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A cellulose graft copolymer (cellulose nanoresin) was synthesized by the all-aqueous functionalization of cellouronic acid with poly (vinyl benzyl trimethyl ammonium chloride) (poly(vbTMAC)). Cellulose was oxidized using the highly reported 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-mediated selective C-6 oxidation reaction. Fischer–Speier esterification of cellouronic acid was used to graft poly(vbTMAC) to the cellulosic backbone in a facile click-like mechanism. Synthesis of cellulose nanoresin was confirmed using dynamic light scattering and zeta potential measurements. Conductometric titration was used to determine the carboxylate content of cellouronic acid and the percent functionalization of the cellulose nanoresin, which was 1.69 ± 0.03 mmol/g and 61.2 ± 4%, respectively. Using a disodium fluorescein (NaFL) surrogate adsorbate, the maximum adsorption capacity of CNR was measured to be 26.8 ± 1.3 mg NaFL per gram of CNR with a Langmuir equilibrium binding constant of Ks = 10.5 ± 2 ppm−1. When examined as a thin film membrane, a breakthrough study of CNR showed that equilibrium loading was achieved in less than 30 s, and that > 90% of loading occurred in under 5 s. This data suggests that these films can be used as contact resins for anion-exchange water purification. We show in this work that these films maintain > 99% of loading performance over 40 trials of regeneration and reuse, meaning that these films are green and regenerable. Initial testing shows that CNR is effective at the removal of perfluorooctane sulfonate (PFOS) from water to below our limit of detection of 100 ppt. 

We present deep upper limits from the 2014 Murchison Widefield Array Phase I observing season, with a particular emphasis on identifying the spectral fingerprints of extremely faint radio frequency interference (RFI) contamination in the 21 cm power spectra (PS). After meticulous RFI excision involving a combination of theSSINSRFI flagger and a series of PS-based jackknife tests, our lowest upper limit on the Epoch of Reionization (EoR) 21 cm PS signal is Δ²≤ 1.61 × 10⁴mK²atk= 0.258h Mpc⁻¹at a redshift of 7.1 using 14.7 hr of data. By leveraging our understanding of how even fainter RFI is likely to contaminate the EoR PS, we are able to identify ultrafaint RFI signals in the cylindrical PS. Surprisingly this signature is most obvious in PS formed with less than 1 hr of data, but is potentially subdominant to other systematics in multiple-hour integrations. Since the total RFI budget in a PS detection is quite strict, this nontrivial integration behavior suggests a need to more realistically model coherently integrated ultrafaint RFI in PS measurements so that its potential contribution to a future detection can be diagnosed.

 

Nanomaterials have been extensively used in polymer nanocomposite membranes due to the inclusion of unique features that enhance water and wastewater treatment performance. Compared to the pristine membranes, the incorporation of nanomodifiers not only improves membrane performance (water permeability, salt rejection, contaminant removal, selectivity), but also the intrinsic properties (hydrophilicity, porosity, antifouling properties, antimicrobial properties, mechanical, thermal, and chemical stability) of these membranes. This review focuses on applications of different types of nanomaterials: zero-dimensional (metal/metal oxide nanoparticles), one-dimensional (carbon nanotubes), two-dimensional (graphene and associated structures), and three-dimensional (zeolites and associated frameworks) nanomaterials combined with polymers towards novel polymeric nanocomposites for water and wastewater treatment applications. This review will show that combinations of nanomaterials and polymers impart enhanced features into the pristine membrane; however, the underlying issues associated with the modification processes and environmental impact of these membranes are less obvious. This review also highlights the utility of computational methods toward understanding the structural and functional properties of the membranes. Here, we highlight the fabrication methods, advantages, challenges, environmental impact, and future scope of these advanced polymeric nanocomposite membrane based systems for water and wastewater treatment applications. 

The heterodimerization of wild-type (WT) Cu, Zn superoxide dismutase-1 (SOD1) and mutant SOD1 might be a critical step in the pathogenesis of SOD1-linked amyotrophic lateral sclerosis (ALS). Post-translational modifications that accelerate SOD1 heterodimerization remain unidentified. Here, we used capillary electrophoresis to quantify the effect of cysteine-111 oxidation on the rate and free energy of ALS mutant/WT SOD1 heterodimerization. The oxidation of Cys111-β-SH to sulfinic and sulfonic acid (by hydrogen peroxide) increased rates of heterodimerization (with unoxidized protein) by ∼3-fold. Cysteine oxidation drove the equilibrium free energy of SOD1 heterodimerization by up to ΔΔG = −5.11 ± 0.36 kJ mol–1. Molecular dynamics simulations suggested that this enhanced heterodimerization, between oxidized homodimers and unoxidized homodimers, was promoted by electrostatic repulsion between the two “dueling” Cys111-SO2–/SO3–, which point toward one another in the homodimeric state. Together, these results suggest that oxidation of Cys-111 promotes subunit exchange between oxidized homodimers and unoxidized homodimers, regardless of whether they are mutant or WT dimers. 

