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Capacitive deionization (CDI), an emerging method to eliminate ions from water at a low cost, has garnered significant interest in recent years. This study evaluates the implication of cation exchange resin loading on the membrane via the nonsolvent-induced phase inversion method. After determining the quantity of resins efficiently loaded on the membrane, it was subsequently utilized as a cation exchange membrane in the membrane capacitive deionization (MCDI) unit to examine the performance removal of Ni2+. The results show that the amount of resins influenced the membrane structure and significantly improved the efficiency of Ni2+ removal. The sulfonic acid group show a strong intensity directly proportional to the quantity of resins based on the FTIR measurement. In conjunction with the enhanced resin amount, ion exchange capacity and water content were increased. Simultaneously, there was an observed elevation in the water contact angle and the roughness of the membrane surface with increased resin amount. In the MCDI unit, membrane M20 (20% by weight resin) was employed to elucidate its roles in the CDI unit, encompassing an examination of various concentrations and flow rates, with Ni2+ utilized as a test contaminant. The results demonstrated that using membrane M20 in the MCDI (MCDI-M20) unit consistently exhibited higher adsorption levels than the CDI unit, reaching 19.80 mg g-1 ACC in the MCDI-M20 unit, while CDI unit achieved 10.27 mg g-1 ACC at 200 mg L-1 Ni2+ concentration and a flow rate of 10 mL min-1 at 1.2 V. Additionally, Ni2+ concentrations and flow rates in CDI system had an evident impact on the duration of adsorption due to the mechanisms of ions transport on the membrane. This study suggests that employing the prepared membrane in the MCDI unit enhanced the removal of Ni2+ from the solution, contributing to sustainable development goals.

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Understanding mercury (Hg) species existing after electrokinetic remediation (EK) for marine-sediment remediation is limited. Herein, the Hg fraction removal of EK from contaminated marine sediment was investigated appertaining to bipolar electrode settings along with the effects of electrode spacing and configuration considered. Based on the selective sequential Hg extractions (Hg SSE), much of the Hg in the sediment originated from F5 (i.e., HgS) and F4 (i.e., HgO). The F5 fraction removed by EK was about 30 %, while the F4 fraction had a slight increase of about 34 %. When it comes to electrode configuration, a hexagonal pattern has a higher Hg removal performance than that of a rectangular shape. The addition of anodes increases the remediation surface area, thus allowing superior Hg removal. This study indicates that the electrode spacing significantly affects the mercury removal and the remediation time. Determining suitable spacing enhances the electrical potentials in the migration flux.

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Electrokinetic remediation (EK) is a promising in-situ technique for removing mercury (Hg) from contaminated sites; yet it demands long operational periods when conventional electrodes are used. Herein, we investigate the effectiveness of lab-prepared cathodes (Cu foam coated with reduced graphene oxide (rGO) or manganese oxide (MnO2)) to enhance Hg removal rates from sediment by EK. Although short term (2 h) Hg removal rates were insignificantly different (p-value > 0.05) when using the uncoated and coated Cu foam cathodes, long term (60 h) operations saw greater Hg removal by coated Cu foam cathodes over pure Cu foam, probably owing to the time required for Hg to migrate towards the electrodes from sediment. The highest Hg removal at the cathode was achieved when an αMnO2-coated Cu foam cathode was used with a strong-base anion exchange membrane (AEM) in the system. Using H3PO4, as a cathodic electrolyte resulted in a higher Hg removal efficiency than using NaCl and HCl electrolytes. Electromigration was found to be the dominant Hg-ions (e.g. HHgO2-, Hg2+) transport mechanism in the marine sediment during remediation. Overall, this research demonstrates that employing enhanced electrodes and AEMs can enhance Hg removal by EK processes in relatively shorter operating times than conventional EK processes.

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Development of slow release fertilizers by tuning dissolution kinetics can reduce the environmental impact of (micro) nutrients added to crops. Mixed metal compounds may have different dissolution kinetics and plant uptake than single metal compounds. In this study, mixed Fe(II)/Zn(II) phosphates (0-100 at% Zn) were prepared by aqueous precipitation and their structural characteristics and dissolution kinetics in a sand column were measured as model for divalent metal and phosphate release in soil. Three minerals were identified, namely vivianite (Fe3(PO4)2·8H2O) at 0-20 at% Zn, phosphophyllite (Zn2Fe(PO4)2·4H2O) at 20-79 at% Zn, and hopeite (Zn3(PO4)2·4H2O) at 79-100 at% Zn. The Fe-rich materials had high SSA of 42-64 m2 g-1, which decreased to ≤4 m2 g-1 for ≥79 at% Zn. The Fe K-edge and Zn K-edge XANES spectroscopy measurements show that the samples had comparable local structure and contained 13-72% of Fe as Fe(III) due to partial oxidation. In the sand column, Zn(II) and Fe(II) phosphates dissolved near-congruently at steady state (>7 h), whereas mixed Fe(II)/Zn(II) phosphates showed preferential release of Zn over P and Fe, likely due to reprecipitation of Fe. Pot experiments demonstrate that Zn from Fe(II)/Zn(II) phosphates is absorbed by bird's eye chili plants (C. annuum), in agreement with the preferential dissolution of Zn(II). These results may provide insight into the dissolution of other divalent metals, which not only aids in the growth of plants and resulting foodstuff but ultimately leads to reductions in environmental contamination.

