Annual Review of Chemical and Biomolecular Engineering - Volume 10, 2019

Following Forest Hills High School in New York City, I attended Cornell University for a five-year program leading to a Bachelor of Chemical Engineering degree. After spending one year at the University of Rochester to obtain a Master of Science in Chemical Engineering, I came to Princeton University in 1951. Four years later, with a fresh PhD, I joined the faculty at the University of California, Berkeley, where I remained, interrupted only by sabbatical leaves in Switzerland, Germany, England, New Zealand, and Australia. Most of my professional work has been in applied chemical thermodynamics for process design, in particular, development of molecular-thermodynamic models for calculating phase equilibria for large-scale separation operations. I have also worked on the properties of electrolytes and hydrates, critical phenomena in fluid mixtures, properties of polymers and gels, adsorption of fluid mixtures, and separation of biomolecules. For many years I was a consultant for Air Projects and Chemicals and for the Fluor Corporation. Throughout my long teaching career, I have stressed the importance of context and of integrating science and engineering with humanities and with the needs of society. Such integration makes better engineers and contributes to personal happiness.

In recent years, 3D printing has led to a disruptive manufacturing revolution that allows complex architected materials and structures to be created by directly joining sequential layers into designed 3D components. However, customized feedstocks for specific 3D printing techniques and applications are limited or nonexistent, which greatly impedes the production of desired structural or functional materials. Colloids, with their stable biphasic nature, have tremendous potential to satisfy the requirements of various 3D printing methods owing to their tunable electrical, optical, mechanical, and rheological properties. This enables materials delivery and assembly across the multiple length scales required for multifunctionality. Here, a state-of-the-art review on advanced colloidal processing strategies for 3D printing of organic, ceramic, metallic, and carbonaceous materials is provided. It is believed that the concomitant innovations in colloid design and 3D printing will provide numerous possibilities for the fabrication of new constructs unobtainable using traditional methods, which will significantly broaden their applications.

Concerns have been raised in multiple scientific fields in recent years about the reproducibility of published results. Systematic efforts to examine this issue have been undertaken in biomedicine and psychology, but less is known about this important issue in the materials-oriented research that underpins much of modern chemical engineering. Here, we relate a dramatic historical episode from our own institution to illustrate the implications of performing reproducible research and describe two case studies based on literature analysis to provide concrete information on the reproducibility of modern materials-oriented research. The two case studies deal with the properties of metal-organic frameworks (MOFs), a class of materials that have generated tens of thousands of papers. We do not claim that research on MOFs is less (or more) reproducible than other subfields; rather, we argue that the characteristics of this subfield are common to many areas of materials-oriented research. We conclude with specific recommendations for action by individual researchers, journal editors, publishers, and research communities.

This review compares droplet-based microfluidic systems used to study crystallization fundamentals in chemistry and biology. An original high-throughput droplet-based microfluidic platform is presented. It uses nanoliter droplets, generates a chemical library, and directly solubilizes powder, thus economizing both material and time. It is compatible with all solvents without the need for surfactant. Its flexibility permits phase diagram determination and crystallization studies (screening and optimizing experiments) and makes it easy to use for nonspecialists in microfluidics. Moreover, it allows concentration measurement via ultraviolet spectroscopy and solid characterization via X-ray diffraction analysis.

Dwindling fossil fuel resources and substantial release of CO2 from their processing have increased the appeal to use biomass as a sustainable platform for synthesis of chemicals and fuels. Steps toward this will require selective upgrading of biomass to suitable intermediates. Traditionally, biomass upgrading has involved thermochemical processes that require excessive amounts of petrochemical-derived H2 and suffer from poor product selectivity. Electrochemical routes have emerged as promising alternatives because of (a) the replacement of petrochemical-derived H2 by protons generated in situ, (b) mild operating temperatures and pressures, and (c) the use of electrode potential to tune reaction rates and product selectivity. In this review, we highlight the advances in the electrocatalytic hydrogenation and oxidation of biomass-derived platform molecules. The effects of important reaction parameters on electrochemical efficiency and catalytic activity/selectivity are thoroughly discussed. We conclude by summarizing current challenges and discussing future research directions.

Industrial biotechnology has the potential to decrease our reliance on petroleum for fuel and bio-based chemical production and also enable valorization of waste streams. Anaerobic microorganisms thrive in resource-limited environments and offer an array of novel bioactivities in this regard that could revolutionize biomanufacturing. However, they have not been adopted for widespread industrial use owing to their strict growth requirements, limited number of available strains, difficulty in scale-up, and genetic intractability. This review provides an overview of current and future uses for anaerobes in biotechnology and bioprocessing in the postgenomic era. We focus on the recently characterized anaerobic fungi (Neocallimastigomycota) native to the digestive tract of large herbivores, which possess a trove of enzymes, pathways, transporters, and other biomolecules that can be harnessed for numerous biotechnological applications. Resolving current genetic intractability, scale-up, and cultivation challenges will unlock the potential of these lignocellulolytic fungi and other nonmodel micro-organisms to accelerate bio-based production.

