The supported H2PtCl6 was reduced to Pt2+ species under air flow around 573 K by eliminating Cl/O ligand atoms until 573 K. High-temperature treatment caused the re-oxidation of the supported Pt species on Al2O3, but it did not affect the oxidation state of SiO2-supported species. The formed platinum oxychloride on Al2O3 was stable under air, but it partly decomposed to atomic-like species above 673 K, followed by migration on the surface, trapping at the cation vacant site because of its defect spinel structure. The lattice oxygen atoms of Al2O3 adjacent to Pt atom captured might cause the re-oxidation, and molecular oxygen was not the oxidant. The partly formed atomic-like species migrates on the SiO2 surface, followed by aggregation to form metallic Pt particles above 573 K.

Degassing-Driven Oxidation Promotes HREE Enrichment in South China Granites

Abstract Heavy rare earth elements (HREEs) are critical metals in advanced technologies. Here, we report unusual REE patterns and O–Hf–Nd isotopic compositions of composite granites from the Zhaibei HREE deposit. The complex consists of two Mesozoic granites with ages of 188 and 170 Ma. The older granites are characterized by higher HREE contents and negative Ce anomaly and contain cerianite veinlets. Their REE-rich minerals also show strong Ce depletion, indicating a high oxidation state. Magmatic zircons have variables δ18O (6.1–9.4‰) and εHf(t) (−6 to 0), towards a depleted mantle contribution. Lower δ18O (~5.4 vs 6.6‰) and higher εNd(t) (approximately −3 vs −11) values in the altered apatite rim compared to the core and primary phase result from subduction-derived fluids. In contrast, the younger granites have lower REE contents and lack a Ce anomaly. They show mantle-derived Nd (apatite εNd(t) = 1–2), Hf (zircon εHf(t) = 3–8), and O (zircon and apatite δ18O = 4.6–5.7‰) isotopic compositions. Therefore, we infer that a REE-rich fluid migrated from the flat subducting slab and flushed the subsolidus granitic mush in the Early Jurassic. This caused volatile saturation and degassing, leading to the generation of highly oxidized fluids. These processes may cause temporary oxidizing conditions in post-magmatic hydrothermal stages, resulting in the oxidation of Ce3+ to Ce4+. The resulting Ce fractionation from other REE3+ promoted HREE enrichment in the granites.

Tailorable Multi-Photoresponsive Behavior Triggered by Different Sulfur Oxidation States

Tailorable Multi-Photoresponsive Behavior Triggered by Different Sulfur Oxidation States

Differences in bulk Fe content and density between type I and type II ordinary chondrite chondrules: Implications for parent body heterogeneities in oxidation state and O‐isotopic composition

AbstractType II chondrules have higher oxidation states than type I chondrules; in ordinary chondrites (OC), type II chondrules tend to be larger, richer in bulk Fe, and have higher densities than type I chondrules. Magnesian type IA chondrules tend to be richer in 16O than type II chondrules. Because the aerodynamic behavior of a particle is a function of the product of its size and density, type I and type II chondrules (or their precursors) were partly separated in the ordinary chondrite zone of the solar nebula prior to the accretion of OC parent asteroids. LL chondrites acquired a chondrule population with the highest type II/type I ratios, L chondrites acquired chondrules with an intermediate ratio, and H chondrites acquired chondrules with the lowest type II/type I ratios. This contributed to the observed differences among OC groups in oxidation state and O‐isotopic composition: in going from H to L to LL, mean oxidation state increases and mean Δ17O values increase. Higher oxidation is marked by increases in the FeO contents of olivine, low‐Ca pyroxene, chromite, and ilmenite; increases in the TiO2 content of chromite; and increases in the Co content of kamacite.