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The report that the central bond photoisomerization of the 1,3,5-hexatrienes (Hts) is highly inefficient has encouraged theoreticians to seek conical intersections (CIs) at geometries that can explain rapid nonradiative return to the initially excited isomer. Because they are photochemically silent, torsional relaxations about the terminal double bonds of the Hts have not been evaluated as significant radiationless decay pathways. Study of the photoisomerization of trans,trans,trans- and trans,cis,trans-1,6-dideuterio-1,3,5-hexatrienes ( ttt- and tct-Htd2) addresses this issue. Degassed cyclohexane- d12 (C6D12) and CD3CN solutions were irradiated at 254 nm in quartz NMR tubes, and the progress of the reactions was followed by 1H NMR. Photoisomerization rates based on the integration of terminal hydrogen NMR peaks are in reasonable agreement with rates obtained by fitting pure isomer NMR spectra to the phase shift and baseline corrected experimental NMR spectra. The results show that terminal bond isomerization is highly efficient, especially when one considers that central bond isomerization is much more efficient than previously reported and is mainly observed together with terminal bond isomerization. A mechanism involving terminal one-bond-twist (OBT) in competition with a bicycle pedal (BP) process accounts for all terminal and most central bond photoisomerization. OBT central bond isomerization is a minor reaction that is observed primarily in the tct to ttt direction. Most surprising is the prominent role of the BP process in central bond photoisomerization. Proposed initially to account for photoisomerization in free volume constraining media, it is observed here in the absence of medium constraints.

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Polyhedral oligomeric silsesquioxane (POSS)-based materials, poly-POSS-Tn [n = 8 (1), 10 (2), 12 (3), and mix (4)], were prepared in high yields via free radical polymerization of corresponding pure forms of methacrylate-functionalized POSS monomers, MMA-POSS-Tn (n = 8, 10, 12), and the mixture form, MMA-POSS-Tmix. Powder X-ray diffraction (XRD) spectra and BET analysis indicate that 1-4 are amorphous materials with high surface areas (683-839 m2 g-1). The surface areas and total pore volumes follow the trend: poly-POSS-T12 > poly-POSS-T10 > poly-POSS-Tmix > poly-POSS-T8. In addition, on the basis of Barrett-Joyner-Halenda (BJH) analysis, poly-POSS-T12 contains the highest amount of mesopores. The Pd nanoparticles immobilized on poly-POSS-Tn [n = 8 (5), 10 (6), 12 (7), and mix (8)] are well dispersed with 4-6 wt % Pd content and similar average particle sizes of 6.2-6.5 nm, according to transmission electron microscopy-energy dispersive X-ray analysis (TEM-EDX) and microwave plasma-atomic emission spectroscopy (MP-AES). At 90 °C, the stabilized Pd nanoparticles in 5-8 catalyzed aerobic oxidation of benzyl alcohol to benzaldehyde in 72-100% yields at 6 h using a mixture of a H2O/Pluronic (P123) solution. The PdNp@poly-POSS-T8 catalyst (5) exhibited the lowest catalytic activity, as a result of its lowest surface areas, total pore volumes, and amounts of mesopores. With the catalyst 8, various benzyl alcohol derivatives were converted to the corresponding aldehydes in good to excellent yields. However, with alcoholic substrates featuring electron-withdrawing substituents, high conversions were achieved with 1 equiv of K2CO3 additive and longer reaction times.

