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Aqueous surfactant free emulsion grafting-through polymerization produced poly(methyl methacrylate) coated cellulose nanofibrils that retained microstructure and strengthened poly(lactic acid) composites.
The phase behavior of ternary blends composed of two homopolymers (A, B) and their corresponding diblock copolymer (A–B) has been widely studied, with emphasis on the volumetrically symmetric isopleth and the formation of bicontinuous microemulsions. However, almost all the previous studies employed linear polymers, and little is known about the impact of polymer architecture on the phase behavior of such ternary blends. Here, in this work, we report the self-assembly of three sets of ternary blends of polystyrene (PS) and poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA n ), with different lengths of oligo(ethylene glycol) side chains n. Small-angle X-ray scattering was used to probe the phase behavior at different compositions and temperatures. The order-to-disorder transition temperature was found to be impacted by the side chain length. It was also observed that longer side chains lead to poorer miscibility of homopolymers in the corresponding block, resulting in a more “dry-brush” like swelling behavior.
Nanosized polymeric vesicles (polymersomes) self-assembled from double hydrophilic copolymers of poly(3-methyl-N-vinylcaprolactam) n -b-poly(N-vinylpyrrolidone) m (PMVC n -b-PVPON m ) using all aqueous media are a promising platform for biomedical applications, because of their superior stability over liposomes in vivo and high loading capacity. Herein, we explored the temperature-sensitive behavior of PMVC 58 -b-PVPON 65 vesicles using transmission electron microscopy (TEM), dynamic light scattering (DLS), atomic force microscopy (AFM), and small-angle neutron scattering (SANS) in response to lowering the solution temperature from 37 to 25, 20, 14 and 4 °C. The copolymer vesicles with an average size of 350 nm at 37 °C were assembled from the diblock copolymer dissolved in aqueous solution at 4 °C. We show that while the polymersome's size gradually decreases upon the temperature decrease from 37 to 4 °C, the average shell thickness increases from 17 nm to 25 nm, respectively. SANS study revealed that the PMVC 58 -b-PVPON 65 vesicle undergoes a gradual structure evolution from a dense-shell vesicle at 37–25 °C to a highly-hydrated shell vesicle at 20–14 °C to molecular chain aggregates at 4 °C. From SANS contrast matching study, this vesicle behavior is found to be driven by the gradual rehydration of PMVC block at 37–14 °C. The shell hydration at 20–14 °C also correlated with the 4.4-fold decrease in the relative fluorescence intensity from vesicle-encapsulated fluorescent dye, indicating ~80% of the dye release within 12 hours after the vesicle exposure to 14 °C. No significant (<5%) dye release was observed for the vesicle solutions at 37–20 °C, indicating excellent cargo retention inside the vesicles. Our study provides new fundamental insights on temperature-sensitive polymer vesicles and demonstrates that the copolymer assembly into polymersomes can be achieved by decreasing a copolymer aqueous solution temperature below 14 °C followed by solution exposure to ≥20 °C. This type of all-aqueous assembly, instead of nanoprecipitation from organic solvents or solvent exchange, can be highly desirable for encapsulating a wide range of biological molecules, including proteins, peptides, and nucleic acids, into stable polymer vesicles without a need for organic solvents for dissolution of the copolymers that are amphiphilic at physiologically relevant temperatures of 20–37 °C.
Superhydrophobicity of MeMOFs, methylated analogues of FMOFs (CF 3 → CH 3 ) is predicted by GCMC simulations (high-RH CO 2 or CH 4 adsorption in MeMOFs > FMOFs) validated experimentally (H 2 O contact angle ∼172° for MeMOF@plastic dry-coated substrates).
