Berberine bridge enzyme-like oxidase-catalysed double bond isomerization acts as the pathway switch in cytochalasin synthesis

Cytochalasans (CYTs), as well as their polycyclic (pcCYTs) and polymerized (meCYTs) derivatives, constitute one of the largest families of fungal polyketide-nonribosomal peptide (PK-NRP) hybrid natural products. However, the mechanism of chemical conversion from mono-CYTs (moCYTs) to both pcCYTs and meCYTs remains unknown. Here, we show the first successful example of the reconstitution of the CYT core backbone as well as the whole pathway in a heterologous host. Importantly, we also describe the berberine bridge enzyme (BBE)-like oxidase AspoA, which uses Glu538 as a general acid biocatalyst to catalyse an unusual protonation-driven double bond isomerization reaction and acts as a switch to alter the native (for moCYTs) and nonenzymatic (for pcCYTs and meCYTs) pathways to synthesize aspochalasin family compounds. Our results present an unprecedented function of BBE-like enzymes and highly suggest that the isolated pcCYTs and meCYTs are most likely artificially derived products.

Continuous isomerization of glucose to fructose using activated hydrotalcite catalyst: Effects of reaction conditions

Isomerization of glucose to fructose was studied over activated hydrotalcite as a catalyst in a continuous-flow tubular reactor. The synthetic hydrotalcite (HT), calcined hydrotalcite (HT-C) and activated hydrotalcite (calcined-rehydrated hydrotalcite (HT-C-R)) were characterized by TGA, XRD, BET surface area, and FT-IR analyses. The effects of operating conditions, including reaction temperature and retention time (in terms of both catalyst loading and feeding flow rate) on the isomerization reaction, were investigated. Glucose conversion and fructose selectivity were found to be more strongly dependent on retention time than reaction temperature. The fructose yield was mostly dependent on the feeding flow rate, and its maximum value of 18% corresponded to the lowest flow rate of 0.5 ml/min. The regenerated hydrotalcite catalyst showed that the catalyst activity could be restored through the calcination-rehydration process, and it showed good potential for recycling and reusability.

Activated Carbon Modification towards Efficient Catalyst for High Value-Added Products Synthesis from Alpha-Pinene

DT0-activated carbons modified with HCl and HNO3 acids, which were used for the first time in the catalytic process of alpha-pinene isomerization, are presented in this study. The carbon materials DT0, DT0_HCl, DT0_HNO3, and DT0_HCl_HNO3 were examined with the following methods: XRF, SEM, EDX, XPS, FT-IR, XRD, and N2 adsorption at −196 °C. It was shown that DT0_HCl_HNO3-activated carbon was the most active material in the alpha-pinene isomerization process. Detailed studies of alpha-pinene isomerization were carried out over this carbon by changing the reaction parameters such as time (5–180 min) and temperature (60–175 °C). The 100% conversion of alpha-pinene was achieved at the temperature of 160 °C and catalyst content of 5 wt% after 3 h over the DT0_HCl_HNO3 catalyst. Camphene and limonene were the main products of the alpha-pinene isomerization reaction.

n-Heptane isomerization activities of Pt catalyst supported on micro/mesoporous composites

Pt loaded on a series of MCM-48 silica and composites with HZSM-5 zeolite, HY zeolite, or TiO2 has been prepared and studied for n-heptane isomerization reaction at 200–350 °C. The structural characterization, acid distribution, and morphology of these catalysts were characterized by X-ray diffraction, Fourier transform infrared, UV–Vis diffuse reflectance, scanning electron microscope, temperature-programmed desorption of NH3, and nitrogen adsorption–desorption methods. The results show that these catalysts have a good selectivity to multi branched isomers, while producing low aromatic compounds. Also, these new composite catalysts prove the catalytic stability during the time of reaction. The most desirable results, and significantly higher n-heptane conversion and isomerization selectivity were achieved with Pt/MCM48-HZSM5 catalyst.

