Hydrazide- and Diazole-Linked Covalent Organic Frameworks and Their Water Harvesting Properties

We report a retrosynthetic strategy and its implementation to making covalent organic frameworks (COFs) with irreversible hydrazide and diazole (oxadiazole and thiadiozole) linkages. This involved the synthesis of a series of 2D and 3D hydrazine-linked frameworks, followed by their oxidation and dehydrative cyclization. Each linkage synthesis and functional group transformation—hydrazine, hydrazide, oxadiazole, and thiadia-zole—was evidenced by 15N multi-CP-MAS NMR. In addition, the isothermal water uptake profiles of these frameworks were studied, leading to the discovery that one hydrazide-linked COF is suitable for water harvest-ing from air in arid conditions. These COFs displayed characteristic S-shaped water sorption profiles, a steep pore-filling step below 18% relative humidity at 25 °C, and a total uptake capacity of 0.45 g g–1 at P/Psat = 0.95. In addition, a total of ten 2D and 3D structures with various such linkages were studies for their affinity to water. We found that even small changes made on the molecular level can lead to major differences in the water isotherm profiles and therefore pointing to the utility of water sorption analysis as a complementary analytical tool to study linkage transformations.

Rice Bran-Based Bioplastics: Effects of Biopolymer Fractions on Their Mechanical, Functional and Microstructural Properties

Rice bran is an underutilized by-product of rice production, containing proteins, lipids and carbohydrates (mainly starches). Proteins and starches have been previously used to produce rice bran-based bioplastics, providing a high-added-value by-product, while contributing to the development of biobased, biodegradable bioplastics. However, rice bran contains oil (18–22%), which can have a detrimental effect on bioplastic properties. Its extraction could be convenient, since rice bran oil is becoming increasingly attractive due to its variety of applications in the food, pharmacy and cosmetic industries. In this way, the aim of this work was to analyze the effect of the different components of rice bran on the final properties of the bioplastics. Rice bran refining was carried out by extracting the oil and fiber fractions, and the effects of these two procedures on the final properties were addressed with mechanical, functional and microstructural measures. Results revealed that defatted rice bran produced bioplastics with higher viscoelastic moduli and better tensile behavior while decreasing the water uptake capacity and the soluble matter loss of the samples. However, no significant improvements were observed for systems produced from fiber-free rice bran. The microstructures observed in the SEM micrographs matched the obtained results, supporting the conclusions drawn.

Cobalt–Carbon Nanoparticles with Silica Support for Uptake of Cationic and Anionic Dyes from Polluted Water

Silica-supported hierarchical graphitic carbon sheltering cobalt nanoparticles Co-HGC@SiO2 (1) were prepared by pyrolysis at 850 °C of [Co(phen)(H2O)4]SO4.2H2O complex with silica in the presence of pyrene as a carbon source under nitrogen atmosphere. Nanocomposites (2) and (3) were obtained by acid treatment of (1) with HCl and HF acid, respectively. The nanocomposites showed rough hierarchical carbon microstructures over silica support decorated with irregular cobalt nanospheres and nanorods 50 to 200 nm in diameter. The nanoparticles consist of graphitic shells and cobalt cores. SEM, EDAX and TEM elemental mapping indicate a noticeable loss of cobalt in the case of (2) and loss of cobalt and silica in the case of (3) with an increase in porosity. Nanocomposite (3) showed the highest BET surface area 217.5 m2g−1. Raman spectrum shows defect D-band and graphitic G-band as expected in carbon nanostructures. PXRD reveals the presence of cobalt(0) nanoparticles. XPS indicates the presence of Co(II) oxides and the successful doping of nitrogen in the nanocomposites. Moreover, TEM elemental mapping provides information about the abundance of Si, Co, C, N and S elements in zones. Nanocomposite (1) showed maximum uptake capacity of 192.3 and 224.5 mg/g for crystal violet CV and methyl orange MO dyes, respectively. Nanocomposite (2) showed a capacity of 94.1 and 225.5 mg/g for CV and MO dyes, respectively. Nanocomposite (4) obtained after treatment of (1) with crystal violet proved successful adsorption of CV. Co-HGC (5) prepared without addition of silica has a capacity for CV equal to 192 mg/g, while it is 769.2 mg/g with MO. Electrostatics and π–π interactions of graphite and cobalt species in the nanocomposites with aromatic rings of cationic and anionic dyes are responsible for the adsorption. Yan et al. was the best model to describe column kinetics. The thomas column adsorption model showed that the maximum uptake capacity of (1) was 44.42 mg/g for CV and 32.62 mg/g for MO. for a column packed with 0.5 gm of (1) and dye concentration of 100 mg/L at a flow rate of 1 mL/min. The column was recycled three times with no noticeable clogging or degradation of nanocomposites. Thus, Co-HGC@SiO2 adsorbents can be used efficiently to treat water contaminated with cationic and anionic dyes.