Essential oil mediated synthesis and application of highly stable copper nanoparticles as coatings on textiles and surfaces for rapid and sustained disinfection of microorganisms

Rampant pathogenesis induced by communicable microbes has necessitated development of technologies for rapid and sustained disinfection of surfaces. Copper nanoparticles (CuNPs) have been widely reported for their antimicrobial properties. However, nanostructured copper is prone to oxidative dissolution in the oil phase limiting its sustained use on surfaces and coatings. The current study reports a systematic investigation of a simple synthesis protocol using fatty acid stabilizers (particularly essential oils) for synthesis of copper nanoparticles in the oil phase. Of the various formulations synthesized, rosemary oil stabilized copper nanoparticles (RMO CuNPs) were noted to have the best inactivation kinetics and were also most stable. Upon morphological characterization by TEM and EELS, these were found to be monodispersed (φ 5–8 nm) with copper coexisting in all three oxidation states on the surface of the nanoparticles. The nanoparticles were drop cast on woven fabric of around 500 threads per inch and exposed to gram positive bacteria (Staphylococcus aureus), gram negative bacteria (Escherichia coli and Pseudomonas aeruginosa), enveloped RNA virus (phi6), non-enveloped RNA virus (MS2) and non-enveloped DNA virus (T4) to encompass the commonly encountered groups of pathogens. It was possible to completely disinfect 107 copies of all microorganisms within 40 min of exposure. Further, this formulation was incorporated with polyurethane as thinners and used to coat non-woven fabrics. These also exhibited antimicrobial properties. Sustained disinfection with less than 9% cumulative copper loss for upto 14 washes with soap water was observed while the antioxidant activity was also preserved. Based on the studies conducted, RMO CuNP in oil phase was found to have excellent potential of integration on surface coatings, paints and polymers for rapid and sustained disinfection of microbes on surfaces.

Release of Radioactive Particles to the Environment.

When environmental impact and risks associated with radioactive contamination of ecosystems are assessed, the source term and deposition must be linked to ecosystem transfer, biological uptake and effects in exposed organisms. Thus, a well-defined source term is the starting point for transport, dose, impact and risk models. After the Chornobyl accident, 3-4 tons of spent nuclear fuel were released and radioactive particles were important ingrediencies of the actual source term. As Chornobyl particles were observed in many European countries, some scientists suggested that radioactive particles were "a peculiarity of the Chornobyl accident." In contrast, research over the years has shown that a major fraction of refractory elements such as uranium (U) and plutonium (Pu) released to the environment has been released as particles following a series of past events such as nuclear weapons tests, non-criticality accidents involving nuclear weapons, military use of depleted uranium ammunition, and nuclear reactor accidents. Radioactive particles and colloids have also been observed in discharges from nuclear installations to rivers or to regional seas and are associated with nuclear waste dumped at sea. Furthermore, radioactive particles have been identified at uranium mining and tailing sites as well as at other NORM sites such as phosphate or oil and gas industrial facilities. Research has also demonstrated that particle characteristics such as elemental composition depend on the emitting source, while characteristics such as size distribution, structure, and oxidation state influencing ecosystem transfer will also depend on the release scenarios. Thus, access to advanced particle characteristic techniques is essential within radioecology. After deposition, localized heterogeneities such as particles will be unevenly distributed in the environment. Thus, inventories can be underestimated, and impact and risk assessments of particle contaminated areas may suffer from unacceptable large uncertainties if radioactive particles are ignored. The present paper will focus on key sources contributing to the release of radioactive particles to the environments, as well as linking particle characteristics to ecosystem behavior and potential biological effects.

Geometry, reactivity descriptors, light harvesting efficiency, molecular radii, diffusion coefficient, and oxidation potential of RE(I)(CO)3Cl(TPA-2, 2′-bipyridine) in DSSC application: DFT/TDDFT study

Dye-sensitized solar cells (DSSCs) are an excellent alternative solar cell technology that is cost-effective and environmentally friendly. The geometry, reactivity descriptors, light-harvesting efficiency, molecular radii, diffusion coefficient, and excited oxidation state potential of the proposed complex were investigated. The calculations in this study were performed using DFT/TDDFT method with B3LYP functional employed on the Gaussian 09 software package. The calculations were used the 6–311 + + G(d, p) basis set for the C, H, N, O, Cl atoms and the LANL2DZ basis set for the Re atom, with the B3LYP functional.. The balance of hole and electron in this complex has increased the efficiency and lifetime of DSSCs for photovoltaic cell applications. The investigated compound shows that the addition of the TPA substituent marginally changes the geometric structures of the 2, 2′-bipyridine ligand in the T1 state. As EDsubstituents were added to the compound, the energy gap widened and moved from ELUMO (− 2.904 eV) (substituted TPA) to ELUMO (− 3.122 eV) (unsubstituted). In the studying of solvent affects; when the polarity of the solvent decreases, red shifts appears in the lowest energy an absorption and emission band. Good light-harvesting efficiency, molecular radii, diffusion coefficient, excited state oxidation potential, emission quantum yield, and DSSC reorganization energy, the complex is well suited for use as an emitter in dye-sensitized solar cells. Among the investigated complexes mentioned in literature, the proposed complex was a suitable candidate for phosphorescent DSSC.