Biobased reinforcements for poly(lactic acid) (PLA) are needed for more additive manufacturing applications requiring higher strength and sustainability. Flax nanofibrils (FNFs) produced through mechanical refining were explored as a lower energy alternative to cellulose nanofibril (CNF) reinforcements. To compatibilize the FNFs for the PLA matrix, a grafting-through surfactant free emulsion polymerization (SFEP) was performed to functionalize the FNF surface with poly(methyl methacrylate) (PMMA). FNFs produced using different refining energy were functionalized under varying solid contents in suspension. Polymerizations performed at 0.7 wt% FNFs in water yielded the highest degree of PMMA functionality. These optimal conditions were scaled up and the PMMA modified FNFs melt compounded into PLA yielding a 12% increase in tensile strength and 92% increase in the modulus of elasticity as compared to the original PLA. Interestingly, the FNFs with the lowest refining energy yielded the strongest composites using these methods, surpassing the higher refining energy CNF reinforcements. This increase was attributed to improved dispersion of the FNF reinforcements in the PLA matrix that was enabled by the PMMA coating on the FNF surface preventing interfibrillar adhesion and aggregation within the PLA matrix.
Room-temperature ionic liquids are promising candidates for applications ranging from electrolytes for energy storage devices to lubricants for food and cellulose processing to compounds for pharmaceutics, biotransformation, and biopreservation. Due to the ion complexity, many room-temperature ionic liquids readily form amorphous phases upon cooling, even at modest rates. Here, we investigate two commonly studied imidazolium-based room-temperature ionic liquids, 1-ethyl-3-methylimidazolium tetrafluoroborate and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, as well as their mixtures, to demonstrate how the complex interplay between the crystalline and amorphous phases is affected by the processing conditions, such as thermal history, liquid mixing, and applied pressure. We show that quantum tunneling in the cation methyl groups, measured by high-resolution inelastic neutron scattering, can be used to probe the order-disorder in room-temperature ionic liquids (crystalline vs amorphous state) that develops as a result of variable processing conditions.
Hydrocarbon polymers are used in a wide variety of practical applications. In the field of dynamic compression at extreme pressures, these polymers are used at several high energy density (HED) experimental facilities. One of the most common polymers is poly(methyl methacrylate) or PMMA, also called Plexiglass® or Lucite®. Here, we present high-fidelity, hundreds of GPa range experimental shock compression data measured on Sandia’s Z machine. We extend the principal shock Hugoniot for PMMA to more than threefold compression up to 650 GPa and re-shock Hugoniot states up to 1020 GPa in an off-Hugoniot regime, where experimental data are even sparser. These data can be used to put additional constraints on tabular equation of state (EOS) models. The present results provide clear evidence for the need to re-examine the existing tabular EOS models for PMMA above ~120 GPa as well as perhaps revisit EOSs of similar hydrocarbon polymers commonly used in HED experiments investigating dynamic compression, hydrodynamics, or inertial confinement fusion.
Methyl nitrite has two stable conformational isomers resulting from rotation about the primary C–O–N–O dihedral angle: cis-CH 3 ONO and trans-CH 3 ONO, with cis being more stable by ∼5 kJ/mol. Here, the barrier to rotational interconversion (∼45 kJ/mol) is too large for isomerization to occur under ambient conditions. This paper presents evidence of a change in conformer abundance when dilute CH 3 ONO is deposited onto a cold substrate; the relative population of the freshly deposited cis conformer is seen to increase compared to its gas-phase abundance, measured by in situ infrared spectroscopy. We observe abundance changes depending on the identity of the bath gas (N 2 , Ar, and Xe) and deposition angle. The observations indicate that the surface properties of the growing matrix influence conformer abundance—contrary to the widely held assumption that conformer abundance in matrices reflects gas-phase abundance. We posit that differences in the angle-dependent host-gas deposition dynamics affect the growing surfaces, causing changes in conformer abundances. Quantum chemistry calculations of the binding energies between CH 3 ONO and a single bath-gas component reveal that significant energetic stabilization is not observed in 1:1 complexes of N 2 :CH 3 ONO, Ar:CH 3 ONO, or Xe:CH 3 ONO. From our results, we conclude that the growing surface plays a significant role in trapping cis-CH 3 ONO more effectively than trans-CH 3 ONO, likely because cis-CH 3 ONO is more compact. Taken together, the observations highlight the necessity for careful characterization of conformers in matrix-isolated systems, emphasizing a need for further study into the deposition dynamics and surface structure of chemically inert matrices.
