Biocatalytic Alkylation Cascades: Recent Advances and Future Opportunities for Late-Stage Functionalization

This Concept article describes the latest developments in the emerging area of late-stage biocatalytic alkylation. Central to these developments is the ability to efficiently prepare S-adenosyl methionine (SAM) cofactor analogues and couple this with enzymatic alkyl transfer. Recent developments in the enzymatic synthesis of SAM cofactor analogues are summarized first, followed by their application as alkyl transfer agents catalyzed by methyltransferases (MTases). Second, innovative methods to regenerate SAM cofactors by enzymatic cascades is reported. Finally, future opportunities towards establishing a generalized platform for late-stage alkylation are described.     

A novel context-aware recommender system based on a deep sequential learning approach (CReS)

Neural Computing and Applications - With an increase in online longitudinal users’ interactions, capturing users’ precise preferences and giving accurate recommendations have become an...     

Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni²⁺ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg²⁺ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO₂ adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO₂ methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg²⁺-containing MOF framework, the composite system retains a portion of its CO₂ adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO₂ utilization.     

Macrophage Immunomodulation Through New Polymers that Recapitulate Functional Effects of Itaconate as a Power House of Innate Immunity

Itaconate (ITA) is an emerging powerhouse of innate immunity with therapeutic potential that is limited in its ability to be administered in a soluble form. A library of polyester materials that incorporate ITA into polymer backbones resulting in materials with inherent immunoregulatory behavior is developed. Harnessing hydrolytic degradation release from polyester backbones, ITA polymers result in the mechanism specific immunoregulatory properties on macrophage polarization in vitro. In a functional assay, the polymer-released ITA inhibits bacterial growth on acetate. Translation to an in vivo model of biomaterial associated inflammation, intraperitoneal injection of ITA polymers demonstrate a rapid resolution of inflammation in comparison to a control polymer silicone, demonstrating the value of sustained biomimetic presentation of ITA.     

Owner’s Risk Allocation and Contractor’s Role Behavior in a Project: A Parallel-mediation Model

Risk allocation decisions are of critical importance in project management. The present study proposes an explanation for how risk allocation in a contract motivates a contractor to cooperate with a project owner. Theories of risk allocation and trust were used to motivate the research. Using a survey methodology, we collected data concerning 124 construction projects in China. We found that risk allocation influenced the contractor’s role behavior through the contractor’s feeling of being trusted but not the contractor’s trust in the owner. Feeling of being trusted partially mediated the effect of risk allocation on the contractor’s in-role (i.e., contractual) behavior and fully mediated the effect on extra-role behavior. The study introduces a social and psychological view of the impacts of risk allocation to the project and engineering management literature. We contribute to theory by arguing and demonstrating the mediating effect of trust on the relationship between risk allocation and contractor behavior. From a practical standpoint, we conclude that contractual risk allocation has a significant impact on building a trusting relationship between owners and contractors and that contractors who feel trusted perform both contractually mandated actions and actions external to the contract more diligently, resulting in the likelihood of improved outcomes for both parties.     

Robust nonlinear feedback–feedforward control of a coupled kinetic Monte Carlo–finite difference simulation

Robust nonlinear feedforward–feedback controllers are designed for a multiscale system that dynamically couples kinetic Monte Carlo (KMC) and finite difference (FD) simulation codes. The coupled codes simulate the copper electrodeposition process for manufacturing on-chip copper interconnects in electronic devices. The control objective is to regulate the current density subject to the condition that the steady-state fluctuation of the overpotential remains bounded within ±0.01 V. The controller designs incorporate a low-order stochastic model that captures the input–output behavior of the coupled KMC–FD code. The controllers achieve the objectives and the closed-loop responses implemented on the low-order model and the coupled KMC–FD code match well within stochastic variations. The nonlinear feedforward control reduces the rise time of the controller response while the feedback control ensures robustness in the presence of model uncertainty.     

Cued recall from image and sentence memory: A shift from episodic to identical elements representation.

The applicability of the identical elements (IE) model of arithmetic fact retrieval (T. C. Rickard, A. F. Healy, & L. E. Bourne, 1994) to cued recall from episodic (image and sentence) memory was explored in 3 transfer experiments. In agreement with results from arithmetic, speedup following even minimal practice recalling a missing word from an episodically bound word triplet did not transfer positively to other cued recall items involving the same triplet. The shape of the learning curve further supported a shift from episode-based to IE-based recall, extending some models of skill learning to cued recall practice. In contrast with previous findings, these results indicate that a form of representation that is independent of the original episodic memory underlies cued-recall performance following minimal practice. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Parallel algorithm for numerical self-consistent field theory simulations of block copolymer structure

An efficient algorithm is presented for numerically evaluating a self-consistent field theoretic (SCFT) model of block copolymer structure. This algorithm is implemented on a distributed memory parallel cluster in order to solve the SCFT equations on large computational grids. Simulation results are presented for a two-component molten mixture of a symmetric ABA triblock copolymer with an A homopolymer. These results illustrate a case in which simulating a large system is required to resolve features with a wide range of length scales.     

Biodegradation of monoaromatic hydrocarbons in aquifer columns amended with hydrogen peroxide and nitrate

The ability of indigenous microorganisms to degrade benzene, toluene, ethylbenzene and xylenes (BTEX) in laboratory scale flow-through aquifer columns was tested separately with hydrogen peroxide (110 mg/l) and nitrate (330 mg/l as NO₃⁻) amendments to air-saturated influent nutrient solution. The continuous removal of individual components from all columns relative to the sterile controls provided evidence for biodegradation. In the presence of hydrogen peroxide, the indigeneous microorganisms degraded benzene and toluene (> 95%), meta- plus para-xylene (80%) and ortho-xylene (70%). Nitrate addition resulted in 90% removal of toluene and 25% removal of ortho-xylene. However, benzene, ethylbenzene, meta- and para-xylene concentrations were not significantly reduced after 42 days of operation. Following this experiment, low dissolved oxygen (< 1 mg/l) conditions were initiated with the nitrate-amended column influent in order to mimic contaminated groundwater conditions distal from a nutrient injection well. Toluene continued to be effectively degraded (> 90%), and more than 25% of the benzene, 40% of the ethylbenzene, 50% of the meta- plus para-xylenes and 60% of the ortho-xylene were removed after several months of operation.