Protein biotherapeutics typically require expensive cold‐chain storage to maintain their fold and function. Packaging proteins in the dry state via lyophilization can reduce these cold‐chain requirements. However, formulating proteins for lyophilization often requires extensive optimization of excipients that both maintain the protein folded state during freezing and drying (i.e., “cryoprotection” and “lyoprotection”), and form a cake to carry the dehydrated protein. Here we show that sweet corn phytoglycogens, which are glucose dendrimers, can act as both a protein lyoprotectant and a cake‐forming agent. Phytoglycogen (PG) dendrimers from 16 different maize sources (PG1‐16) were extracted via ethanol precipitation. PG size was generally consistent at ~70–100 nm for all variants, whereas the colloidal stability in water, protein contaminant level, and maximum density of cytocompatibility varied for PG1‐16. 10 mg/mL PG1, 2, 9, 13, 15, and 16 maintained the activity of various proteins, including green fluorescent protein, lysozyme, β‐galactosidase, and horseradish peroxidase, over a broad range of concentrations, through multiple rounds of lyophilization. PG13 was identified as the lead excipient candidate as it demonstrated narrow dispersity, colloidal stability in phosphate‐buffered saline, low protein contaminants, and cytocompatibility up to 10 mg/mL in NIH3T3 cell cultures. All dry protein‐PG13 mixtures had a cake‐like appearance and all frozen protein‐PG13 mixtures had a Tg' of ~ −26°C. The lyoprotection and cake‐forming properties of PG13 were density‐dependent, requiring a minimum density of 5 mg/mL for maximum activity. Collectively these data establish PG dendrimers as a new class of excipient to formulate proteins in the dry state.

Every year, there are approximately 500 000 peripheral nerve injury (PNI) procedures due to trauma in the US alone. Autologous and acellular nerve grafts are among current clinical repair options; however, they are limited largely by the high costs associated with donor nerve tissue harvesting and implant processing, respectively. Therefore, there is a clinical need for an off-the-shelf nerve graft that can recapitulate the native microenvironment of the nerve. In our previous work, we created a hydrogel scaffold that incorporates mechanical and biological cues that mimic the peripheral nerve microenvironment using chemically modified hyaluronic acid (HA). However, with our previous work, the degradation profile and cell adhesivity was not ideal for tissue regeneration, in particular, peripheral nerve regeneration. To improve our previous hydrogel, HA was conjugated with fibrinogen using Michael-addition to assist in cell adhesion and hydrogel degradability. The addition of the fibrinogen linker was found to contribute to faster scaffold degradation via active enzymatic breakdown, compared to HA alone. Additionally, cell count and metabolic activity was significantly higher on HA conjugated fibrinogen compared previous hydrogel formulations. This manuscript discusses the various techniques deployed to characterize our new modified HA fibrinogen chemistry physically, mechanically, and biologically. This work addresses the aforementioned concerns by incorporating controllable degradability and increased cell adhesivity while maintaining incorporation of hyaluronic acid, paving the pathway for use in a variety of applications as a multi-purpose tissue engineering platform.

We report on a cycling scheme for Doppler cooling of trapped OH^+ ions using transitions between the electronic ground state X^3Σ^- and the first excited triplet state A^3Π. We have identified relevant transitions for photon cycling and repumping, have found that coupling into other electronic states is strongly suppressed, and have calculated the number of photon scatterings required to cool OH^+ to a temperature where Raman sideband cooling can take over. In contrast to the standard approach, where molecular ions are sympathetically cooled, our scheme does not require co-trapping of another species and opens the door to the creation of pure samples of cold molecular ions with potential applications in quantum information, quantum chemistry, and astrochemistry. The laser cooling scheme identified for OH^+ is efficient despite the absence of near-diagonal Franck-Condon factors, suggesting that broader classes of molecules and molecular ions are amenable to laser cooling than commonly assumed.

A multitude of weaker Fe IX lines have been predicted in the vicinity of the strong 171 Å line that dominates the spectra of many astrophysical and laboratory sources. Some of these weaker lines have only recently been identified in the laboratory, albeit some only tentatively. Here, we present measurements on the Livermore EBIT-I electron beam ion trap that span the region from 170.0 to 173.6 Å, which surrounds the 171 Å line. The measurements stepped through electron beam energy to determine the charge state of iron associated with each observed feature. Moreover, we have minimized the presence of oxygen in the trap, because oxygen lines obscured possible Fe IX lines in past measurements and prevented their identification. Our measurement confirms formerly tentative identifications and adds several new assignments.

Selective aerogel has become an attractive adsorbent for removing oil and organic contaminants due to its low density and excellent adsorption capacity. However, aerogels usually use non-sustainable or expensive nanomaterials and require complicated fabrication processes. Herein, using low-cost lignin reclaimed from the biorefinery waste stream as the starting material, we fabricated a highly porous, mechanically strong, and stable aerogel via a simple and one-step method under mild conditions. This aerogel exhibits a controllable micropore structure and achieves quick and efficient adsorption for oil (435% g/g), as well as toxic solvents such as THF (365% g/g). The selective and stable adsorbent can be reused multiple times and the oil adsorption capacity after 5 cycles remained at 89%. This highly efficient, mechanically strong, stable, and regenerable aerogel is a potential candidate for multiple applications such as cleaning up organic contaminants, oil remediation, and oil/water separation. Meanwhile, it also employs a “waste-treat-waste” concept by adding extra value to the biorefinery process for high-efficiency circular bioeconomy.

