Enzyme immobilization strategies for the design of robust and efficient biocatalysts

Different strategies for the preparation of efficient and robust immobilized biocatalysts are here reviewed. Different physico-chemical approaches are discussed.i.- The stabilization of enzyme by any kind of immobilization on pre-existing porous supports.ii.- The stabilization of enzymes by multipoint covalent attachment on support surfaces.iii.- Additional stabilization of immobilized-stabilized enzyme by physical or chemical modification with polymers.These three strategies can be easily developed when enzymes are immobilized in pre-existing porous supports. In addition to that, these immobilized-stabilized derivatives are optimal to develop enzyme reaction engineering and reactor engineering. Stabilizations ranging between 1000 and 100,000 folds regarding diluted soluble enzymes are here reported.     

The use of untargeted and widely targeted metabolomics to distinguish between asphyxia and sudden cardiac death as the cause of death in rats: A preliminary study

It is important to determine the cause of death in the case of asphyxia. However, it is difficult to conclude death by asphyxia, especially when the deceased has underlying heart disease, because there are often no specific and representative corpse signs for both asphyxia and sudden cardiac death (SCD). The aim of the present work was to investigate the potential of metabolomics to discriminate asphyxia from SCD as the cause of death. A total of thirty male Sprague–Dawley rats were used to construct models of asphyxia, SCD (interfering cause of death), and cervical dislocation (control). Untargeted and widely targeted metabolomics approaches were used to obtain rat pulmonary metabolic profiles in this study. First, the metabolic alterations resulting from asphyxia were explored. There were significant changes found in carbohydrate metabolism, the endocrine system, and the sensory system. Second, we screened potential biomarkers and built classification models to determine the cause of death. Moreover, some biomarkers remained differentiated at 24 h and 48 h postmortem, so the cause of death could still be determined after death. This study showed the application potential of metabolomics to investigate the metabolic changes occurring in the process of death, as well as to determine the cause of death on the basis of metabolic differences even after death.     

Multivariate optimization and comparison between conventional extraction (CE) and ultrasonic-assisted extraction (UAE) of carotenoid extraction from cashew apple

Carotenoids are an essential component of cashew and can be used in pharmaceuticals, cosmetics, natural pigment, food additives, among other applications. The present work focuses on optimizing and comparing conventional and ultrasound-assisted extraction methods. Every optimization step took place with a 1:1 (w:w) mixture of yellow and red cashew apples lyophilized and ground in a cryogenic mill. A Simplex-centroid design was applied for both methods, and the solvents acetone, methanol, ethanol, and petroleum ether were evaluated. After choosing the extractor solvent, a central composite design was applied to optimize the sample mass (59–201 mg) and extraction time (6–34 min). The optimum conditions for the extractor solvent were 38% acetone, 30% ethanol, and 32% petroleum ether for CE and a mixture of 44% acetone and 56% methanol for UAE. The best experimental conditions for UAE were a sonication time of 19 min and a sample mass of 153 mg, while the CE was 23 min and 136 mg. Comparing red and yellow cashews, red cashews showed a higher carotenoid content in both methodologies. The UAE methodology was ca. 21% faster, presented a more straightforward composition of extracting solution, showed an average yield of superior carotenoid content in all samples compared to CE. Therefore, UAE has demonstrated a simple, efficient, fast, low-cost adjustment methodology and a reliable alternative for other applications involving these bioactive compounds in the studied or similar matrix.     

Chelating Metal Ions in a Metal-Organic Framework for Constructing a Biomimetic Catalyst Through Post-modification

Crystal engineering, as a burgeoning technology, has been widely used to construct metalloporphyrins biomimetic catalysts. Herein, a bimetallic metal-organic framework (MOF) was constructed by 4-(4-carboxyphenyl)-1,2,4-triazole ligand, Co²⁺ and Zr⁴⁺ metal ions by solvothermal reaction(named PFC-88). A N,N-chelation site was found between the two adjacent ligands in PFC-88, consequently a porphyrin-like structure was obtained through chelating Fe³⁺ in this site by post-modification, named PFC-88-Fe. The result of a single crystal X-ray technology verified that Fe ions were successfully metalated in the N,N-chelation site of PFC-88, which is assisted by the X-ray absorption near-edge structure(XANES) spectra. An o-phenylenediamine oxidation reaction was applied to assessing the catalytic activity of PFC-88-Fe, in which the absorbance increases of phenazine-2,3-diamine at λ=418 nm were recorded by absorption spectroscopy in kinetic mode, exhibiting the application potential as a biomimetic catalyst.     