Electrochemical sensing platform using cerium tungstate for highly sensitive sensing of chromium in water

Chromium, in some forms and large amounts, can be hazardous to human health and the environment. In particular, hexavalent chromium Cr(VI) and its derivatives are the most poisonous forms of Cr, whose toxicity depends on its oxidation state. Herein, cerium tungstate (CeW) is demonstrated as an efficient sensing material for Cr(VI) detection in aqueous medium. Two different surfactants are used to hydrothermally synthesize flake-like and sphere-like morphology. The flake-like morphology shows excellent Cr(VI) detection ability owing to its larger surface area, oxygen vacancy defects, and electrochemically active surface area. The sensitivity and limit of detection (LoD) value of the CeW nanoflakes are found to be 0.71 μA/ppb and 6.1 ppb, respectively. The LoD is lower than the WHO recommended standard value, which suggests that the synthesized material can be used for determining Cr(VI) concentration in domestic and potable water. The presence of different ions, such as Fe3+, Zn2+, Cu2+, Hg2+and Pb2+in the medium is found not interfere the Cr(VI) detection ability of CeW nanoflakes and thereby enhancing its practical applicability in Cr(VI) detection.

Understanding Ligand Effects on Bielectronic Transitions: Chemo- and Electroreduction of Rhodium Bis(Diphosphine) Complexes to Low Oxidation States.

Rhodium complexes in the -I and 0 oxidation states are of great potential interest in catalytic applications. In contrast to their rhodium +I congeners, however, the structural and electronic parameters governing their access and stability are far less understood. Herein, we investigate the two-electron reduction of a parameterized series of bis(diphosphine) Rh complexes [Rh(dxpy)2]NTf2 (x = P-substituent, y = alkanediyl bridging P atoms). Through (electro)reductions from the RhI parents, Rh-Id10-complexes were obtained and characterized spectroscopically, including 103Rh NMR data. The reductive steps convolute with structural rearrangements from square planar to tetrahedral coordination. We found that the extent of these reorganisations defines whether the first E0(RhI/0) and second E0(Rh0/-I) reduction potentials are normally ordered, leading to monoelectronic stepwise events, or inverted, giving bielectronic transitions. Reductionist approaches based on Hammett parameters or the P-Rh-P bite angles provide only partial correlations with the redox potentials. However, we identified the C-O stretch of analogue diphosphine complexes as an expedient computational parameter that enables these correlations through both electronic and geometric features, even in a predictive manner. Gaining control over two-electron reduction behaviors through rationalized ligand effects has potential impact beyond Rh complexes, for molecular and enzymatic metal sites commonly exhibiting bielectronic transitions.

Unraveling dynamic Jahn-Teller effect and magnetism in FeTiF6×6H2O single crystal

Hydrated iron fluoridotitanate (FeTiF6 × 6 H2O) single crystals are fascinating magnetic materials with unique properties. To understand the underlying mechanisms, this study combines X-ray absorption near-edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) techniques, complemented by density functional theory (DFT) calculations. Polarization-dependent X-ray absorption spectroscopy, encompassing XANES and XMCD, is a powerful technique for probing the local structures and magnetic properties of materials. It is element-selective, bulk-sensitive, and compatible with a wide range of experimental conditions. In this study, we used XANES and XMCD spectroscopies to investigate the local structures and magnetic properties of Fe and Ti in FeTiF6 × 6 H2O single crystals. XANES analysis revealed distinct local environments around Fe and Ti, providing insights into their coordination environments. Element-selective magnetization measurement at the Fe K-edge demonstrated that iron sites in the oxidation state Fe2+ have an unambiguous paramagnetic contribution to the magnetization along the b-axis. Notably, the absence of an XMCD signal at the Ti K-edge confirmed the absence of a magnetic moment in Ti atoms within the crystal. DFT calculations corroborate the experimental findings and provide insights into the electronic structure and magnetic interactions. The combined results provide a comprehensive understanding of the dynamic Jahn-Teller effect in FeTiF6 × 6 H2O single crystals, highlighting the significance of polarization-dependent X-ray absorption spectroscopy in unraveling the intricate magnetic behavior of such materials. This study contributes to the fundamental understanding of magnetism in these materials and paves the way for the development of novel magnetic materials with tailored properties.

