Chemically Cross-Linked Graphene Oxide as a Selective Layer on Electrospun Polyvinyl Alcohol Nanofiber Membrane for Nanofiltration Application

Graphene oxide (GO) nanosheets were utilized as a selective layer on a highly porous polyvinyl alcohol (PVA) nanofiber support via a pressure-assisted self-assembly technique to synthesize composite nanofiltration membranes. The GO layer was rendered stable by cross-linking the nanosheets (GO-to-GO) and by linking them onto the support surface (GO-to-PVA) using glutaraldehyde (GA). The amounts of GO and GA deposited on the PVA substrate were varied to determine the optimum nanofiltration membrane both in terms of water flux and salt rejection performances. The successful GA cross-linking of GO interlayers and GO-PVA via acetalization was confirmed by FTIR and XPS analyses, which corroborated with other characterization results from contact angle and zeta potential measurements. Morphologies of the most effective membrane (CGOPVA-50) featured a defect-free GA cross-linked GO layer with a thickness of ~67 nm. The best solute rejections of the CGOPVA-50 membrane were 91.01% for Na2SO4 (20 mM), 98.12% for Eosin Y (10 mg/L), 76.92% for Methylene blue (10 mg/L), and 49.62% for NaCl (20 mM). These findings may provide one of the promising approaches in synthesizing mechanically stable GO-based thin-film composite membranes that are effective for solute separation via nanofiltration

Draft genome sequence of newly isolated agarolytic bacteria cellulophaga omnivescoria sp. nov. W5C carrying several gene loci for marine polysaccharide degradation

The continued research in the isolation of novel bacterial strains is inspired by the fact that native microorganisms possess certain desired phenotypes necessary for recombinant microorganisms in the biotech industry. Most studies have focused on the isolation and characterization of strains from marine ecosystems as they present a higher microbial diversity than other sources. In this study, a marine bacterium, W5C, was isolated from red seaweed collected from Yeosu, South Korea. The isolate can utilize several natural polysaccharides such as agar, alginate, carrageenan, and chitin. Genome sequence and comparative genomics analyses suggest that strain W5C belongs to a novel species of the Cellulophaga genus, from which the name Cellulophaga omnivescoria sp. nov. is proposed. Its genome harbors 3,083 coding sequences and 146 carbohydrate-active enzymes (CAZymes). Compared to other reported Cellulophaga species, the genome of W5C contained a higher proportion of CAZymes (4.7%). Polysaccharide utilization loci (PUL) for agar, alginate, and carrageenan were identified in the genome, along with other several putative PULs. These PULs are excellent sources for discovering novel hydrolytic enzymes and pathways with unique characteristics required for biorefinery applications, particularly in the utilization of marine renewable biomass. The type strain is JCM 32108T (= KCTC 13157BPT). © 2018, Springer Science+Business Media, LLC, part of Springer Nature

Recyclable composite nanofiber adsorbent for Li+ recovery from seawater desalination retentate

Composite poly(acrylonitrile) (PAN) nanofibers with H1.6Mn1.6O4 (HMO) lithium ion-sieves were prepared, characterized and tested for lithium ion (Li+) recovery. Nanofibers were prepared by electrospinning 10wt% HMO/PAN dope solutions in dimethylformamide with varied HMO loadings. Characterizations performed via XRD, SEM-EDS, capillary flow porometry and mechanical testing revealed highly porous, mechanically and chemically stable composite nanofibers with high water absorption capacity. The similar nanofiber diameters (\u3c300nm) and HMO particle sizes (\u3c100nm) rendered PAN as a binder to have minimal hindrance to the HMOs. Exposure of HMOs on the fiber surface provided good accessibility to the Li+ source, as indicated by the minimal loss of Li+ adsorption capacity of HMOs in PAN as compared to the support-free powdered HMO. All tested adsorbents followed Langmuir-type Li+ adsorption (qm). Increased HMO loadings resulted in improved adsorption performance as more HMOs were exposed on fiber surface and became less affected by the binder; the highest qm=10.3mg/g obtained from 60wt% HMO/PAN was only 4% lower than the support-free HMO. Adsorption loss after ten reuses was minor (\u3c4%), which suggests the long-term stability of HMO/PAN. In seawater desalination retentate, HMO/PAN (60wt%) preferentially adsorbed Li+ over other cations, achieving 99-5312 Li+ separation factors and high Li+ distribution coefficient (KD=770). Li+ was concentrated up to 486 times while interfering cations were enriched only up to \u3c7 times. Overall results demonstrate the potential use and recyclability of the developed HMO/PAN composite nanofiber for Li+ recovery from seawater or other prospective sources. © 2014 Elsevier B.V

Liquid-liquid extraction of lithium using lipophilic dibenzo-14-crown-4 ether carboxylic acid in hydrophobic room temperature ionic liquid