Accurate continuum models of flow and segregation of dense granular flows are now possible. This is the result of extensive comparisons, over the last several years, of computer simulations of increasing accuracy and scale, experiments, and continuum models, in a variety of flows and for a variety of mixtures. Computer simulations—discrete element methods (DEM)—yield remarkably detailed views of granular flow and segregation. Conti-nuum models, however, offer the best possibility for parametric studies of outcomes in what could be a prohibitively large space resulting from the competition between three distinct driving mechanisms: advection, diffusion, and segregation. We present a continuum transport equation–based framework, informed by phenomenological constitutive equations, that accurately predicts segregation in many settings, both industrial and natural. Three-way comparisons among experiments, DEM, and theory are offered wherever possible to validate the approach. In addition to the flows and mixtures described here, many straightforward extensions of the framework appear possible.

Nanoparticle-based systems offer fascinating possibilities for biomedicine, but their translation into clinics is slow. Missing sterile, reproducible, and scalable methods for their synthesis along with challenges in characterization and poor colloidal stability of nanoparticles in body fluids are key obstacles. Flame aerosol technology gives proven access to scalable synthesis of nanoparticles with diverse compositions and architectures. Although highly promising in terms of product reproducibility and sterility, this technology is frequently overlooked, as its products are of fractal-like aggregated and/or agglomerated morphology. However, coagulation is a widely occurring phenomenon in all kinds of particle-based systems. In particular, protein-rich body fluids encountered in biomedical settings often lead to destabilization of colloidal nanoparticle suspensions in vivo. We aim to provide insights into how particle–particle interactions can be measured and controlled. Moreover, we show how particle coupling effects driven by coagulation may even be beneficial for certain sensing, therapeutic, and bioimaging applications.

The ability to behave in a fluidlike manner fundamentally separates thermoset and thermoplastic polymers. Bridging this divide, covalent adaptable networks (CANs) structurally resemble thermosets with permanent covalent crosslinks but are able to flow in a manner that resembles thermoplastic behavior only when a dynamic chemical reaction is active. As a consequence, the rheological behavior of CANs becomes intrinsically tied to the dynamic reaction kinetics and the stimuli that are used to trigger those, including temperature, light, and chemical stimuli, providing unprecedented control over viscoelastic properties. CANs represent a highly capable material that serves as a powerful tool to improve mechanical properties and processing in a wide variety of polymer applications, including composites, hydrogels, and shape-memory polymers. This review aims to highlight the enabling material properties of CANs and the applied fields where the CAN concept has been embraced.

This article reviews recent theoretical developments on incipient ignition induced by radical runaway in systems described by detailed chemistry. Employing eigenvalue analysis, we first analyze the canonical explosion limits of mixtures of hydrogen and oxygen, yielding explicit criteria that well reproduce their characteristic Z-shaped response in the pressure–temperature plot. Subsequently, we evaluate the role of hydrogen addition to the explosion limits of mixtures of oxygen with either carbon monoxide or methane, demonstrating and quantifying its strong catalytic effect, especially for the carbon monoxide cases. We then discuss the role of low-temperature chemistry in the autoignition of large hydrocarbon fuels, with emphasis on the first-stage ignition delay and the associated negative-temperature coefficient phenomena. Finally, we extend the analysis to problems of nonhomogeneous ignition in the presence of convective–diffusive transport, using counterflow as an example, demonstrating the canonical similarity between homogeneous and nonhomogeneous systems. We conclude with suggestions for potential directions for future research.

Hydrogen is an important part of any discussion on sustainability and reduction in emissions across major energy sectors. In addition to being a feedstock and process gas for many industrial processes, hydrogen is emerging as a fuel alternative for transportation applications. Renewable sources of hydrogen are therefore required to increase in capacity. Low-temperature electrolysis of water is currently the most mature method for carbon-free hydrogen generation and is reaching relevant scales to impact the energy landscape. However, costs still need to be reduced to be economical with traditional hydrogen sources. Operating cost reductions are enabled by the recent availability of low-cost sources of renewable energy, and the potential exists for a large reduction in capital cost withmaterial and manufacturing optimization. This article focuses on the current status and development needs by component for the low-temperature electrolysis options.