Inhibiting Demetalation of Fe─N─C via Mn Sites for Efficient Oxygen Reduction Reaction in Zinc-Air Batteries.

Demetalation caused by the electrochemical dissolution of metallic Fe atoms is a major challenge for the practical application of Fe─N─C catalysts. Herein, an efficient single metallic Mn active site is constructed to improve the strength of the Fe─N bond, inhibiting the demetalation effect of Fe─N─C. Mn acts as an electron donor inducing more delocalized electrons to reduce the oxidation state of Fe by increasing the electron density, thereby enhancing the Fe─N bond and inhibiting the electrochemical dissolution of Fe. The oxygen reduction reaction pathway for the dissociation of Fe─Mn dual sites can overcome the high energy barriers to direct O─O bond dissociation and modulate the electronic states of Fe─N4 sites. The resulting FeMn─N─C exhibits excellent ORR activity with a high half-wave potential of 0.92V in alkaline electrolytes. FeMn─N─C as a cathode catalyst for Zn-air batteries has a cycle stability of 700h at 25°C and a long cycle stability of more than 210h under extremely cold conditions at -40°C. These findings contribute to the development of efficient and stable metal-nitrogen-carbon catalysts for various energy devices.

Aspartame, as an artificial sweetener, does not affect renal function and antioxidative states in mice

Background and objectiveAspartame (l-aspartyl l-phenylalanine methyl ester) is an artificial sweetener widely used as a sugar substitute. There are concerns regarding the effects of high aspartame doses on the kidney owing to oxidative stress; however, whether the maximum allowed dose of aspartame in humans affects the kidneys remains unknown. Therefore, in this study, we investigated whether the maximum allowed dose of aspartame in humans affects the kidneys.MethodsIn this study, animals were fed a folate-deficient diet to mimic human aspartame metabolism. Eight-week-old ICR mice were divided into control (CTL), 40 mg/kg/day of aspartame-administered (ASP), folate-deficient diet (FD), and 40 mg/kg/day of aspartame-administered with a folate-deficient diet (FD + ASP) groups. Aspartame was administered orally for eight weeks. Thereafter, we evaluated aspartame’s effect on kidneys via histological analysis.ResultsThere were no differences in serum creatinine and blood urea nitrogen levels between the CTL and ASP groups or between the FD and FD + ASP groups. There was no histological change in the kidneys in any group. The expression of superoxide dismutase and 4-hydroxy-2-nonenal in the kidney did not differ between the CTL and ASP groups or the FD and FD + ASP groups.ConclusionOur findings indicate that the allowed doses of aspartame in humans may not affect kidney function or oxidative states.

Alternatively Connected Corrole‐Porphyrin Multimetallic Complexes: Synthesis, Structure, and Properties

AbstractSynthetic multimetallic porphyrinoids are potential candidates in catalysis, molecular magnetism and as modern optoelectronic materials. Introducing electronic heterogenity in these multi‐porphyrinoids shall bring in novel electronic and redox characteristics. In this direction, herein we report four discrete Corrole‐Porphyrin‐Corrole C[10] ⋅ P[5,15] ⋅ C[10] hybrids that have both corrole and porphyrin units covalently connected together. Metal ions in diverse oxidation states have been incorporated into respective cores to achieve homo and heterotrinuclear metal complexes. Selective metalation at the porphyrin and corrole cores was achieved by step‐wise insertion of Zn(II)/Cu(II), Zn(II)/Ga(III) and Cu(II)/Cu(II) ions to suit the dianionic and trianionic pockets, respectively. Single crystal X‐ray diffraction studies reveal the solid‐state structural evidence for both homo‐, and hetero‐trinuclear metal complexes. The Zn(II) and Ga(III) moieties have two distinct geometries in the molecular assembly. The geometry of Zn(II) at the porphyrin core is a perfect square planar, whereas the Ga(III) geometry at the corrole is square pyramidal with pyridine as an axial ligand. In case of homotrinuclear Cu(II) complex, the Cu(II) ions adopt square planar geometry irrespective of the core. Similar to all porphyrin trimers, C[10] ⋅ P[5,15] ⋅ C[10] trimers exhibit significant excitonic coupling between corrole and porphyrin units in the absorption spectra. The cyclic voltametric investigations also reveal electronic coupling between the individual chromophores despite the non‐coplanar arrangement amongst the individual macrocycles.