A green liquid-liquid extraction (LLE) system was developed for the recovery of lithium (Li+) from sodium and potassium ions, which are typically present at high concentrations in seawater. Dibenzo-14-crown-4ether (DB14C4) was functionalized with a long lipophilic alkyl C18 chain and a pendent proton ionizable carboxylic acid group to obtain a lithium (Li+) carrier system (DB14C4-C18-COOH) with high Li+ extraction performance and good stability in the room temperature ionic liquid diluent, CYPHOSIL 109. The Li+ extraction efficiency of DB14C4-C18-COOH/CYPHOSIL 109 can be enhanced by increasing the solution pH and DB14C4-C18-COOH concentration. Further examination of extraction results reveal 1:1 coordination between DB14C4-C18-COOH and Li+ which was also supported by density functional theory calculations. At room temperature, the developed LLE system effectively extracted dilute Li+ from Na+ (selectivity alpha(++)(Li)(/Na) = 1954) and K+ (alpha K-++(Li)/ = 138). Kinetic and thermodynamic parameters were evaluated for optimum Li+ extraction conditions. Sequestered Li+ can be easily recovered from the LLE system using dilute hydrochloric acid. Results from recycling tests showed stable Li+ extraction performance hence it can be used for long term application. Overall results indicate the potential application of DB14C4-C18-COOH/CYPHOSIL 109 as a treatment step to recover Li+ from brine or seawater. (C) 2016 Elsevier B.V. All rights reserved. A green liquid-liquid extraction (LLE) system was developed for the recovery of lithium (Li+) from sodium and potassium ions, which are typically present at high concentrations in seawater. Dibenzo-14-crown-4ether (DB14C4) was functionalized with a long lipophilic alkyl C18 chain and a pendent proton ionizable carboxylic acid group to obtain a lithium (Li+) carrier system (DB14C4-C18-COOH) with high Li+ extraction performance and good stability in the room temperature ionic liquid diluent, CYPHOSIL 109. The Li+ extraction efficiency of DB14C4-C18-COOH/CYPHOSIL 109 can be enhanced by increasing the solution pH and DB14C4-C18-COOH concentration. Further examination of extraction results reveal 1:1 coordination between DB14C4-C18-COOH and Li+ which was also supported by density functional theory calculations. At room temperature, the developed LLE system effectively extracted dilute Li+ from Na+ (selectivity alpha(++)(Li)(/Na) = 1954) and K+ (alpha K-++(Li)/ = 138). Kinetic and thermodynamic parameters were evaluated for optimum Li+ extraction conditions. Sequestered Li+ can be easily recovered from the LLE system using dilute hydrochloric acid. Results from recycling tests showed stable Li+ extraction performance hence it can be used for long term application. Overall results indicate the potential application of DB14C4-C18-COOH/CYPHOSIL 109 as a treatment step to recover Li+ from brine or seawater. (C) 2016 Elsevier B.V. All rights reserved.11Nsciescopu

Aerosol Cross-Linked Crown Ether Diols Melded with Poly(vinyl alcohol) as Specialized Microfibrous Li+ Adsorbents

Crown ether (CE)-based Li+ adsorbent micro fibers (MFs) were successfully fabricated through a combined use of CE diols, electrospinning, and aerosol cross-linking. The 14- to 16-membered CEs, with varied ring subunits and cavity dimensions, have two hydroxyl groups for covalent attachments to poly(vinyl alcohol) (PVA) as the chosen matrix. The CE diols were blended with PVA and transformed into microfibers via electrospinning, a highly effective technique in minimizing CE loss during MF fabrication. Subsequent aerosol glutaraldehyde (GA) cross-linking of the electrospun CE/PVA MFs stabilized the adsorbents in water. The aerosol technique is highly effective in cross-linking the MFs at short time (5 h) with minimal volume requirement of GA solution (2.4 mL g(-1) MF). GA cross-linking alleviated CE leakage from the fibers as the CEs were securely attached with PVA through covalent CE GA PVA linkages. Three types of CE/PVA MFs were fabricated and characterized through Fourier transform infrared-attenuated total reflection, C-13 cross-polarization magic angle spinning NMR, field emission scanning electron microscope, N-2 adsorption/desorption, and universal testing machine. The MFs exhibited pseudo-second-order rate and Langmuir-type Li+ adsorption. At their saturated states, the MFs were able to use 90-99% CEs for 1:1 Li+ complexation, suggesting favorability of their microfibrous structures for CE accessibility to Lit. The MFs were highly Li+ selective in seawater. Neopentyl-bearing CE was most effective in blocking larger monovalents Na+ and K+, whereas the dibenzo CE was best in discriminating divalents Mg2+ and Ca2+. Experimental selectivity trends concur with the reaction enthalpies from density functional theory calculations, confirming the influence of CE structures and cavity dimensions in their "size-match" Li+ selectivity.11Nsciescopu

