Annual Review of Chemical and Biomolecular Engineering - Volume 7, 2016

The first three decades of my research career closely map the development of neutron scattering techniques for the study of molecular behavior. At the same time, the theoretical understanding of organization and motion of polymer molecules, especially in the bulk state, was developing rapidly and providing many predictions crying out for experimental verification. Neutron scattering is an ideal technique for providing the necessary evidence. This autobiographical essay describes the applications by my research group and other collaborators of increasingly sophisticated neutron scattering techniques to observe and understand molecular behavior in polymeric materials. It has been a stimulating and rewarding journey.

Although thermal desalination technology provides potable water in arid regions (e.g., Israel and the Gulf), its relatively high cost has limited application to less arid regions with large populations (e.g., California). Energy-intensive distillation is currently being replaced with less costly pressure- and electrically driven membrane-based processes. Reverse osmosis (RO) is a preferred membrane technology owing to process and pre- and posttreatment improvements that have significantly reduced energy requirements and cost. Further technical advances will require a deeper understanding of the fundamental science underlying RO. This includes determining the mechanism for water selectivity; elucidating the behavior of molecular water near polar and apolar surfaces, as well as the advantages and limitations of hydrophobic versus hydrophilic pores; learning the rules of selective water transport from nature; and designing synthetic analogs for selective water transport. Molecular dynamics simulations supporting experiments will play an important role in advancing these efforts. Finally, future improvements in RO are limited by inherent technical mass transfer limitations.

In this review, we sketch the materials modeling process in industry. We show that predictive and fast modeling is a prerequisite for successful participation in research and development processes in the chemical industry. Stable and highly automated workflows suitable for handling complex systems are a must. In particular, we review approaches to build and parameterize soft matter systems. By satisfying these prerequisites, efficiency for the development of new materials can be significantly improved, as exemplified here for formulation polymer development. This is in fact in line with recent Materials Genome Initiative efforts sponsored by the US government. Valuable contributions to product development are possible today by combining existing modeling techniques in an intelligent fashion, provided modeling and experiment work hand in hand.

Accelerated molecular dynamics (AMD) is a class of MD-based methods used to simulate atomistic systems in which the metastable state-to-state evolution is slow compared with thermal vibrations. Temperature-accelerated dynamics (TAD) is a particularly efficient AMD procedure in which the predicted evolution is hastened by elevating the temperature of the system and then recovering the correct state-to-state dynamics at the temperature of interest. TAD has been used to study various materials applications, often revealing surprising behavior beyond the reach of direct MD. This success has inspired several algorithmic performance enhancements, as well as the analysis of its mathematical framework. Recently, these enhancements have leveraged parallel programming techniques to enhance both the spatial and temporal scaling of the traditional approach. We review the ongoing evolution of the modern TAD method and introduce the latest development: speculatively parallel TAD.

Ion exchange membranes are used in various membrane-based processes (e.g., electrodialysis, fuel cells). Charged solute transport is largely governed by the charged groups on the polymer backbone. In this review, fundamental relationships describing salt permeability and ionic conductivity, as well as water permeability, in charged polymers are developed within the framework of the Nernst-Planck and solution-diffusion models. The influence of fixed charge groups and polymer structure on water sorption and diffusion is discussed. Current understanding of ion partitioning in charged polymers, focusing on the use of thermodynamic models (i.e., Donnan theory) to describe such phenomena, is summarized. Ion diffusivity data from the literature are interpreted using a model developed by Mackie and Meares to assess relative and absolute effects of the polymer and fixed charge groups on ion diffusivity. Furthermore, membrane requirements for several important technologies are listed. Knowledge gaps and opportunities for fundamental research are also discussed.

The advent of the industrial revolution in the nineteenth century increased the volume and variety of manufactured goods and enriched the quality of life for society as a whole. However, industrialization was also accompanied by new manufacturing and complex processes that brought about the use of hazardous chemicals and difficult-to-control operating conditions. Moreover, human-process-equipment interaction plus on-the-job learning resulted in further undesirable outcomes and associated consequences. These problems gave rise to many catastrophic process safety incidents that resulted in thousands of fatalities and injuries, losses of property, and environmental damages. These events led eventually to the necessity for a gradual development of a new multidisciplinary field, referred to as process safety. From its inception in the early 1970s to the current state of the art, process safety has come to represent a wide array of issues, including safety culture, process safety management systems, process safety engineering, loss prevention, risk assessment, risk management, and inherently safer technology. Governments and academic/research organizations have kept pace with regulatory programs and research initiatives, respectively. Understanding how major incidents impact regulations and contribute to industrial and academic technology development provides a firm foundation to address new challenges, and to continue applying science and engineering to develop and implement programs to keep hazardous materials within containment. Here the most significant incidents in terms of their impact on regulations and the overall development of the field of process safety are described.