Polyhydroxyalkanoates (PHAs) Production from Volatile Fatty Acids (VFAs) from Organic Wastes by Pseudomonas oleovorans

This study aimed to investigate the production of polyhydroxyalkanoates (PHAs), a biodegradable polymer from organic wastes by Pseudomonas oleovorans. Volatile fatty acids (VFAs) from acidogenic fermentations of chicken manure (VFAs-CM) and potato peels (VFAs-PP), rich in organic matter majorly acetic (49.9%), butyric (15%) and propionic acids (11.1%) were utilized as substrates for microbial processes. During 72 h of cultivations, samples were withdrawn at intervals and analyzed for cell growth parameters, PHAs accumulation and polymeric properties. The highest biopolymer accumulation (0.39 g PHAs/g DCW) was achieved at 48 h of cultivation from medium containing VFAs-PP as the sole source of carbon. On characterization, the produced biopolymers were shown to be semi-crystalline of carbonyl C=O group. Additionally, thermogravimetric analysis (TGA) showed that the produced biopolymers demonstrated the capability to withstand thermal degradation above prescribed temperatures at which cross-linking isomerization reaction occurs, which is a vital property denoting the thermal stability of biopolymer.

Distribution of Peptidyl-Prolyl Isomerase (PPIase) in the Archaea

Cis-trans isomerization of the peptide bond prior to proline is an intrinsically slow process but plays an essential role in protein folding. In vivo cis-trans isomerization reaction is catalyzed by Peptidyl-prolyl isomerase (PPIases), a category of proteins widely distributed among all the three domains of life. The present study is majorly focused on the distribution of different types of PPIases in the archaeal domain. All the three hitherto known families of PPIases (namely FKBP, Cyclophilin and parvulin) were studied to identify the evolutionary conservation across the phylum archaea. The basic function of cyclophilin, FKBP and parvulin has been conserved whereas the sequence alignment suggested variations in each clade. The conserved residues within the predicted motif of each family are unique. The available protein structures of different PPIase across various domains were aligned to ascertain the structural variation in the catalytic site. The structural alignment of native PPIase proteins among various groups suggested that the apo-protein may have variable conformations but when bound to their specific inhibitors, they attain similar active site configuration. This is the first study of its kind which explores the distribution of archaeal PPIases, along with detailed structural and functional analysis of each type of PPIase found in archaea.

A Mechanism for the Rare Fluctuation that Powers Protein Conformational Change

Most functional processes of biomolecules are rare events. Key to a rare event is the rare fluctuation that enables the energy activation process, which powers the system across the activation barrier. But the physical nature of this rare fluctuation and how it enables barrier crossing are unknown. With the help of a novel metric, the reaction capacity pC, that rigorously defines the beginning and parameterizes the progress of energy activation, the rare fluctuation was identified as a special phase-space condition that is necessary and sufficient for initiating systematic energy flow from the non-reaction coordinates into the reaction coordinates. The energy activation of a prototype biomolecular isomerization reaction is dominated by kinetic energy transferring into and accumulating in the reaction coordinates, administered by inertial forces alone. The two major reaction coordinates move in precise synergy, with one acting as a gating mechanism on the other. This mechanism is enabled by the structural features of biomolecules and may the cause of their unique functions that are not possible in small molecules.

n-Heptane Isomerization Activities of Pt Catalyst Supported On Micro/Mesoporous Composites

Pt loaded on a series of MCM-48 and composites with HZSM-5, HY or TiO2 has been prepared and studied for n-heptane isomerization reaction at 200–350°C. The structural characterization, acid distribution and morphology of these catalysts were characterized by XRD, FT-IR, UV-Vis DRS, SEM, NH3-TPD, and nitrogen adsorption-desorption methods. These new catalysts have good ability for n-heptane isomerization. The ideal catalytic performance was observed on Pt/MCM48-HZSM5 catalyst.

Filming ultrafast roaming-mediated isomerization of bismuth triiodide in solution

Roaming reaction, defined as a reaction yielding products via reorientational motion in the long-range region (3 – 8 Å) of the potential, is a relatively recently proposed reaction pathway and is now regarded as a universal mechanism that can explain the unimolecular dissociation and isomerization of various molecules. The structural movements of the partially dissociated fragments originating from the frustrated bond fission at the onset of roaming, however, have been explored mostly via theoretical simulations and rarely observed experimentally. Here, we report an investigation of the structural dynamics during a roaming-mediated isomerization reaction of bismuth triiodide (BiI3) in acetonitrile solution using femtosecond time-resolved x-ray liquidography. Structural analysis of the data visualizes the atomic movements during the roaming-mediated isomerization process including the opening of the Bi-Ib-Ic angle and the closing of Ia-Bi-Ib-Ic dihedral angle, each by ~40°, as well as the shortening of the Ib···Ic distance, following the frustrated bond fission.