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This study emphasizes the development of a novel surface modified liposome as an anticancer drug nanocarrier. Quaternized N,O-oleoyl chitosan (QCS) was synthesized and incorporated into liposome vesicles, generating QCS-liposomes (Lip-QCS). The Lip-QCS liposomes were spherical in shape (average size diameter 171.5±0.8nm), with a narrow size distribution (PDI 0.1±0.0) and zeta potential of 11.7±0.7mV. In vitro mucoadhesive tests indicated that Lip-QCS possesses a mucoadhesive property. Moreover, the presence of QCS was able to induce the cationic charge on the surface of liposome. Cellular internalization of Lip-QCS was monitored over time, with the results revealing that the cell entry level of Lip-QCS was elevated at 24h. Following this, Lip-QCS were then employed to load cisplatin, a common platinum-containing anti-cancer drug, with a loading efficiency of 27.45±0.78% being obtained. The therapeutic potency of the loaded Lip-QCS was investigated using a 3D spheroid cervical cancer model (SiHa) which highlighted their cytotoxicity and apoptosis effect, and suitability as a controllable system for sustained drug release. This approach has the potential to assist in development of an effective drug delivery system against cervical cancer.

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Bituminous activated carbon (AC) has been widely used as a sorbent for adsorption of non-polar species, but its performance for removal of ionic species such as heavy metals has not been as efficient. In this study, AC was modified with chitosan nanoparticles (CN) using facile methods of dip coating and wet impregnation. The CN-coated AC demonstrated an increase in Cr(VI) removal efficiency in both kinetics and adsorption capacity. The adsorption capacity of the CN-coated AC (mg/g) was more than twice that of the uncoated AC (36.36 mg/g), or pure chitosan (32.57 mg/g). The sizes of the synthesized CN (160-2,000 nm) can be controlled by varying the concentration of the chitosan/reagents used. The adsorption isotherms are better described using the Freundlich rather than the Langmuir model and are in agreement with the heterogeneity of the surfaces. Adsorption kinetics followed that of the pseudo-second-order kinetics, suggesting chemisorption as a rate limiting step.

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A titania-entrapped silica hollow nanostructure was prepared using two consecutive coating processes, followed by calcination. The hydrothermal treatment of D-glucose assisted by polyethylene glycol was used to form a carbon layer over the titania surface. The resulting composite was used to fabricate a silica layer on top by hydrolyzing tetraethyl orthosilicate in strong base. The titania nanoparticles were then released but still trapped inside the silica hollow after calcination. Scanning and transmission electron microscopic techniques were employed to determine the morphology of the obtained product; nitrogen gas adsorption and X-ray diffraction methods were also used. Photocatalytic studies on five organic dyes showed that efficient dye-removal due to photocatalysis and adsorption with selectivity based on the charge-charge interaction between the dye and silica surface was possible. Other factors including the structures of the dyes and their molecular interaction also influenced the observed removal efficiency.

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Quantum yields for the photoisomerization of trans,trans-1,4-diphenyl-1,3-butadiene (tt-DPB), determined in benzene, cyclohexane, methylcyclohexane, hexane, and perfluorohexane, confirm the low values reported earlier for benzene and cyclohexane and reveal even lower values in the last two solvents. In contrast to trans-stilbene (t-St), fluorescence and torsional relaxation leading to photoisomerization do not account exclusively for S(1)tt-DPB decay. Competing radiationless singlet excited-state decay pathways exist in tt-DPB, which do not lead to photoisomerization and may not involve large-amplitude torsional motions. Our results invalidate analyses of tt-DPB fluorescence quantum yields and lifetimes that assign all radiationless decay to the isomerization channel. Gas-phase chromatography analysis of tt-DPB photoisomerization in hexane shows the reaction to be concentration-independent and reveals, for the first time, a significant, two-bond photoisomerization pathway, φ(tt→tc) = 0.092 and φ(tt→cc) = 0.020. The dominant one-bond-twist (OBT) process is accompanied by a bicycle pedal (BP) process that accounts for almost 20% of tt-DPB photoisomerization. The OBT tt-DPB photoisomerization quantum yield is largest in benzene (Bz) and smallest in perfluorohexane (PFH). Contrary to expectations, reduction in medium friction in PFH is accompanied by a decrease in φ(tt→tc). The 1(1)B(u)/2(1)A(g) order and energy gap appear to control the contribution of torsional relaxation to radiationless decay. Lowering the 1(1)B(u) energy as in Bz favors photoisomerization. Reversal of the 1(1)B(u)/2(1)A(g) order in PFH is accompanied by short τ(f) and small φ(f) and φ(tt→tc) values that suggest the presence of competing 2(1)A(g) → 1(1)Ag relaxation paths that are unproductive with respect to photoisomerization. We conclude that the Birks extension to diphenylpolyenes of the Orlandi-Siebrand cis-trans photoisomerization mechanism is not valid. Photoisomerization appears to occur in the 1(I)B(u) state, and we argue that this applies to t-St as well.

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