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1. Enhanced Thermal Conductivity in a Diamine-Appended Metal–Organic Framework as a Result of Cooperative CO ₂ Adsorption

   https://doi.org/10.1021/acsami.0c10233  

   Babaei, Hasan ; Lee, Jung-Hoon ; Dods, Matthew N. ; Wilmer, Christopher E. ; Long, Jeffrey R. ( September 2020 , ACS Applied Materials & Interfaces)

   Diamine-appended variants of the metal–organic framework M2(dobpdc) (M = Mg, Mn, Fe, Co, Zn; dobpdc4– = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) exhibit exceptional CO2 capture properties owing to a unique cooperative adsorption mechanism, and thus hold promise for use in the development of energy- and cost-efficient CO2 separations. Understanding the nature of thermal transport in these materials is essential for such practical applications, however, as temperature rises resulting from exothermic CO2 uptake could potentially offset the energy savings offered by such cooperative adsorbents. Here, molecular dynamics (MD) simulations are employed in investigating thermal transport in bare and e-2-appended Zn2(dobpdc) (e-2 = N-ethylethylenediamine), both withmore »and without CO2 as a guest. In the absence of CO2, the appended diamines function to enhance thermal conductivity in the ab-plane of e-2–Zn2(dobpdc) relative to the bare framework, as a result of noncovalent interactions between adjacent diamines that provide additional heat transfer pathways across the pore channel. Upon introduction of CO2, the thermal conductivity along the pore channel (the c-axis) increases due to the cooperative formation of metal-bound ammonium carbamates, which serve to create additional heat transfer pathways. In contrast, the thermal conductivity of the bare framework remains unchanged in the presence of zinc-bound CO2 but decreases in the presence of additional adsorbed CO2.« less
2. One-pot synthesis of enzyme@metal–organic material (MOM) biocomposites for enzyme biocatalysis

   https://doi.org/DOI https://doi.org/10.1039/D1GC00775K  

   Pan, Y. ; Li, H. ; Lenertz, M. ; Han, Y. ; Ugrinov, A. ; Kilin, D. ; Chen, B. ; Yang, Z. ( March 2021 , Green chemistry)

   Metal–organic frameworks/materials (MOFs/MOMs) are advanced enzyme immobilization platforms that improve biocatalysis, materials science, and protein biophysics. A unique way to immobilize enzymes is co-crystallization/co-precipitation, which removes the limitation on enzyme/substrate size. Thus far, most enzyme@MOF composites rely on the use of non-sustainable chemicals and, in certain cases, heavy metals, which not only creates concerns regarding environmental conservation but also limits their applications in nutrition and biomedicine. Here, we show that a dimeric compound derived from lignin, 5,5′-dehydrodivanillate (DDVA), co-precipitates with enzymes and low-toxicity metals, Ca2+ and Zn2+, and forms stable enzyme@Ca/Zn–MOM composites. We demonstrated this strategy on four enzymes withmore »different isoelectric points (IEPs), molecular weights, and substrate sizes. Furthermore, we found that all enzymes displayed slightly different but reasonable catalytic efficiencies upon immobilization in the Ca–DDVA and Zn–DDVA MOMs, as well as reasonable reusability in both composites. We then probed the structural basis of such differences using a representative enzyme and found enhanced restriction of enzymes in Zn–DDVA than in Ca–DDVA, which might have caused the activity difference. To the best of our knowledge, this is the first aqueous-phase, one-pot synthesis of a lignin-derived “green” enzyme@MOF/MOM platform that can host enzymes without any limitations on enzyme IEP, molecular weight, and substrate size. The different morphologies and crystallinities of the composites formed by Ca–DDVA and Zn–DDVA MOMs broaden their applications depending on the problem of interest. Our approach of enzyme immobilization not only improves the sustainability/reusability of almost all enzymes but also reduces/eliminates the use of non-sustainable resources. This synthesis method has a negligible environmental impact while the products are non-toxic to living things and the environment. The biocompatibility also makes it possible to carry out enzyme delivery/release for nutritional or biomedical applications via our “green” biocomposites.« less
3. Translation of protein charge and hydrophilicity to materials surface properties using thermal treatment in fluorous media

   https://doi.org/10.1039/C7MH00933J  

   Wang, Li-Sheng ; Gopalakrishnan, Sanjana ; Lee, Yi-Wei ; Zhu, Jiaxin ; Nonnenmann, Stephen S. ; Rotello, Vincent M. ( January 2018 , Materials Horizons)