Liquid crystals (LCs) are widely known for their use in liquid crystal displays (LCDs). Indeed, LCDs represent one of the most successful technologies developed to date using a responsive soft material: An electric field is used to induce a change in ordering of the LC and thus a change in optical appearance. Over the past decade, however, research has revealed the fundamental underpinnings of potentially far broader and more pervasive uses of LCs for the design of responsive soft material systems. These systems involve a delicate interplay of the effects of surface-induced ordering, elastic strain of LCs, and formation of topological defects and are characterized by a chemical complexity and diversity of nano- and micrometer-scale geometry that goes well beyond that previously investigated. As a reflection of this evolution, the community investigating LC-based materials now relies heavily on concepts from colloid and interface science. In this context, this review describes recent advances in colloidal and interfacial phenomena involving LCs that are enabling the design of new classes of soft matter that respond to stimuli as broad as light, airborne pollutants, bacterial toxins in water, mechanical interactions with living cells, molecular chirality, and more. Ongoing efforts hint also that the collective properties of LCs (e.g., LC-dispersed colloids) will, over the coming decade, yield exciting new classes of driven or active soft material systems in which organization (and useful properties) emerges during the dissipation of energy.

Disulfide bonds represent versatile posttranslational modifications whose roles encompass the structure, catalysis, and regulation of protein function. Due to the oxidizing nature of the extracellular environment, disulfide bonds found in secreted proteins were once believed to be inert. This notion has been challenged by the discovery of redox-sensitive disulfides that, once cleaved, can lead to changes in protein activity. These functional disulfides are twisted into unique configurations, leading to high strain and potential energy. In some cases, cleavage of these disulfides can lead to a gain of function in protein activity. Thus, these motifs can be referred to as switches. We describe the couples that control redox in the extracellular environment, examine several examples of proteins with switchable disulfides, and discuss the potential applications of disulfides in molecular biology.

This review presents a selection of recent publications related to the chemistry and catalysis of C1 molecules, including methane, methanol, carbon monoxide, and carbon dioxide. These molecules play an important role in the current supply of energy and chemicals and will likely become even more relevant because of the need to decarbonize fuels (shift from coal to natural gas) in line with CO2 capture and use to mitigate global warming, as well as a gradual shift on the supply side from crude oil to natural gas. This review includes both recent industrial developments, such as the huge increase in methanol-to-olefins-capacity build in China and the demonstration of oxidative coupling of methane, and scientific developments in these chemistries facilitated by improved capabilities in, for example, analytical tools and computational modeling.

As the global population grows in size and increasingly lives in cities, and with lifestyles based on greater material consumption, more attention is being given to the integrated system that supplies our energy, water, and food, the Nexus. There is also mounting concern about effects on the Nexus of climate change and damage to the natural environment that provides essential ecosystem services. Nexus analysis applies existing techniques, such as computational modelling and Life Cycle Assessment, but new frameworks and tools are needed, including those that will integrate societal and technical dimensions. Case studies show the vital role played by stakeholder involvement in clarifying issues, priorities, and values. They also demonstrate the importance of an integrated systems view of the complex interrelationships of the Nexus when planning effective remedies. Assessments conclude that transformative social and political change is needed to create new structures, markets, and governance to deal with the Nexus if we are to meet agreed-upon sustainable development goals.

After decades of research and development on fabrication of efficient light-emitting diodes (LEDs) throughout the visible spectrum, LED-based lighting has reached unparalleled performance with respect to energy efficiency and has become the light source for virtually all new lighting products being designed today. The development of the core light sources and their subsequent integration into lighting systems continue to present unique challenges and opportunities for product designers. We review these systems and the current development status, as well as provide context for the trends in solid state lighting that are leading to the development of value-added lighting solutions that extend the domain of lighting beyond light generation, into fields as diverse as communications, healthcare, and agricultural production.

This article reviews the basic principles of and recent developments in electrochromic, photochromic, and thermochromic materials for applications in smart windows. Compared with current static windows, smart windows can dynamically modulate the transmittance of solar irradiation based on weather conditions and personal preferences, thus simultaneously improving building energy efficiency and indoor human comfort. Although some smart windows are commercially available, their widespread implementation has not yet been realized. Recent advances in nanostructured materials provide new opportunities for next-generation smart window technology owing to their unique structure-property relations. Nanomaterials can provide enhanced coloration efficiency, faster switching kinetics, and longer lifetime. In addition, their compatibility with solution processing enables low-cost and high-throughput fabrication. This review also discusses the importance of dual-band modulation of visible and near-infrared (NIR) light, as nearly 50% of solar energy lies in the NIR region. Some latest results show that solution-processable nanostructured systems can selectively modulate the NIR light without affecting the visible transmittance, thus reducing energy consumption by air conditioning, heating, and artificial lighting.

The immune system is an incredibly complex biological network that plays a significant role in almost all disease pathogenesis. With an increased understanding of how this vital system operates, there has been a great emphasis on leveraging, manipulating, and/or supplementing endogenous immunity to better prevent or treat different disease states. More recently, the advent of nanotechnology has ushered in a plethora of new nanoparticle-based platforms that can be used to improve existing immunomodulation modalities. As the ability to engineer at the nanoscale becomes increasingly sophisticated, nanoparticles can be finely tuned to effect the desired immune responses, leading to exciting new avenues for addressing pressing issues in public health. In this review, we give an overview of the different areas in which nanoparticle technology has been applied toward modulating the immune system and highlight the recent advances within each.