Green synthesis and characterization of Tb-Fe-O-Cu ceramic nanocomposite and its application in simultaneous electrochemical sensing of zinc,cadmium and lead

In this work, a green technique for preparing TbFeO₃/CuO was reported by employing Crataegus and Lantana Camara leaves as fuel and alkalizing agents, respectively. The new sensor based on the perovskite-type nanocomposite was employed as a sensitive and selective platform to detect Pb(II), Zn(II) and Cd(II) simultaneously. TbFeO₃/CuO/Carbon paste electrode (CPE) exhibited a large specific surface area and great electrical conductivity, which enhanced electron transport in the electrochemical process considerably. Moreover, square wave anodic stripping voltammetry (SWASV) was used for the investigation of some factors influencing the sensor sensitivity like pH, modifier concentration, as well as accumulation time and potential. Therefore, the low detection limit (LOD) and a wide linear range were obtained at optimum conditions. In this study, a linear range between 0.9 and 110 µg/L for three ions and LOD of 0.48, 0.29 and 0.12 for zinc, cadmium and lead were achieved, respectively. Moreover, TbFeO₃/CuO/CPE was employed to detect zinc, cadmium and lead ions simultaneously in the real samples so that the results have shown consistency with a standard inductively coupled plasma (ICP).     

Carbohydrate-based nanostructured catalysts: applications in organic transformations

The requirement of green and sustainable materials to prepare heterogeneous catalysts has intensified for practical reasons over the past few decades. Carbohydrates are possibly the most plentiful and renewable organic materials in nature with inimitable physiochemical properties, plausible low-cost and large-scale production, and sustainability features could be exploited in the generation of nanostructured heterogeneous catalysts. This review article outlines the organic transformations catalyzed by diverse carbohydrate-based nanostructured catalysts in greener and environmentally friendly processes. Selected examples are highlighted for a variety of organic reactions exploiting the proposed catalysts’ reactivity and reusability, and interactions with the intrinsic nature of the applied carbohydrate supports; advantages and speculated challenges of the introduced catalysts are deliberated as well.     

Current trends in the description of lanthanum strontium manganite oxygen electrode reaction mechanism in a high-temperature solid oxide cell

This review summarizes recent progress in understanding the oxygen reduction and evolution reactions at the lanthanum strontium manganite electrode of a high-temperature solid oxide cell. Information provided here is put into the perspective of the defect chemistry of lanthanum strontium manganite and its impact on the electrode reaction mechanisms itself. After summarizing recent views on the oxygen reduction reaction mechanism, the focus turns to the oxygen evolution reaction, which is significantly less treated in the literature. A combination of the information in the literature on both reactions was the basis for modified reaction mechanism of the oxygen evolution reaction to be proposed under consideration of recent experimental observations and theoretical findings.     

以磷化铁为添加剂沿(111)面生长磷掺杂金刚石大单晶

掺杂是调控金刚石性能的一种重要手段。本文采用温度梯度法,在5.6 GPa、1 312 ℃的条件下,选用Fe₃P作为磷源进行磷掺杂金刚石大单晶的合成。金刚石样品的显微光学照片表明,随着Fe₃P添加比例的增加,金刚石晶体的颜色逐渐变深,包裹体数量逐渐增加,晶形由板状转变为塔状直至骸晶。金刚石晶形的变化表明Fe₃P的添加使生长金刚石的V形区向右偏移,这是Fe₃P改变触媒特性的缘故。红外光谱分析表明,Fe₃P的添加使金刚石晶体中氮含量上升,这说明磷的进入诱使氮原子更容易进入金刚石晶格中。激光拉曼光谱测试表明,随着Fe₃P添加比例的增加,所合成的掺磷金刚石的拉曼峰位变化不大,其半峰全宽(FWHM)值变大,这说明磷的进入使得金刚石晶格畸变增加。XPS测试结果显示,随着Fe₃P添加比例的增加,金刚石晶体中磷相对碳的原子百分含量也会增加,这意味着添加Fe₃P所合成的金刚石晶体中有磷存在。     

Effect of strain on charge density wave order in α-U

The effect of strain on charge density wave (CDW) order in $\alpha$-U is investigated within the framework of relativistic density-functional theory. The energetical stability of $\alpha$-U with CDW distortion is enhanced by the tensile strain along $a$ and $b$ axes, which is similar to the case of negative pressure and normal. However, the tensile strain along $c$ axis suppresses the energetical stability of CDW phase. This abnormal effect could be understood from the emergence of a new one-dimensional atomic chain along $c$ axis in $\alpha$-U. Furthermore, this effect is supported by the calculations of Fermi surface and phonon mode, in which the topological objects and the dynamical instability show opposite behaviors between strains along $a$/$b$ and $c$ axes.