Design of lithium selective crown ethers: Synthesis, extraction and theoretical binding studies

Lithium-selective (Li+) di-hydroxy crown ethers (CEs 3a-3h) were efficiently synthesized via intermolecular cyclization of bulky bis-epoxide with 1,2-dihydroxybenzene. Bis-epoxides were produced by etherifying allyl bromides with bulky diols to afford diene intermediates, which were subsequently epoxidized. Optimized cyclization reactions were established by changing the solvent, catalyst, and reaction temperature. Complexation abilities of CEs 3a-3h with Li+ and other alkali metals (Na+, K+, Cs+) were assessed by liquid-liquid extraction in dichloromethane-water system. Among the CEs, the highest Li+/Na+ selectivities were obtained from 3d (alpha(Li/Na) = 2519) and 3e (alpha(Li/Na) = 1768). DFT calculations reveal that 3d (1.28-1.37 angstrom) and 3e (1.23-1.38 angstrom) had the closest cavity sizes with Li+ diameter (1.36 angstrom). This result affirms that the size-match selectivity of CEs with Li+ was due to the presence of bulky tetramethyl (3d) or bicyclopentyl (3e) subunits with the rigid benzo groups. Complexation with larger cations like Na+, K+ and Cs+ greatly distorted the 3d and 3e rings as indicated by the larger O-M+ distances on their bulky sides than on their benzo sides. Thus, their (3d, 3e) superior selectivities were due to their Li+ preference and unstable complexation with larger M+. Enthalpy exchange reaction mechanisms reveal the tendency of all CEs to form 2:1 CE-M+ complexes with larger cations except for 3d, which mainly forms 1:1 CE-M+ hence it is considered most suitable for Li+. The efficient synthesis of di-hydroxy CEs widens their application not only as extractants but also as solid-supported Li+ adsorbents given the amenability of their OH- groups to further functionalization. (C) 2017 Elsevier B.V. All rights reserved.11Nsciescopu

Multidentate thia-crown ethers as hyper-crosslinked macroporous adsorbent resins for the efficient Pd/Pt recovery and separation from highly acidic spent automotive catalyst leachate

Multidentate thia-crown ether (CE) diols containing different number of sulfur heteroatoms (2S-4S) were developed as ligands for Pd and Pt. Seven thia-CE diols (denoted as: 2g-2m) were synthesized at 63–93% yields through ring-opening cyclization of bis-epoxide intermediates with 1,2-benzenedithiol. Each thia-CE contains 2 –OH groups as reactive sites for adsorbent fabrication. Initial screening of thia-CE diols through liquid–liquid extraction and density functional theory (DFT) calculations reveal that bidentate (2S, 2O) dithia-CE diol 2i with cavity size Ø2i = 1.61 Å is most selective towards Pd (ØPd2+=1.56 Å) and tetradentate (4S) tetrathia-CE diol 2m (Ø2m = 1.57 Å) to Pt (ØPt2+=1.48 Å). DFT calculations indicate that size-match relationship and denticity difference dictated the coordination stability of 2i with Pd and 2m with Pt, which ultimately defined their respective selectivities. Thia-CEs 2i and 2m were subsequently fabricated as macroporous adsorbent resins (2i-X and 2m-X) via crosslinking of their bis-epoxide derivatives with ethylenediamine in porogenic PEG 400 solvent. Metal ion uptakes were Langmuir-type with high capacities (2i-X: QPd = 212 mg g−1; 2m-X: QPt = 345 mg g−1) and kinetic rates follow the pseudo-second order rate model. Metal ion uptakes are mainly due to neutral coordination with the thia-CEs (84–86%) and to some extent, due to anion complexation with ammonium groups (14–16%). Recovery of Pd by 2i-X and Pt by 2m-X can be carried out effectively and repeatedly in highly acidic feed (6 M HCl) without performance deterioration. Sequential adsorption of Pd by 2i-X and Pt by 2m-X are highly selective in the presence of base metal ions (Mg2+, Al3+, Cr3+, Mn2+, Fe3+, Ni2+, and Pb2+) making these resins ideal for the treatment of highly acidic spent auto-catalyst leachate.11Nsciescopu

Substrate consumption, isoprene and biomass productions from different feeding modules^a.

a<p>Module 1, 2 and 3 used 10 g L⁻¹ glucose as substrate; module 4 and 5 used 10 g L⁻¹ D-xylose as substrate. Data reported were average values of duplicate cultivation runs.</p

Four glycolytic pathways present in <i>E. coli</i>.

<p>EMP, Embden-Meyerhof pathway; PPP, pentose phosphate pathway; EDP, Entner-Doudoroff pathway.</p

Pyruvate and G3P generation, energy and reducing equivalents production of different glycolytic pathways.

<p>Pyruvate and G3P generation, energy and reducing equivalents production of different glycolytic pathways.</p