PEGylation is a promising approach to address the central challenge of applying biologics, i.e., lack of protein stability in the demanding environment of the human body. Wider application is hindered by lack of atomic level understanding of protein-PEG interactions, preventing design of conjugates with predicted properties. We deployed an integrative structural and biophysical approach to address this critical challenge with the PEGylated carbohydrate recognition domain of human galectin-3 (Gal3C), a lectin essential for cell adhesion and potential biologic. PEGylation dramatically increased Gal3C thermal stability, forming a stable intermediate and redirecting its unfolding pathway. Structural details revealed by NMR pointed to a potential role of PEG localization facilitated by charged residues. Replacing these residues subtly altered the protein-PEG interface and thermal unfolding behavior, providing insight into rationally designing conjugates while preserving PEGylation benefits.

Amphiphilic polymers have been covalently grafted from a SiO2 core with room temperature polymerizations. These amphiphilic grafted nanoparticles have been found to uptake up to 30 times their mass in crude oil within a 24 hour window.

The photoinduced intrachain crosslinking of coumarin-containing copolymers in various organic solvents was mediated through the solvophobic effect, providing control over the reaction rate and the compaction of the final single-chain nanoparticles.

Large amounts of food are wasted during the food supply chain. This loss is in part due to consumer confusion over dates on food packages that can indicate a variety of quality indicators in the product (e.g., expiration date, "best by" date, "sell by" dates, etc.). To reduce this food loss, much research has been focused on the films that offer simple and easily manipulated indication systems to detect food spoilage. However, these materials are usually hydrophilic biopolymers that can detect the food spoilage in a wide pH range but do not provide highly sensitive real-time measurements. In this work, a glycerol-based nanocomposite core-shell latex film was synthesized to create a responsive packaging material that can provide real-time pH detection of food with high sensitivity. First, the pH-responsive dendrimer comonomer was synthesized from glycerol and diamine. Then, the nanoencapsulation polymerization process via miniemulsion was conducted to form a core-shell structure with tunable nanoshell thickness for a sensible pH-responsive release (<0.5 pH change). Next, the flexible film encapsulated a color-indicative dye that provided highly sensitive and visible color changes as both the pH dropped and the time elapsed in the food. This film also provided a barrier to water and heat and resisted deformation. Ultimately, this nanocomposite flexible film pending a pH sensor has the potential as an intelligent food packaging material for a universal, accurate, easy-to-use, and real-time food spoilage monitoring system to reduce food waste.

The size and size variability of bis-MPA dendrimers is shown to be smaller by DOSY-1H NMR than their linear analog, PBBM. This was accomplished using five different solvents and for the first time confirms, experimentally, what has been theorized.

ADVERTISEMENT RETURN TO ISSUEViewpointNEXTBob Cave MemorialDaniel A. SavinDaniel A. SavinDepartment of Chemistry, University of Florida, Gainesville, Florida 32611, United StatesMore by Daniel A. Savin, Joseph E. SubotnikJoseph E. SubotnikDepartment of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United StatesMore by Joseph E. Subotnik, Kieron BurkeKieron BurkeDepartment of Chemistry, University of California-Irvine, Irvine, California 92617, United StatesMore by Kieron Burkehttp://orcid.org/0000-0002-6159-0054, Evelyn M. GoldfieldEvelyn M. GoldfieldDepartment of Chemistry, Wayne State University, Detroit, Michigan 48202, United StatesMore by Evelyn M. Goldfield, Marshall D. NewtonMarshall D. NewtonChemistry Department, Brookhaven National Laboratory, Upton, New York 11973, United StatesMore by Marshall D. Newtonhttp://orcid.org/0000-0002-3435-2085, and John F. Stanton*John F. StantonDepartment of Chemistry, University of Florida, Gainesville, Florida 32611, United States*[email protected]More by John F. Stantonhttp://orcid.org/0000-0003-2345-9781Cite this: J. Phys. Chem. A 2021, 125, 19, 4037–4038Publication Date (Web):April 23, 2021Publication History Published online23 April 2021Published inissue 20 May 2021https://pubs.acs.org/doi/10.1021/acs.jpca.1c03256https://doi.org/10.1021/acs.jpca.1c03256editorialACS PublicationsCopyright © Published 2021 by American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views1746Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (559 KB) Get e-AlertscloseSUBJECTS:Post-secondary education Get e-Alerts

Launching a startup company is like synthesizing a new molecule. There is a starting point and a general concept for how to achieve the desired end. Known steps may be taken, but a successful synthesis is rarely the result of the original plan and relies on perseverance and creativity. If done well, the starting molecule (idea) gives rise to a new final product (business). Having personally lived these journeys, the authors of this viewpoint distilled their combined experiences into relevant topics for scientific entrepreneurs. This viewpoint is not a how-to guide for launching a startup. Instead, relatable personal insights and potential best practices are shared to catalyze discussions around a topic of growing relevance to both the polymer community and workforce of the future.