Preparation and Characterization of Super-Absorbing Gel Formulated from κ-Carrageenan–Potato Peel Starch Blended Polymers

κ-carrageenan is useful for its superior gelling, hydrogel, and thickening properties. The purpose of the study was to maximize the hydrogel properties and water-absorbing capacity of κ-carrageenan by blending it with starch from potato peels to be used as safe and biodegradable water-absorbent children’s toys. The prepared materials were analyzed using FTIR and Raman spectroscopy to analyze the functional groups. Results showed that there was a shift in the characteristic peaks of starch and κ-carrageenan, which indicated their proper reaction during blend formation. In addition, samples show a peak at 1220 cm−1 corresponding to the ester sulfate groups, and at 1670 cm−1 due to the carbonyl group contained in D-galactose. SEM micrographs showed the presence of rough surface topology after blending the two polymers, with the appearance of small pores. In addition, the presence of surface cracks indicates the biodegradability of the prepared membranes that would result after enzymatic treatment. These results are supported by surface roughness results that show the surface of the κ-carrageenan/starch membranes became rougher after enzymatic treatment. The hydrophilicity of the prepared membranes was evaluated from contact angle (CA) measurements and the swelling ratio. The swelling ratio of the prepared membranes increased gradually as the starch ratio increased, reaching 150%, while the water-uptake capacity increased from 48 ± 4% for plain κ-carrageenan to 150 ± 5% for 1:2 κ-carrageenan/starch blends. The amylase enzyme showed an effective ability to degrade both the plain κ-carrageenan and κ-carrageenan/starch membranes, and release glucose units for up to 236 and 563, respectively. According to these results, these blends could be effectively used in making safe and biodegradable molded toys with superior water-absorbing capabilities.

Functional roles of multiple Ton complex genes in a Sphingobium degrader of lignin-derived aromatic compounds

TonB-dependent transporters (TBDTs) mediate outer membrane transport of nutrients using the energy derived from proton motive force transmitted from the TonB–ExbB–ExbD complex localized in the inner membrane. Recently, we discovered ddvT encoding a TBDT responsible for the uptake of a 5,5-type lignin-derived dimer in Sphingobium sp. strain SYK-6. Furthermore, overexpression of ddvT in an SYK-6-derivative strain enhanced its uptake capacity, improving the rate of platform chemical production. Thus, understanding the uptake system of lignin-derived aromatics is fundamental for microbial conversion-based lignin valorization. Here we examined whether multiple tonB-, exbB-, and exbD-like genes in SYK-6 contribute to the outer membrane transport of lignin-derived aromatics. The disruption of tonB2–6 and exbB3 did not reduce the capacity of SYK-6 to convert or grow on lignin-derived aromatics. In contrast, the introduction of the tonB1–exbB1–exbD1–exbD2 operon genes into SYK-6, which could not be disrupted, promoted the conversion of β-O-4-, β-5-, β-1-, β-β-, and 5,5-type dimers and monomers, such as ferulate, vanillate, syringate, and protocatechuate. These results suggest that TonB-dependent uptake involving the tonB1 operon genes is responsible for the outer membrane transport of the above aromatics. Additionally, exbB2/tolQ and exbD3/tolR were suggested to constitute the Tol-Pal system that maintains the outer membrane integrity.

Accelerated Discovery of CH4 Uptake Capacity MOFs using Bayesian Optimization

High-throughput computational studies for discovery of metal-organic frameworks (MOFs) for separations and storage applications are often limited by the costs of computing thermodynamic quantities, with recent studies reliant ab initio results for a narrow selection of MOFs and empirical force-field methods for larger selections. Here, we conduct a proof-of-concept study using Bayesian optimization on CH4 uptake capacity of hypothetical MOFs for an existing dataset (Wilmer et al, Nature Chem. 2012, 4, 83). We show that less than 0.1% of the database needs to be screened with our Bayesian optimization approach to recover the top candidate MOFs. This opens the possibility of efficient screening of MOF databases using accurate ab-initio calculations for future adsorption studies on a minimal subset of MOFs. Furthermore, Bayesian optimization and the surrogate model presented here can offer interpretable material design insights and our framework will be applicable in the context of other target properties.

Periphytic Algae and Cyanobacteria from the Rio Doce Basin Respond Differently to Metals and Salinity, Showing Different Potential for Bioremediation

We have studied the isolated and combined effects of metals (Fe and Mn) and NaCl the on growth, physiology, and metal-uptake capacity of two photosynthetic periphytic species—Synechococcus elongatus (Cyanobacteria) and Chlorococcum infusionum (Chlorophyta)—isolated from an impacted area of the Rio Doce River (Brazil) after the Fundão dam collapse. The effective concentrations found to reduce 10 and 50% growth were 15.2 and 31.6 mg Fe l−1, and 2.5 and 7.9 mg Mn l−1 for S. elongatus and 53.9 and 61.6 mg Fe l−1, and 53.2 and 60.9 mg Mn l−1 for C. infusionum. Although the metal toxicity was related to oxidative stress, both species showed activation of antioxidant systems under phytotoxic concentrations of Fe and Mn. By binding large concentrations of metals on its cell surface and thus avoiding their entrance into the cells, C. infusionum presents greater resistance to Fe and Mn than S. elongatus. Under environmental realistic concentrations of Fe and Mn in river water from the Rio Doce Basin, S. elongatus and C. infusionum showed a metal removal efficiency of 42 and 65% and 53 and 79%, respectively after 96 h. These species were insensitive to increased NaCl concentrations which, in addition, did not disrupt the metal removal capacity of the species. Due to their salt and metal tolerance, S. elongatus and C. infusionum can be used for the remediation of waters contaminated with Fe and Mn.