Annual Review of Chemical and Biomolecular Engineering - Volume 14, 2023

Active colloids use energy input at the particle level to propel persistent motion and direct dynamic assemblies. We consider three types of colloids animated by chemical reactions, time-varying magnetic fields, and electric currents. For each type, we review the basic propulsion mechanisms at the particle level and discuss their consequences for collective behaviors in particle ensembles. These microscopic systems provide useful experimental models of nonequilibrium many-body physics in which dissipative currents break time-reversal symmetry. Freed from the constraints of thermodynamic equilibrium, active colloids assemble to form materials that move, reconfigure, heal, and adapt. Colloidal machines based on engineered particles and their assemblies provide a basis for mobile robots with increasing levels of autonomy. This review provides a conceptual framework for understanding and applying active colloids to create material systems that mimic the functions of living matter. We highlight opportunities for chemical engineers to contribute to this growing field.

Thermophysical properties of fluid mixtures are important in many fields of science and engineering. However, experimental data are scarce in this field, so prediction methods are vital. Different types of physical prediction methods are available, ranging from molecular models over equations of state to models of excess properties. These well-established methods are currently being complemented by new methods from the field of machine learning (ML). This review focuses on the rapidly developing interface between these two approaches and gives a structured overview of how physical modeling and ML can be combined to yield hybrid models. We illustrate the different options with examples from recent research and give an outlook on future developments.

Drying drops of colloidal dispersions have attracted attention from researchers since the nineteenth century. The multiscale nature of the problem involving physics at different scales, namely colloidal and interfacial phenomena as well as heat, mass, and momentum transport processes, combined with the seemingly simple yet nontrivial shape of the drops makes drying drop problems rich and interesting. The scope of such studies widens as the physical and chemical nature of dispersed entities in the drop vary and as evaporation occurs in more complex configurations. This review summarizes past and contemporary developments in the field, emphasizing the physicochemical and hydrodynamical principles that govern the processes occurring within a drying drop and the resulting variety of patterns generated on the substrate.

Electrochemical synthesis of organic chemical commodities provides an alternative to conventional thermochemical manufacturing and enables the direct use of renewable electricity to reduce greenhouse gas emissions from the chemical industry. We discuss electrochemical synthesis approaches that use abundant carbon feedstocks for the production of the largest petrochemical precursors and basic organic chemical products: light olefins, olefin oxidation derivatives, aromatics, and methanol. First, we identify feasible routes for the electrochemical production of each commodity while considering the reaction thermodynamics, available feedstocks, and competing thermochemical processes. Next, we summarize successful catalysis and reaction engineering approaches to overcome technological challenges that prevent electrochemical routes from operating at high production rates, selectivity, stability, and energy conversion efficiency. Finally, we provide an outlook on the strategies that must be implemented to achieve large-scale electrochemical manufacturing of major organic chemical commodities.

Alternative polymer feedstocks are highly desirable to address environmental, social, and security concerns associated with petrochemical-based materials. Lignocellulosic biomass (LCB) has emerged as one critical feedstock in this regard because it is an abundant and ubiquitous renewable resource. LCB can be deconstructed to generate valuable fuels, chemicals, and small molecules/oligomers that are amenable to modification and polymerization. However, the diversity of LCB complicates the evaluation of biorefinery concepts in areas including process scale-up, production outputs, plant economics, and life-cycle management. We discuss aspects of current LCB biorefinery research with a focus on the major process stages, including feedstock selection, fractionation/deconstruction, and characterization, along with product purification, functionalization, and polymerization to manufacture valuable macromolecular materials. We highlight opportunities to valorize underutilized and complex feedstocks, leverage advanced characterization techniques to predict and manage biorefinery outputs, and increase the fraction of biomass converted into valuable products.

Are deep eutectic solvents (DESs) a promising alternative to conventional solvents? Perhaps, but their development is hindered by a plethora of misconceptions. These are carefully analyzed here, beginning with the very meaning of DESs, which has strayed far beyond its original scope of eutectic mixtures of Lewis or Brønsted acids and bases. Instead, a definition that is grounded on thermodynamic principles and distinguishes between eutectic and deep eutectic is encouraged, and the types of precursors that can be used to prepare DESs are reviewed. Landmark works surrounding the sustainability, stability, toxicity, and biodegradability of these solvents are also discussed, revealing piling evidence that numerous DESs reported thus far, particularly those that are choline based, lack sufficient sustainability-related traits to be considered green solvents. Finally, emerging DES applications are reviewed, emphasizing their most remarkable feature: the ability to liquefy a solid compound with a target property, allowing its use as a liquid solvent.