Here, the photoabsorption and photoionization dynamics of the I 4d and valence orbitals in methyl iodide have been studied both experimentally and theoretically. Synchrotron radiation has been employed to measure the total ion yield in the vicinity of the I 4d ionization thresholds. The observed structure, due to excitations into Rydberg or valence states, has been assigned using transition energies and relative intensities computed with time-dependent density functional theory within the Tamm–Dancoff approximation. Photoelectron spectra, recorded with plane polarized radiation in two polarization geometries, have allowed the effect of autoionization on the valence electron angular distributions to be investigated. The spectra obtained at photon energies of 50.62 and 52.34 eV, coinciding respectively with the I 4d 5/2 → σ* and 4d 3/2 → σ* transitions, reveal, in addition to valence shell photoelectron bands, features not associated with simple photoionization of the parent molecule. High resolution photoelectron spectra of the I 4d main-lines display structure resulting from spin–orbit coupling and molecular field splitting. The binding energies of the five states contributing to the (I 4d) -1 ionization have been determined. The iodine (in CH 3 I) N 45 VV Auger spectrum has been measured and the observed structure has been assigned using the core hole binding energies derived in the present work together with established ionization energies of the doubly charged ion. The experimentally determined Auger electron angular distributions have been discussed in relation to the theoretical angular distribution parameter characterizing the spatial alignment of molecular axes in the (I 4d) -1 state.
Abstract Ethyl formate (EF) was evaluated as a potential alternative to methyl bromide (MB) for phytosanitary treatment of imported citrus fruit in the Republic of Korea. Planococcus citri (Risso) (Hemiptera: Pseudococcidae), a mealybug with known tolerance against EF and MB, was used as a representative pest to test efficacy of the two fumigants against eggs. In nine commercial-scale refrigerated container (67.5 m3) trials using imported orange, lemon and grapefruit, EF applied at the currently approved dose for citrus (70 g·m-3 at 5°C for 4 h, developed for Aspidiotus excisus Green (Hemiptera: Diaspididae), a species less EF tolerant than P. citri) resulted in 76.9–98.3% mortality of P. citri eggs. The EF treatment did not affect the sugar content or the color of peel and pulp of the treated fruit. When oranges were treated according to the current MB (64 g·m-3 at >5°C for 2 h) or EF treatment guidelines, the concentration of fumigant around the fruit fluctuated between 9.4 and 185.1 ppm for EF and 9.5–203.0 ppm for MB during the 72-h post-fumigation processes (venting [0–2 h], transportation to storage [2–24 h], and storage periods [24–72 h]) with both EF and MB maintained between 10 and 100 ppm during the storage period. Considering the efficacy of EF, its apparent lack of phytotoxicity, and its more manageable threshold limit value for humans (100 ppm EF compared to 1 ppm MB for an 8-h time weighted average exposure), our results suggest that EF may be a promising alternative to MB for the phytosanitary treatment of imported citrus in Korea.
