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Abstract In this study, adsorption of volatile organic compounds (VOCs) (here just gasoline vapor) by activated carbon- modified UIO-66 was investigated. First, activated carbon prepared from mesquite grain (ACPMG) and then UIO/ACPMG nanohybrid was synthesized by the solvothermal method. In following, the effect of main key parameters which effect on the surface and adsorption capacity such as the ratio of ACPMG to UIO-66 was studied. Physiochemical changes of as- synthesized samples were investigated by TGA, HR-TEM, PSD, SEM, EDX/MAP, BET, FT-IR, XRD, and XPS. It was found the UIO/ACPMG20% nanohybrid had the highest adsorption capacity (391.304 mg/g) for VOCs compared with the other samples, while the adsorption capacity of UIO-66, UIO/ACPMG10% nanohybrid, and UIO/ACPMG30% nanohybrid was 298.871, 309.523, and 320 mg/g respectively. UIO/ACPMG20% nanohybrid desorbed 285.71 mg/g of the adsorbed gasoline, which is an excellent result in desorption. So, the sample of UIO/ACPMG20% nanohybrid was selected as the optimum nano-adsorbent. In other hand, all the nano-adsorbent showed a rapid kinetic behavior for gasoline vapor adsorption and the maximum time for reaching a high adsorption capacity approximately was obtained in 20 min. Density functional theory calculations also performed to understand the adsorption characteristics of gasoline vapor on activated carbon-modified UIO-66.

Abstract A series of 4-ferrcenylbutyl carboxylate esters with different alkyl chain length (C2-C4) of carboxylic acids were synthesized using Fe3O4@SiO2@(CH2)3-Im-bisEthylFc[I] nanoparticles as catalyst and have been characterized with FT-IR, 1H NMR, and 13C NMR. Ferrocenyl-based esters were used as corrosion inhibitors of mild steel in the 1M HCl solution as corrosive media. The corrosion inhibition efficiency of the synthesized ferrocenyl-based esters has been assessed by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The 4-ferrocenylbutyl propionate showed a more effective corrosion inhibition behavior among the studied esters with 96% efficiency after immersion in the corrosive media for 2 weeks. The corrosion inhibition mechanism is dominated by formation of passive layer of inhibitor on the surface of the mild steel by adsorption. Moreover, the adsorption characteristics of 4-butylferrcenyl carboxylate esters on mild steel were thoroughly explored using density functional theory calculations. It was found that the Fe atoms located around the C impurity in the mild steel are the most efficient and active sites to adsorb 4-butylferrcenyl carboxylate esters.

This study examines the ability of Ca-decorated C48B12 fullerene (Ca/C48B12) to adsorb and store carbon dioxide (CO2) molecules through density functional theory calculations. The most stable structure of the Ca/C48B12 is achived by placing a Ca atom on the center of each C4B2 ring. To address the issue of clustering, six Ca atoms were favourably decorated on the C48B12 fullerene. Additionally, up to five CO2 molecules can be adsorbed on each decorated Ca atom, with an average adsorption energy of −0.44 eV and a gravimetric density of 58 %. Furthermore, the Ca/C48B12 fullerene exhibits high selectivity in separating CO2 from natural gas mixtures containing CO2/H2, CO2/N2, and CO2/CH4. These findings suggest that Ca/C48B12 fullerene holds potential as an effective solution for CO2 storage and separation in real-world applications.

MIL-101(Cr), a class of metal-organic framework, is a potential candidate for CO2 capture applications because of its high capacity of adsorption and separation capability. However, the intrinsic microporous structure of this nanomaterial poses limitations on its adsorption kinetics. Techniques employed to enhance its adsorption kinetics often adversely impact its adsorption capacity at equilibrium. Herein, as a new approach, we prepared amine-functionalized FAC@MIL-101(Cr) composites with adjustable micro-mesoporous structure and tunable nitrogen content by embedding different ratios of amine-functionalized activated carbon throughout the framework of MIL-101(Cr). This led to a simultaneous improvement in both kinetics and adsorption capacity for CO2. The best adsorbent, FAC-6@MIL-101(Cr), has excellent textural properties with a high surface area (1763.1 m2.g−1), great pore volume (1.29 cm3.g−1), and suitable nitrogen content (4.7 wt%). The adsorption analysis revealed that the modification of MIL-101(Cr) improved its CO2 adsorption capacity from 3.21 to 5.27 mmol/g under standard conditions of 1 bar and 25 °C. Furthermore, the FAC-6@MIL-101(Cr) adsorbent demonstrated fast CO2 adsorption kinetics (three times more relative to the pure MIL-101(Cr)), high CO2/N2 selectivity, and remarkable cyclic stability. The results confirmed that hybridization enhanced the polarizability of FAC@MIL-101(Cr) samples, causing more robust CO2-adsorbent surface interactions. Simultaneously, the existence of mesopores in the structure facilitated the transport of CO2 into the interior pores, resulting in a more efficient contact of CO2 molecules with all of the amine sites and a faster adsorption rate as well as more efficient regeneration. According to density functional theory (DFT) calculations, hybridization process induces significant changes in composites’ electronic structure, enhancing their capacity to interact with CO2 molecules more effectively. On the other hand, DFT calculations confirm that N2 molecule is less activated on the FAC@MIL-101(Cr) as evidenced by calculated small adsorption energy and charge-transfer values.