The ability to control the shape of metal nanocrystals allows us to not only maneuver their physicochemical properties but also optimize their activity in a variety of applications. Heterogeneous catalysis, in particular, would benefit tremendously from the availability of metal nanocrystals with controlled shapes and well-defined facets or surface structures. The immediate benefits may include significant enhancements in catalytic activity and/or selectivity along with reductions in the materials cost. We provide a brief account of recent progress in the development of metal nanocrystals with controlled shapes and thereby enhanced catalytic performance for several reactions, including formic acid oxidation, oxygen reduction, and hydrogenation. In addition to monometallic nanocrystals, we also cover a bimetallic system, in which the two metals are formulated as alloyed, core-shell, or core-frame structures. We hope this article will provide further impetus for the development of next-generation heterogeneous catalysts essential to a broad range of applications.

Understanding the mechanisms and optimizing ion transport in polymer membranes have been the subject of active research for more than three decades. We present an overview of the progress and challenges involved with the modeling and simulation aspects of the ion transport properties of polymer membranes. We are concerned mainly with atomistic and coarser level simulation studies and discuss some salient work in the context of pure binary and single ion conducting polymer electrolytes, polymer nanocomposites, block copolymers, and ionic liquid–based hybrid electrolytes. We conclude with an outlook highlighting future directions.

Chemical vapor deposition (CVD) polymerization uses vapor phase monomeric reactants to synthesize organic thin films directly on substrates. These thin films are desirable as conformal surface engineering materials and functional layers. The facile tunability of the films and their surface properties allow successful integration of CVD thin films into prototypes for applications in surface modification, device fabrication, and protective films. CVD polymers also bridge microfabrication technology with chemical and biological systems. Robust coatings can be achieved via CVD methods as antifouling, anti-icing, and antihydrate surfaces, as well as stimuli-responsive or biocompatible polymers and novel nanostructures. Use of low-energy input, modest vacuum, and room-temperature substrates renders CVD polymerization compatible with thermally sensitive substrates and devices. Compared with solution-based methods, CVD is particularly useful for insoluble materials, such as electrically conductive polymers and controllably crosslinked networks, and has the potential to reduce environmental, health, and safety impacts associated with solvents. This review discusses the relevant background and selected applications of recent advances by two methods that display and use the high retention of the organic functional groups from their respective monomers, initiated CVD (iCVD) and oxidative CVD (oCVD) polymerization.

Thermodynamic principles have been applied to enzyme-catalyzed reactions since the beginning of the 1930s in an attempt to understand metabolic pathways. Currently, thermodynamics is also applied to the design and analysis of biotechnological processes. The key thermodynamic quantity is the Gibbs energy of reaction, which must be negative for a reaction to occur spontaneously. However, the application of thermodynamic feasibility studies sometimes yields positive Gibbs energies of reaction even for reactions that are known to occur spontaneously, such as glycolysis. This article reviews the application of thermodynamics in enzyme-catalyzed reactions. It summarizes the basic thermodynamic relationships used for describing the Gibbs energy of reaction and also refers to the nonuniform application of these relationships in the literature. The review summarizes state-of-the-art approaches that describe the influence of temperature, pH, electrolytes, solvents, and concentrations of reacting agents on the Gibbs energy of reaction and, therefore, on the feasibility and yield of biological reactions.

Nearly 70 years old, hydraulic fracturing is a core technique for stimulating hydrocarbon production in a majority of oil and gas reservoirs. Complex fluids are implemented in nearly every step of the fracturing process, most significantly to generate and sustain fractures and transport and distribute proppant particles during and following fluid injection. An extremely wide range of complex fluids are used: naturally occurring polysaccharide and synthetic polymer solutions, aqueous physical and chemical gels, organic gels, micellar surfactant solutions, emulsions, and foams. These fluids are loaded over a wide range of concentrations with particles of varying sizes and aspect ratios and are subjected to extreme mechanical and environmental conditions. We describe the settings of hydraulic fracturing (framed by geology), fracturing mechanics and physics, and the critical role that non-Newtonian fluid dynamics and complex fluids play in the hydraulic fracturing process.

Stem cells and other functionally defined therapeutic cells (e.g., T cells) are promising to bring hope of a permanent cure for diseases and disorders that currently cannot be cured by conventional drugs or biological molecules. This paradigm shift in modern medicine of using cells as novel therapeutics can be realized only if suitable manufacturing technologies for large-scale, cost-effective, reproducible production of high-quality cells can be developed. Here we review the state of the art in therapeutic cell manufacturing, including cell purification and isolation, activation and differentiation, genetic modification, expansion, packaging, and preservation. We identify current challenges and discuss opportunities to overcome them such that cell therapies become highly effective, safe, and predictively reproducible while at the same time becoming affordable and widely available.