In marine industries, the accumulation of organic matter and marine organisms on ship hulls and instruments limits performance, requiring frequent maintenance and increasing fuel costs. Current coatings technology to combat this biofouling relies heavily on the use of toxic, biocide-containing paints. These pose a serious threat to marine ecosystems, affecting both target and nontarget organisms. Innovation in the design of polymers offers an excellent platform for the development of alternatives, but the creation of a broad-spectrum, nontoxic material still poses quite a hurdle for researchers. Surface chemistry, physical properties, durability, and attachment scheme have been shown to play a vital role in the construction of a successful coating. This review explores why these characteristics are important and how recent research accounts for them in the design and synthesis of new environmentally benign antifouling and fouling release materials.

Products from chemical engineering are essential for human well-being, but they also contribute to the degradation of ecosystem goods and services that are essential for sustaining all human activities. To contribute to sustainability, chemical engineering needs to address this paradox by developing chemical products and processes that meet the needs of present and future generations. Unintended harm of chemical engineering has usually appeared outside the discipline's traditional system boundary due to shifting of impacts across space, time, flows, or disciplines, and exceeding nature's capacity to supply goods and services. Being a subdiscipline of chemical engineering, process systems engineering (PSE) is best suited for ensuring that chemical engineering makes net positive contributions to sustainable development. This article reviews the role of PSE in the quest toward a sustainable chemical engineering. It focuses on advances in metrics, process design, product design, and process dynamics and control toward sustainability. Efforts toward contributing to this quest have already expanded the boundary of PSE to consider economic, environmental, and societal aspects of processes, products, and their life cycles. Future efforts need to account for the role of ecosystems in supporting industrial activities, and the effects of human behavior and markets on the environmental impacts of chemical products. Close interaction is needed between the reductionism of chemical engineering science and the holism of process systems engineering, along with a shift in the engineering paradigm from wanting to dominate nature to learning from it and respecting its limits.

This article seeks to be a handy document for the academy and the industry to get quickly up to speed on the current status and prospects of biomass pretreatment for biorefineries. It is divided into two biomass sources: vegetal and animal. Vegetal biomass is the material produced by plants on land or in water (algae), consuming sunlight, CO2, water, and soil nutrients. This includes residues or main products from, for example, intensive grass crops, forestry, and industrial and agricultural activities. Animal biomass is the residual biomass generated from the production of food from animals (e.g., manure and whey). This review does not mean to include every technology in the area, but it does evaluate physical pretreatments, microwave-assisted extraction, and water treatments for vegetal biomass. A general review is given for animal biomass based in physical, chemical, and biological pretreatments.

Polymers play an essential role in drug formulation and production of medical devices, implants, and diagnostics. Following drug discovery, an appropriate formulation is selected to enable drug delivery. This task can be exceedingly challenging owing to the large number of potential delivery methods and formulation and process variables that can interact in complex ways. This evolving solubility challenge has inspired an increasing emphasis on the developability of drug candidates in early discovery as well as various advanced drug solubilization strategies. Among the latter, formulation approaches that lead to prolonged drug supersaturation to maximize the driving force for sustained intestinal absorption of an oral product, or to allow sufficient time for injection after reconstitution of a parenteral lyophile formulation, have attracted increasing interest. Although several kinetic and thermodynamic components are involved in stabilizing amorphous dispersions, it is generally assumed that maximum physical stability, defined in terms of inhibition of drug crystallization, requires that the drug and excipient remain intimately mixed. Phase separation of the drug from its excipient may be the first step that ultimately leads to crystallization. We discuss the role of advanced thermodynamics using two examples: ASD and vitamin E–stabilized ultrahigh–molecular weight polyethylene implants.

Although vaccines have been the primary defense against widespread infectious disease for decades, there is a critical need for improvement to combat complex and variable diseases. More control and specificity over the immune response can be achieved by using only subunit components in vaccines. However, these often lack sufficient immunogenicity to fully protect, and conjugation or carrier materials are required. A variety of protein and peptide biomaterials have improved effectiveness and delivery of subunit vaccines for infectious, cancer, and autoimmune diseases. They are biodegradable and have control over both material structure and immune function. Many of these materials are built from naturally occurring self-assembling proteins, which have been engineered for incorporation of vaccine components. In contrast, others are de novo designs of structures with immune function. In this review, protein biomaterial design, engineering, and immune functionality as vaccines or immunotherapies are discussed.

Responsive polymers undergo reversible or irreversible physical or chemical modifications in response to a change in environment or stimulus, e.g., temperature, pH, light, and magnetic or electric fields. Polymeric nanoparticles (NPs), which constitute a diverse set of morphologies, including micelles, vesicles, and core-shell geometries, have been successfully prepared from responsive polymers and have shown great promise in applications ranging from drug delivery to catalysis. In this review, we summarize pH, thermo-, photo-, and enzymatic responsiveness for a selection of polymers. We then discuss the formation of NPs made from responsive polymers. Finally, we highlight how NPs and other nanomaterials are enabling a wide range of smart applications with improved efficiency, as well as improved sustainability and recyclability of polymeric systems.