Modular proteins are regulatory proteins that carry out more than one function. These proteins upregulate or downregulate a biochemical cascade to establish homeostasis in cells. To switch the function or alter the efficiency (based on cellular needs), these proteins require different facilitators that bind to a site different from the catalytic (active/orthosteric) site, aka ‘allosteric site’, and fine-tune their function. These facilitators (or effectors) are allosteric modulators. In this Review, we have discussed the allostery, characterized them based on their mechanisms, and discussed how allostery plays an important role in the activity modulation and function fine-tuning of proteins. Recently there is an emergence in the discovery of allosteric drugs. We have also emphasized the role, significance, and future of allostery in therapeutic applications.

In this study, we synthesized and employed the amine impregnated activated carbon as an efficacious adsorbent for uptaking gasoline vapor. For this regard, anthracite as activated carbon source and hexamethylenetetramine (HMTA) as amine were selected and utilized. Physiochemical characterization of made sorbents were evaluated and investigated using SEM, FESEM, BET, FTIR, XRD, zeta potential, and elemental analysis. The synthesized sorbents provided an excellent textural features as compared with the literature and other activated carbon based sorbents and impregnated with amine. Our findings also suggested that in addition to high surface area (up to 2150 m2 / g), the micro- meso pores created (Vmeso / V micro = 0.79 Cm 3 / g) surface chemistry may significantly affect the gasoline sorption capacity, which here the role of mesoporous is further highlighted. V meso for amine impregnated sample and free activated carbon was 0.89 and 0.31 Cm 3 / g, respectively. According to the results, the prepared sorbents have a potential capability in uptaking gasoline vapor and with line this, we report a high sorption capacity of 572.56 mg / g. After, four cycles used the sorbent had a high durability and about 99.11% of the initial uptake was maintained. Taking together the synthesized adsorbents as an activated carbon provided an excellent and unique features and enhanced gasoline uptake, therefore its applicability in uptaking gasoline vapor can be substantially considered.

Ionic liquids (IL) and aqueous ionic liquids (aIL) are attractive (co-)solvents for green industrial processes involving biocatalysts, but often reduce enzyme activity. Experimental and computational methods are applied to predict favorable substitution sites and, most often, subsequent site-directed surface charge modifications are introduced to enhance enzyme resistance towards aIL. However, almost no studies evaluate the prediction precision with random mutagenesis or the application of simple data-driven filtering processes. Here, we systematically and rigorously evaluated the performance of 22 previously described structure-based approaches to increase enzyme resistance to aIL based on an experimental complete site-saturation mutagenesis library of Bacillus subtilis Lipase A (BsLipA) screened against four aIL. We show that, surprisingly, most of the approaches yield low gain-in-precision (GiP) values, particularly for predicting relevant positions: 14 approaches perform worse than random mutagenesis. Encouragingly, exploiting experimental information on the thermostability of BsLipA or structural weak spots of BsLipA predicted by rigidity theory yields GiP = 3.03 and 2.39 for relevant variants and GiP = 1.61 and 1.41 for relevant positions. Combining five simple-to-compute physicochemical and evolutionary properties substantially increases the precision of predicting relevant variants and positions, yielding GiP = 3.35 and 1.29. Finally, combining these properties with predictions of structural weak spots identified by rigidity theory additionally improves GiP for relevant variants up to 4-fold to ∼10 and sustains or increases GiP for relevant positions, resulting in a prediction precision of ∼90% compared to ∼9% in random mutagenesis. This combination should be applicable to other enzyme systems for guiding protein engineering approaches towards improved aIL resistance.

Histamine is a biogenic amine found in fish-derived and fermented food products with physiological relevance since its concentration is proportional to food spoilage and health risk for sensitive consumers. There are various analytical methods for histamine quantification from food samples; however, a simple and quick enzymatic detection and quantification method is highly desirable. Histamine dehydrogenase (HDH) is a candidate for enzymatic histamine detection; however, other biogenic amines can change its activity or produce false positive results with an observed substrate inhibition at higher concentrations. In this work, we studied the effect of site saturation mutagenesis in Rhizobium sp. Histamine Dehydrogenase (Rsp HDH) in nine amino acid positions selected through structural alignment analysis, substrate docking, and proximity to the proposed histamine-binding site. The resulting libraries were screened for histamine and agmatine activity. Variants from two libraries (positions 72 and 110) showed improved histamine/agmatine activity ratio, decreased substrate inhibition, and maintained thermal resistance. In addition, activity characterization of the identified Phe72Thr and Asn110Val HDH variants showed a clear substrate inhibition curve for histamine and modified kinetic parameters. The observed maximum velocity (Vmax) increased for variant Phe72Thr at the cost of an increased value for the Michaelis–Menten constant (Km) for histamine. The increased Km value, decreased substrate inhibition, and biogenic amine interference observed for variant Phe72Thr support a tradeoff between substrate affinity and substrate inhibition in the catalytic mechanism of HDHs. Considering this tradeoff for future enzyme engineering of HDH could lead to breakthroughs in performance increases and understanding of this enzyme class.