The photoluminescent eight-coordinate zirconium complex Zr( H PMP H ) 4 supported by four monoanionic 2-(2′-pyridine)pyrrolide ligands was synthesized. This molecule shows dual emission via fluorescence and phosphorescence with an overall quantum efficiency of 4% at room temperature in solution. The phosphorescence lifetime is dependent on concentration, indicating excimer formation at higher concentrations, and reaches almost 800 μs at high dilution. 

Abstract The electrostatic effects of protein crowding have not been systematically explored. Rather, protein crowding is generally studied with co‐solvents or crowders that are electrostatically neutral, with no methods to measure how the net charge ( Z ) of a crowder affects protein function. For example, can the activity of an enzyme be affected electrostatically by the net charge of its neighbor in crowded milieu? This paper reports a method for crowding proteins of different net charge to an enzyme via semi‐random chemical crosslinking. As a proof of concept, RNase A was crowded (at distances ≤ the Debye length) via crosslinking to different heme proteins with Z  = +8.50 ± 0.04, Z  = +6.39 ± 0.12, or Z  = −10.30 ± 1.32. Crosslinking did not disrupt the structure of proteins, according to amide H/D exchange, and did not inhibit RNase A activity. For RNase A, we found that the electrostatic environment of each crowded neighbor had significant effects on rates of RNA hydrolysis. Crowding with cationic cytochrome c led to increases in activity, while crowding with anionic “supercharged” cytochrome c or myoglobin diminished activity. Surprisingly, electrostatic crowding effects were amplified at high ionic strength ( I  = 0.201 M) and attenuated at low ionic strength ( I  = 0.011 M). This salt dependence might be caused by a unique set of electric double layers at the dimer interspace (maximum distance of 8 Å, which cannot accommodate four layers). This new method of crowding via crosslinking can be used to search for electrostatic effects in protein crowding. 

We use the Galaxy and Mass Assembly (GAMA) and the Deep Extragalactic Visible Legacy Survey (DEVILS) observational data sets to calculate the cosmic star formation rate (SFR) and active galactic nuclei (AGN) bolometric luminosity history (CSFH/CAGNH) over the last 12.5 billion years. SFRs and AGN bolometric luminosities were derived using the spectral energy distribution fitting code ProSpect, which includes an AGN prescription to self-consistently model the contribution from both AGN and stellar emission to the observed rest-frame ultra-violet to far-infrared photometry. We find that both the CSFH and CAGNH evolve similarly, rising in the early Universe up to a peak at look-back time ≈10 Gyr (z ≈ 2), before declining towards the present day. The key result of this work is that we find the ratio of CAGNH to CSFH has been flat ($\approx 10^{42.5}\, \mathrm{erg \, s^{-1}\, {\rm M}_{\odot }^{-1}\, yr}$) for 11 Gyr up to the present day, indicating that star formation and AGN activity have been coeval over this time period. We find that the stellar masses of the galaxies that contribute most to the CSFH and CAGNH are similar, implying a common cause, which is likely gas inflow. The depletion of the gas supply suppresses cosmic star formation and AGN activity equivalently to ensure that they have experienced similar declines over the last 10 Gyr. These results are an important milestone for reconciling the role of star formation and AGN activity in the life cycle of galaxies.

 

A series of boron, aluminum, gallium, and indium chelates containing the underexplored bis(phenolate) aza-dipyrromethene (aza-DIPY) core were prepared. These compounds were found to possess near-infrared absorption and emission profiles in the 710 to 770 nm domain and exhibit quantum yield values up to 14%. X-ray diffraction analysis revealed that heavier group 13 bis(phenolate) aza-DIPY chelates possessed octahedral geometries with either THF or pyridine groups occupying the axial positions as opposed to the tetrahedral geometry of the boron chelate. 

We use two independent galaxy-formation simulations, flares, a cosmological hydrodynamical simulation, and shark, a semi-analytic model, to explore how well the JWST will be able to uncover the existence and parameters of the star-forming main sequence (SFS) at z = 5 → 10, i.e. shape, scatter, normalization. Using two independent simulations allows us to isolate predictions (e.g. stellar mass, star formation rate, SFR, luminosity functions) that are robust to or highly dependent on the implementation of the physics of galaxy formation. Both simulations predict that JWST can observe ≥70–90 per cent (for shark and flares, respectively) of galaxies up to z ∼ 10 (down to stellar masses of ${\approx}10^{8.3}\rm M_{\odot }$ and SFRs of ${\approx}10^{0.5}{\rm M}_{\odot }\,{\rm yr}^{-1}$) in modest integration times and given current proposed survey areas (e.g. the Web COSMOS 0.6 deg2) to accurately constrain the parameters of the SFS. Although both simulations predict qualitatively similar distributions of stellar mass and SFR. There are important quantitative differences, such as the abundance of massive, star-forming galaxies with flares predicting a higher abundance than shark; the early onset of quenching as a result of black hole growth in flares (at z ≈ 8), not seen in shark until much lower redshifts; and the implementation of synthetic photometry with flares predicting more JWST-detected galaxies (∼90 per cent) than shark (∼70 per cent) at z = 10. JWST observations will distinguish between these models, leading to a significant improvement upon our understanding of the formation of the very first galaxies.