Intramolecular Disulfide Bridges in Voltage-Dependent Anion Channel 2 (VDAC2) Protein from Rattus norvegicus Revealed by High-Resolution Mass Spectrometry.

Voltage-Dependent Anion Channel isoforms (VDAC1, VDAC2, and VDAC3) are relevant components of the outer mitochondrial membrane (OMM) and play a crucial role in regulation of metabolism and in survival pathways. As major players in the regulation of cellular metabolism and apoptosis, VDACs can be considered at the crossroads between two broad families of pathologies, namely, cancer and neurodegeneration, the former being associated with elevated glycolytic rate and suppression of apoptosis in cancer cells, the latter characterized by mitochondrial dysfunction and increased cell death. Recently, we reported the characterization of the oxidation pattern of methionine and cysteines in rat and human VDACs showing that each cysteine in these proteins is present with a preferred oxidation state, ranging from the reduced to the trioxidized form, and such an oxidation state is remarkably conserved between rat and human VDACs. However, the presence and localization of disulfide bonds in VDACs, a key point for their structural characterization, have so far remained undetermined. Herein we have investigated by nanoUHPLC/High-Resolution nanoESI-MS/MS the position of intramolecular disulfide bonds in rat VDAC2 (rVDAC2), a protein that contains 11 cysteines. To this purpose, extraction, purification, and enzymatic digestions were carried out at slightly acidic or neutral pH in order to minimize disulfide bond interchange. The presence of six disulfide bridges was unequivocally determined, including a disulfide bridge linking the two adjacent cysteines 4 and 5, a disulfide bridge linking cysteines 9 and 14, and the alternative disulfide bridges between cysteines 48, 77, and 104. A disulfide bond, which is very resistant to reduction, between cysteines 134 and 139 was also detected. In addition to the previous findings, these results significantly extend the characterization of the oxidation state of cysteines in rVDAC2 and show that it is highly complex and presents unusual features. Data are available via ProteomeXchange with the identifier PXD044041.

Leonardite humic acid activated carbon/MnO\(_{2}\) composite nanostructures for supercapacitors

Abstract This work reports the preparation and electrochemical studies of activated carbon derived from leonardite humic acid composited with MnO2 for supercapacitors. Activated carbon contains high conductivity, high specific surface area, and accommodates large volume expansion/contraction during charging/discharging process. Meanwhile, MnO2 has very high theoretical specific capacity (1370 F∙g‒1). Their composite could significantly improve both the storage performance and cycle stability of supercapacitors. Moreover, humic acid from leonardite was selected to add value to this waste and reduce environmental pollution. By varying the carbonization temperature (500℃ to 800℃), the prepared samples carbonized at 800℃ exhibited fascinating properties. The oxidation state of Mn ions was in the mixed state of Mn+2 (41.2%) and Mn+2, +3 (52.8%). A gravimetric capacitance of 329 F∙g‒1 and 294 F∙g‒1 were observed at 2 mVs-1 and 0.5 Ag-1, respectively. The remaining gravimetric capacitance of 193 F∙g‒1 was evaluated at 1000 cycles, indicating its high cycle performance. Moreover, the gravimetric energy of 37.51 Wh∙kg‒1 and gravimetric power of 272.96 W∙kg‒1 were observed. When combined, the interesting electrochemical properties of leonardite humic acid-activated carbon/MnO2 composite nanostructures make them important options for supercapacitor application.