Summary Our work reveals the structure of the active state of Methyl-Coenzyme M Reductase (MCR), the key and rate-limiting enzyme in biological methane formation. We find large differences between the active Ni(I) and inactive Ni(II) proteins and provide insight into how nature makes and breaks the C-H bond of methane. The Ni(II)-F430 center in inactive MCR contains four planar nitrogen ligands, a lower axial glutamine oxo, and an upper axial thiolate. The Ni(I)-enzyme replaces the axial ligands with a single water. The one-electron redox change results in movement of the Ni ion and upward swing of the β-lactam ring in the tetrapyrrole coupled to a domino-like protein quake through second sphere residues, inter-subunit interactions, a substrate tunnel, affecting even the dimensions of the unit cell. These structural changes lead Ni(I)-MCR to release a charge clamp that, in the Ni(II) state, locks down substrate Coenzyme B. Determining the Ni(I)-MCR structure required development of rigorous anaerobic crystallographic techniques. Validation of the MCR redox state was accomplished by in-line and parallel spectroscopic and unit cell analyses. This structure has large implications for developing technologies to limit methane emissions and efficiently produce biofuels. Methodology described here will enhance structural biology for other oxygen-sensitive enzymes.
The crystal structure of methyl 2-acetamido-2-deoxy-β-D-glycopyranosyl-(1→4)-β-D-mannopyranoside monohydrate, C 15 H 27 NO 11 ·H 2 O, was determined and its structural properties compared to those in a set of mono- and disaccharides bearing N -acetyl side-chains in βGlcNAc aldohexopyranosyl rings. Valence bond angles and torsion angles in these side chains are relatively uniform, but C—N (amide) and C—O (carbonyl) bond lengths depend on the state of hydrogen bonding to the carbonyl O atom and N—H hydrogen. Relative to N -acetyl side chains devoid of hydrogen bonding, those in which the carbonyl O atom serves as a hydrogen-bond acceptor display elongated C—O and shortened C—N bonds. This behavior is reproduced by density functional theory (DFT) calculations, indicating that the relative contributions of amide resonance forms to experimental C—N and C—O bond lengths depend on the solvation state, leading to expectations that activation barriers to amide cis – trans isomerization will depend on the polarity of the environment. DFT calculations also revealed useful predictive information on the dependencies of inter-residue hydrogen bonding and some bond angles in or proximal to β-(1→4) O -glycosidic linkages on linkage torsion angles φ and ψ. Hypersurfaces correlating φ and ψ with the linkage C—O—C bond angle and total energy are sufficiently similar to render the former a proxy of the latter.
Rev1 has two important functions in the translesion synthesis pathway, including dCMP transferase activity, and acts as a scaffolding protein for other polymerases involved in translesion synthesis. However, the role of Rev1 in mutagenesis and tumorigenesis in vivo remains unclear. We previously generated Rev1-overexpressing (Rev1-Tg) mice and reported that they exhibited a significantly increased incidence of intestinal adenoma and thymic lymphoma (TL) after N-methyl-N-nitrosourea (MNU) treatment. In this study, we investigated mutagenesis of MNU-induced TL tumorigenesis in wild-type (WT) and Rev1-Tg mice using diverse approaches, including whole-exome sequencing (WES). In Rev1-Tg TLs, the mutation frequency was higher than that in WT TL in most cases. However, no difference in the number of nonsynonymous mutations in the Catalogue of Somatic Mutations in Cancer (COSMIC) genes was observed, and mutations involved in Notch1 and MAPK signaling were similarly detected in both TLs. Mutational signature analysis of WT and Rev1-Tg TLs revealed cosine similarity with COSMIC mutational SBS5 (aging-related) and SBS11 (alkylation-related). Interestingly, the total number of mutations, but not the genotypes of WT and Rev1-Tg, was positively correlated with the relative contribution of SBS5 in individual TLs, suggesting that genetic instability could be accelerated in Rev1-Tg TLs. Finally, we demonstrated that preleukemic cells could be detected earlier in Rev1-Tg mice than in WT mice, following MNU treatment. In conclusion, Rev1 overexpression accelerates mutagenesis and increases the incidence of MNU-induced TL by shortening the latency period, which may be associated with more frequent DNA damage-induced genetic instability.