Electrocatalytic conversion of carbon dioxide to valuable chemicals and fuels driven by renewable energy plays a crucial role in achieving net-zero carbon emissions. Understanding the structure–activity relationship and the reaction mechanism is significant for tuning electrocatalyst selectivity. Therefore, characterizing catalyst dynamic evolution and reaction intermediates under reaction conditions is necessary but still challenging. We first summarize the most recent progress in mechanistic understanding of heterogeneous CO2/CO reduction using in situ/operando techniques, including surface-enhanced vibrational spectroscopies, X-ray- and electron-based techniques, and mass spectroscopy, along with discussing remaining limitations. We then offer insights and perspectives to accelerate the future development of in situ/operando techniques.

The storage of electric energy in a safe and environmentally friendly way is of ever-growing importance for a modern, technology-based society. With future pressures predicted for batteries that contain strategic metals, there is increasing interest in metal-free electrode materials. Among candidate materials, nonconjugated redox-active polymers (NC-RAPs) have advantages in terms of cost-effectiveness, good processability, unique electrochemical properties, and precise tuning for different battery chemistries. Here, we review the current state of the art regarding the mechanisms of redox kinetics, molecular design, synthesis, and application of NC-RAPs in electrochemical energy storage and conversion. Different redox chemistries are compared, including polyquinones, polyimides, polyketones, sulfur-containing polymers, radical-containing polymers, polyphenylamines, polyphenazines, polyphenothiazines, polyphenoxazines, and polyviologens. We close with cell design principles considering electrolyte optimization and cell configuration. Finally, we point to fundamental and applied areas of future promise for designer NC-RAPs.

There is growing interest in identifying antibodies that protect against infectious diseases, especially for high-risk individuals and pathogens for which no vaccine is yet available. However, pathogens that manifest as opportunistic or latent infections express complex arrays of virulence-associated proteins and are adept at avoiding immune responses. Some pathogens have developed strategies to selectively destroy antibodies, whereas others create decoy epitopes that trick the host immune system into generating antibodies that are at best nonprotective and at worst enhance pathogenesis. Antibody engineering strategies can thwart these efforts by accessing conserved neutralizing epitopes, generating Fc domains that resist capture or degradation and even accessing pathogens hidden inside cells. Design of pathogen-resistant antibodies can enhance protection and guide development of vaccine immunogens against these complex pathogens. Here, we discuss general strategies for design of antibodies resistant to specific pathogen defense mechanisms.

From the first clinical trial by Dr. W.F. Anderson to the most recent US Food and Drug Administration–approved Luxturna (Spark Therapeutics, 2017) and Zolgensma (Novartis, 2019), gene therapy has revamped thinking and practice around cancer treatment and improved survival rates for adult and pediatric patients with genetic diseases. A major challenge to advancing gene therapies for a broader array of applications lies in safely delivering nucleic acids to their intended sites of action. Peptides offer unique potential to improve nucleic acid delivery based on their versatile and tunable interactions with biomolecules and cells. Cell-penetrating peptides and intracellular targeting peptides have received particular focus due to their promise for improving the delivery of gene therapies into cells. We highlight key examples of peptide-assisted, targeted gene delivery to cancer-specific signatures involved in tumor growth and subcellular organelle–targeting peptides, as well as emerging strategies to enhance peptide stability and bioavailability that will support long-term implementation.

Oxidative stress is an important and pervasive physical stress encountered by all kingdoms of life, including bacteria. In this review, we briefly describe the nature of oxidative stress, highlight well-characterized protein-based sensors (transcription factors) of reactive oxygen species that serve as standards for molecular sensors in oxidative stress, and describe molecular studies that have explored the potential of direct RNA sensitivity to oxidative stress. Finally, we describe the gaps in knowledge of RNA sensors—particularly regarding the chemical modification of RNA nucleobases. RNA sensors are poised to emerge as an essential layer of understanding and regulating dynamic biological pathways in oxidative stress responses in bacteria and, thus, also represent an important frontier of synthetic biology.

In the past two decades, we have witnessed a rapid emergence of new and powerful photochemical and photocatalytic synthetic methods. Although these methods have been used mostly on a small scale, there is a growing need for efficient scale-up of photochemistry in the chemical industry. This review summarizes and contextualizes the advancements made in the past decade regarding the scale-up of photo-mediated synthetic transformations. Simple scale-up concepts and important fundamental photochemical laws have been provided along with a discussion concerning suitable reactor designs that should facilitate scale-up of this challenging class of organic reactions.

Scientific and engineering capabilities in hydrocarbon supply chains developed over decades in international oil and gas companies (IOCs) uniquely position these companies to drive rapid scale-up and transition to a net-zero emission economy. Flexible large-scale production of energy carriers such as hydrogen, ammonia, methanol, and other synthetic fuels produced with low- or zero-emission renewable power, nuclear energy, or hydrogen derived from natural gas with carbon capture and storage will enable long-distance transport and permanent storage options for clean energy. Use of energy carriers can overcome the inherent constraints of a fully electrified energy system by providing the energy and power densities, as well as transport and storage capacity, required to achieve energy supply and security in a net-zero emission economy, and over time allow optimization to the lowest cost for a consumer anywhere on the globe.