Protein engineering campaigns are driven by the demand for superior enzyme performance under non-natural process conditions, such as elevated temperature or non-neutral pH, to achieve utmost efficiency and conserve limited resources. Phytases are industrial relevant feed enzymes that contribute to the overall phosphorus (P) management by catalyzing the stepwise phosphate hydrolysis from phytate, which is the main phosphorus storage in plants. Phosphorus is referred to as a critical disappearing nutrient, emphasizing the urgent need to implement strategies for a sustainable circular use and recovery of P from renewable resources. Engineered phytases already contribute today to an efficient phosphorus mobilization in the feeding industry and might pave the way to a circular P-bioeconomy. To date, a bottleneck in its application is the drastically reduced hydrolysis on lower phosphorylated reaction intermediates (lower inositol phosphates, ≤InsP4) and their subsequent accumulation. Here, we report the first KnowVolution campaign of the E. coli phytase toward improved hydrolysis on InsP4 and InsP3. As a prerequisite prior to evolution, a suitable screening setup was established and three isomers Ins(2,4,5)P3, Ins(2,3,4,5)P4 and Ins(1,2,5,6)P4 were generated through enzymatic hydrolysis of InsP6 and subsequent purification by HPLC. Screening of epPCR libraries identified clones with improved hydrolysis on Ins(1,2,5,6)P4 carrying substitutions involved in substrate binding and orientation. Saturation of seven positions and screening of, in total, 10,000 clones generated a dataset of 46 variants on their activity on all three isomers. This dataset was used for training, testing, and inferring models for machine learning guided recombination. The PyPEF method used allowed the prediction of recombinants from the identified substitutions, which were analyzed by reverse engineering to gain molecular understanding. Six variants with improved InsP4 hydrolysis of >2.5 were identified, of which variant T23L/K24S had a 3.7-fold improved relative activity on Ins(2,3,4,5)P4 and concomitantly shows a 2.7-fold improved hydrolysis of Ins(2,4,5)P3. Reported substitutions are the first published Ec phy variants with improved hydrolysis on InsP4 and InsP3.

In this study, adsorption of volatile organic compounds (VOCs) (here just gasoline vapor) by activated carbon- modified UIO-66 was investigated. First, activated carbon prepared from mesquite grain (ACPMG) and then UIO/ACPMG nanohybrid was synthesized by the solvothermal method. In following, the effect of main key parameters which effect on the surface and adsorption capacity such as the ratio of ACPMG to UIO-66 was studied. Physiochemical changes of as- synthesized samples were investigated by TGA, HR-TEM, PSD, SEM, EDX/MAP, BET, FT-IR, XRD, and XPS. It was found the UIO/ACPMG20% nanohybrid had the highest adsorption capacity (391.304 mg/g) for VOCs compared with the other samples, while the adsorption capacity of UIO-66, UIO/ACPMG10% nanohybrid, and UIO/ACPMG30% nanohybrid was 298.871, 309.523, and 320 mg/g respectively. UIO/ACPMG20% nanohybrid desorbed 285.71 mg/g of the adsorbed gasoline, which is an excellent result in desorption. So, the sample of UIO/ACPMG20% nanohybrid was selected as the optimum nano-adsorbent. In other hand, all the nano-adsorbent showed a rapid kinetic behavior for gasoline vapor adsorption and the maximum time for reaching a high adsorption capacity approximately was obtained in 20 min. Density functional theory calculations also performed to understand the adsorption characteristics of gasoline vapor on activated carbon-modified UIO-66. [ABSTRACT FROM AUTHOR]

The new species Cortinarius steglichii is described from Chilean Nothofagus forest based on morphological and microscopical attributes, molecular phylogeny, and chemical analysis of secondary metabolites. C. steglichii is characterized by abundant, long, ramified cystidia on the lamellar edges and stipe apex, further by a deep violet color reaction after treatment with KOH. As responsible secondary metabolite for the cytoplasmatic color reaction of cystidia and some hyphae, the new diterpenoid steglichon (1) could be recognized, showing also remarkable antibacterial and anticancer activity. Phylogenetic analyses (ITS, LSU, RPB1) confirm the close relationship to species of the Cortinarius dulciolens group. [ABSTRACT FROM AUTHOR]