Desulfobulbus oligotrophicus Prop6 is a sulfate-reducing, propionate-oxidizing Deltabacterota (formerly Deltaproteobacteria) strain from sewage sludge. Desulfobulbus species are found in anoxic environments, in animal microbiota, and some produce the neurotoxin methylmercury. The 3.1-Mbp D. oligotrophicus genome sequence enables studies of diverse environmental adaptations and the evolutionary genomics of mercury methylation mechanisms.
The G-quadruplex (GQ) is a well-studied non-canonical DNA structure formed by G-rich sequences found at telomeres and gene promoters. Biological studies suggest that GQs may play roles in regulating gene expression, DNA replication, and DNA repair. Small molecule ligands were shown to alter GQ structure and stability and thereby serve as novel therapies, particularly against cancer. In this work, we investigate the interaction of a G-rich sequence, 5’-GGGTTGGGTTGGGTTGGG-3’ (T1), with a water-soluble porphyrin, N- methyl mesoporphyrin IX (NMM) via biophysical and X-ray crystallographic studies. UV-vis and fluorescence titrations, as well as a Job plot, revealed a 1:1 binding stoichiometry with an impressively tight binding constant of 30–50 μM -1 and ΔG 298 of -10.3 kcal/mol. Eight extended variants of T1 (named T2 –T9) were fully characterized and T7 was identified as a suitable candidate for crystallographic studies. We solved the crystal structures of the T1- and T7-NMM complexes at 2.39 and 2.34 Å resolution, respectively. Both complexes form a 5’-5’ dimer of parallel GQs capped by NMM at the 3’ G-quartet, supporting the 1:1 binding stoichiometry. Our work provides invaluable details about GQ-ligand binding interactions and informs the design of novel anticancer drugs that selectively recognize specific GQs and modulate their stability for therapeutic purposes.
Thirdhand smoke (THS) is a newly described health hazard composed of toxicants, mutagens and carcinogens, including nicotine-derived tobacco specific nitrosamines (TSNAs), one of which is 1-(N-methyl-N-nitrosamino)-1-(3-pyridinyl)-4-butanal (NNA). Although TSNAs are generally potent carcinogens, the risk of NNA, which is specific to THS, is poorly understood. We recently reported that THS exposure-induced adverse impact on DNA replication and transcription with implications in the development of cancer and other diseases. Here, we investigated the role of NNA in THS exposure-induced harmful effects on fundamental cellular processes. We exposed cultured human lung epithelial BEAS-2B cells to NNA. The formation of DNA base damages was assessed by Long Amplicon QPCR (LA-QPCR); DNA double-strand breaks (DSBs) and NNA effects on replication and transcription by immunofluorescence (IF); and genomic instability by micronuclei (MN) formation. We found increased accumulation of oxidative DNA damage and DSBs as well as activation of DNA damage response pathway, after exposure of cells to NNA. Impaired S phase progression was also evident. Consistent with these results, we found increased MN formation, a marker of genomic instability, in NNA-exposed cells. Furthermore, ongoing RNA synthesis was significantly reduced by NNA exposure, however, RNA synthesis resumed fully after a 24h recovery period only in wild-type cells but not in those deficient in transcription-coupled nucleotide excision repair (TC-NER). Importantly, these cellular effects are common with the THS-exposure induced effects. Our findings suggest that NNA in THS could be a contributing factor for THS exposure-induced adverse health effect.
This report describes the chemical separations used to measure the amount and chemical form of mercury in Hanford tank waste and provides the technical basis and recommendations for transferring and implementing this new ultra-trace mercury analytical technique at Hanford’s 222-S Laboratory. In the Hanford tank waste, mercury can exist as either elemental, inorganic, or organic mercury species. Of key interest is understanding the quantification and speciation of total (elemental + inorganic + organic), elemental, and organic (assumed to be only methyl mercury) mercury. The tanks may also have other organic mercury species, but their direct measurement is outside the scope of this report.
Crystal structure of KRED F147L/L153Q/Y190P/L199A/M205F/M206F variant and methyl methacrylate complex