Adaptive evolution of Clostridium thermocellum ATCC 27405 on alternate carbon sources leads to altered fermentation profiles.

Consolidated bioprocessing candidate, Clostridium thermocellum, is a cellulose hydrolysis specialist, with the ability to ferment the released sugars to produce bioethanol. C. thermocellum is generally studied with model substrates Avicel and cellobiose to understand the metabolic pathway leading to ethanol. In the present study, adaptive laboratory evolution, allowing C.thermocellum DSM 1237 to adapt to growth on glucose, fructose, and sorbitol, with the prospect that some strains will adapt their metabolism to yield more ethanol. Adaptive growth on glucose and sorbitol resulted in an approximately 1mM and 2mM increase in ethanol yield per millimolar glucose equivalent, respectively, accompanied by a shift in the production of the other expected fermentation end products. The increase in ethanol yield observed for sorbitol adapted cells was due to the carbon source being more reduced compared to cellobiose. Glucose and cellobiose have similar oxidation states thus the increase in ethanol yield is due to the rerouting of electrons from other reduced metabolic products excluding H2 which did not decrease in yield. There was no increase in ethanol yield observed for fructose adapted cells, but there was an unanticipated elimination of formate production, also observed in sorbitol adapted cells suggesting that fructose has regulatory implications on formate production either at the transcription or protein level.

Intrinsic flame-retardant epoxy resin based on phosphorus-containing liquid imidazole compound: Simultaneously improving fire safety, mechanical property and heat resistance

In this work, two phosphorus-containing liquid imidazole compounds with different phosphorus oxidation states (1,1′-(phenylphosphanediyl)bis(1H-imidazole) (DCPPI) with + 1 valence phosphorus, and imidazole-phenylphosphate (PPOAI) with + 3 valence phosphorus) were designed and synthesized. Both of DCPPI and PPOAI were used as curing agents to obtain intrinsic flame-retardant epoxy resin (EP-DCPPI and EP-PPOAI), in which the imidazole group was used as the curing group of EP, and the phosphorus-containing group was directly connected to the EP crosslinking network. On the one hand, the efficient flame-retardant groups containing + 1 or + 3 valence phosphorus were incorporated into the EP system to obtain excellent flame-retardant properties; on the other hand, the introduction of phenylphosphine or phenoxyphosphine groups in the molecular chain of EP greatly enhanced the interaction between molecular chains, adjusted crosslinking density and endowed EP with excellent tensile strength and toughness. Compared with imidazole cured EP (EP-MZ), the peak heat release rate (PHRR) of EP-15DCPPI and EP-15PPOAI decreased by 70 % and 68 %, and the total heat release rate (THR) decreased by 37 % and 36 %, respectively. Meanwhile, EP-15DCPPI passed UL-94 V-0 rating, and the limiting oxygen index (LOI) reached 36.1 %. EP-15PPOAI passed UL-94 V-1 rating and the LOI reached 29.1 %. The flame-retardant mechanism was analyzed and discussed. Compared with EP-MZ, the dynamic and static mechanical properties of EP-15DCPPI and EP-15PPOAI were enhanced simultaneously, and the glass transition temperature (Tg) was obviously increased.

Survey of Recent Trends of IB-IVB Metals and Their Compounds in Cancer Treatment

Metals from IB to IVB groups of the periodic table, because of their flexible oxidation states, natures of coordinated bioligands, and geometries upon complexation, display various properties and efficiency of metal-based cytotoxic drugs. Recent decades have witnessed remarkable progress in the synthesis and therapeutic application of numerous inorganic compounds in cancer investigations. The main potential therapeutic agents, such as the complexes of platinum group metals possessing antineoplastic activity have been broadly described previously in the literature and are beyond the space of this analysis. The key objective of the present study is to analyze the possible activity of IB-IVB group metals their coordination compounds against the cancer cell types. The increasing number of anticancer drug candidates among these metals proves this field offers a remarkably variation of novel opportunities for the synthesis of advanced new pharmaceutics with diverse and specific modes of action. Furthermore, the review provides forthcoming insights into prospective clinical scenarios for approaching treatment applications. That is why this field of research deserves more attention. It is expected that this review can serve as a guiding framework for future investigations in cancer chemotherapy.