Melanin is a ubiquitous natural pigment found in a diverse array of organisms. Allomelanin is a class of nitrogen-free melanin often found in fungi. Herein, we find artificial allomelanin analogues exhibit high intrinsic microporosity and describe an approach for further increasing and tuning that porosity. Notably, the synthetic method involves an oxidative polymerization of 1,8-DHN in water, negating the need for multiple complex templating steps and avoiding expensive or complex chemical precursors. The well-defined morphologies of these nanomaterials were elucidated by a combination of electron microscopy and scattering methods, yielding to high-resolution 3D reconstruction based on small-angle X-ray scattering (SAXS) results. Synthetic allomelanin nanoparticles exhibit high BET areas, up to 860 m2/g, and are capable of ammonia capture up to 17.0 mmol/g at 1 bar. In addition, these nanomaterials can adsorb nerve agent simulants in solution and as a coating on fabrics with high breathability where they prevent breakthrough. We also confirmed that naturally derived fungal melanin can adsorb nerve gas simulants in solution efficiently despite lower porosity than synthetic analogues. Our approach inspires further analysis of yet to be discovered biological materials of this class where melanins with intrinsic microporosity may be linked to evolutionary advantages in relevant organisms and may in turn inspire the design of new high surface area materials.

MONITORED USING A GENE EXPRESSION BIOMARKER IN FATHEAD MINNOW JUVENILES Hajime Kurita1, Kevin Kroll1, Wayne Reed3, Scott Grayson4, Daniel Savin2, Nancy Denslow1 1Department of Physiological Sciences, University of Florida, Gainesville, FL, USA 2Department of Chemistry, University of Florida, Gainesville, FL, USA 3Department of Physics, Tulane University, New Orleans, LA, USA 4Department of Chemistry, Tulane University, New Orleans, LA, USA

The self-assembly behavior of an ABC triblock copolypeptide consisting of poly(ethylene oxide-b-(leucine-s-valine)-b-lysine) (PEO-PLV-PK) was examined via dynamic light scattering in dilute aqueous solution. Leucine is a hydrophobic, a-helix forming polypeptide that exhibits a "zipper effect" in coiled-coil dimers. We hypothesize that the specific interaction afforded by the leucine zipper dominates the thermodynamics of self-assembly through the side-by-side ordering of a-helices, which drives veside formation in a polymer with only 6 wt % hydrophobic content. Additionally, a multitude of assembly sizes and morphologies were attainable from a single polymer, depending on the solution processing method. Thermodynamic effects of the leucine zipper can be interpreted, in part, from solubility parameters determined from molecular modeling. The combination of synthesis, solvent processing, and computational studies helps to elucidate the thermodynamic effects of this unique assembly motif on classical self-assembly processes.

We present a modular platform from which biohybrid protein-polymer nanostructures can be generated in a straightforward and facile manner. Specifically, an aqueous polymerization-induced self-assembly (PISA) AB block copolymerization system was derived from a mutant superfolder green fluorescent protein (sfGFP) as the solvophilic, stabilizing A block. By genetically encoding sfGFP with an isobutyryl bromide functionality, we grafted a quintessential atom-transfer radical polymerization initiation site with hydroxypropyl methacrylate (HPMA) to form the solvophobic B block. Monitoring nanostructure formation using dynamic light scattering, gel permeation chromatography, and transmission electron microscopy revealed uniform micellar morphologies. The radii of the micelles increased with increasing HPMA block length, resulting in nanoparticle sizes ranging from 15 to 48 nm. Solvophilic stabilization afforded by the encoded sfGFP makes this an ideal PISA initiator, and we posit this platform has potential for generating complex biohybrid nanostructures for other protein-polymer systems.

Multidrug resistance continues to be a barrier to the effectiveness of highly active antiretroviral therapy in the treatment of human immunodeficiency virus 1 (HIV-1) infection. Darunavir (DRV) is a highly potent protease inhibitor (PI) that is oftentimes effective when drug resistance has emerged against first-generation inhibitors. Resistance to darunavir does evolve and requires 10–20 amino acid substitutions. The conformational landscapes of six highly characterized HIV-1 protease (PR) constructs that harbor up to 19 DRV-associated mutations were characterized by distance measurements with pulsed electron double resonance (PELDOR) paramagnetic resonance spectroscopy, namely double electron–electron resonance (DEER). The results show that the accumulated substitutions alter the conformational landscape compared to PI-naïve protease where the semi-open conformation is destabilized as the dominant population with open-like states becoming prevalent in many cases. A linear correlation is found between values of the DRV inhibition parameter Ki and the open-like to closed-state population ratio determined from DEER. The nearly 50% decrease in occupancy of the semi-open conformation is associated with reduced enzymatic activity, characterized previously in the literature.