   Protein-based materials provide an inherently biocompatible and sustainable platform for the generation of functional materials. Translating protein properties into protein films resistant to aqueous degradation is crucial for most applications such as tissue engineering and controlled drug delivery. Current methods to stabilize protein films use three main strategies: employing the relatively limited variety of naturally self-assembling proteins, using added cross-linkers or heat curing. While the cross-linking strategy generates functionally diverse structures, unreacted additives retained in cross-linked protein films can adversely affect their final behavior. Traditional heat curing results in hydrophobic surface and loss of protein inherent properties. We demonstrate heremore »a scalable, additive-free, fluorous media assisted thermal treatment for the fabrication of stable, hydrophilic protein films. This approach is general in terms of protein building block, retaining much of their native structure and surface properties upon heating. We demonstrate the versatility of this strategy through fabrication of antifouling coatings on complex three-dimensional surfaces. The utility of these films as biomaterials is highlighted through the generation of highly biocompatible non-fouling surfaces and regulation of cellular adhesion through choice of protein precursor.« less
4. Comparing Interfacial Trp, Interfacial His and pH Dependence for the Anchoring of Tilted Transmembrane Helical Peptides

   https://doi.org/10.3390/biom10020273  

   Afrose, Fahmida ; Koeppe II, Roger E. ( February 2020 , Biomolecules)

   Charged and aromatic amino acid residues, being enriched toward the terminals of membrane-spanning helices in membrane proteins, help to stabilize particular transmembrane orientations. Among them, histidine is aromatic and can be positively charge at low pH. To enable investigations of the underlying protein-lipid interactions, we have examined the effects of single or pairs of interfacial histidine residues using the constructive low-dynamic GWALP23 (acetyl-GG2ALW5LALALALALALALW19LAG22A-amide) peptide framework by incorporating individual or paired histidines at locations 2, 5, 19 or 22. Analysis of helix orientation by means of solid-state 2H NMR spectra of labeled alanine residues reveals marked differences with H2,22 compared tomore »W2,22. Nevertheless, the properties of membrane-spanning H2,22WALP23 helices show little pH dependence and are similar to those having Gly, Arg or Lys at positions 2 and 22. The presence of H5 or H19 influences the helix rotational preference but not the tilt magnitude. H5 affects the helical integrity, as residue 7 unwinds from the core helix; yet once again the helix orientation and dynamic properties show little sensitivity to pH. The overall results reveal that the detailed properties of transmembrane helices depend upon the precise locations of interfacial histidine residues.« less
5. Is there such a thing as a molecular organic alloy?

   https://doi.org/10.1039/c9mh01351b  

   Huang, Xinjing ; Liu, Xiao ; Ding, Kan ; Forrest, Stephen R. ( January 2020 , Materials Horizons)

   In inorganic materials, an alloy is a mixture of two or more substances that generally exhibits electronic and/or physical properties that differ from those of its constituents. In organic systems, the formation of a “molecular alloy” comprising mixtures of molecular organic materials has also been proposed. We test the validity of this concept via the study of the optoelectronic properties of a ternary system that has previously been identified to form a molecular acceptor alloy, namely a blend of a poly(3-hexylthiophene) (P3HT) donor, with two acceptors indene-C 60 bisadduct (ICBA) and phenyl-C 61 -butyric acid methyl ester (PC 61 BM)more »[R. A. Street, et al. , J. Am. Chem. Soc. , 2013, 135 , 986–989]. Using photoelectron spectroscopy, we find that the ICBA:PC 61 BM blend shows the same highest occupied molecular orbital and exciton energies as that of ICBA, indicating the absence of a new exciton state in the blend. Furthermore, charge transfer state spectra of ternary blends are found to comprise a simple linear superposition of the corresponding binaries. From these results, no evidence of new, emergent electronic states is found to support the existence of a molecular alloy in this system. To our knowledge there is as yet no clear evidence of the existence of an alloy in any organic semiconductor system. We discuss the criteria that should be met by a molecular organic alloy and procedures needed for their unambiguous identification.« less