Adsorption of Hg(II) on polyethyleneimine-functionalized carboxymethylcellulose beads: Characterization, toxicity tests, and adsorption experiments.

Mercury (Hg) is widely used in many industrial processes and is released into the environment. Therefore, efficient removal of Hg from water is of vital importance worldwide. Here, we explored the adsorption characteristics of Hg(II) on polyethyleneimine-functionalized carboxymethylcellulose (PEI-CMC) beads and studied the toxicity of the beads toward Daphnia magna and Pseudokirchneriella subcapitata. The PEI-CMC beads had an average particle size of 2.04 ± 0.25 mm, a point of zero charge (pHpzc) of 5.8, and a swelling ratio of 2.45. Acute toxicity tests demonstrated that the PEI-CMC beads had no toxic effects on D. magna. The growth inhibition tests revealed that growth inhibition of P. subcapitata could be attributed to adsorption of trace elements in growth media on the PEI-CMC beads. The adsorption experiments exhibited that the Matthews and Weber model best described the kinetic data, whereas the Redlich-Peterson model was well fitted to the isotherm data. The theoretical maximum Hg(II) adsorption capacity of the PEI-CMC beads was 313.1 mg/g. The thermodynamic experiments showed endothermic nature of the Hg(II) adsorption on the PEI-CMC beads at 10-40 °C. The adsorption experiments exhibited that the Hg(II) adsorption capacity decreased gradually as pH increased from 2 to 12. The adsorption of Hg(II) on the PEI-CMC beads can occur through chelation and electrostatic attraction. The FTIR and XPS spectra before and after Hg(II) adsorption confirmed that chelation of neutral Hg(II) species (HgCl2, HgClOH, and Hg(OH)2) can occur with amino and oxygen-containing functional groups on the PEI-CMC beads. Considering species distribution of Hg(II) and the pHpzc of the PEI-CMC beads, electrostatic attraction between the positively-charged beads and anionic Hg(II) species (HgCl3- and HgCl42-) can take place in highly acidic solutions. The PEI-CMC beads were regenerated and reused for Hg(II) adsorption using 0.1 M HCl.

Acetaminophen adsorption to spherical carbons hydrothermally synthesized from sucrose: experimental, molecular, and mathematical modeling studies.

Acetaminophen (AAP) is an analgesic and non-steroidal anti-inflammatory drug and a micropollutant that has been detected in waterbodies worldwide. Here, we explore the characteristics of AAP adsorption onto spherical carbons (SCs) hydrothermally synthesized from pure sucrose as a carbon source. In one-factor-at-a-time experiments, the adsorption capacity of AAP remained relatively constant between pH 2 and 10 but became negligible at pH 12. The Raman, FTIR, and XPS spectra illustrate that hydrogen bonding, π-π interactions, and n-π* interactions could contribute to the AAP adsorption onto the SCs. CHEM3D modeling was used to explore hydrogen-bond formation, π-π interactions, n-π* interactions, and electrostatic repulsion between AAP and the SCs. In view of the pHpzc of the SCs (3.1) and the pKa of AAP (10.96), electrostatic repulsion could occur between negatively charged SCs and anionic AAP above pH 10. In consideration of the average pore diameter of the SCs (1.89 nm) and the AAP molecular size (8.94 Å × 7.95 Å × 4.93 Å), a pore-filling mechanism could contribute to the adsorption. A pseudo-second-order model was best fitted to the kinetic data (equilibrium time = 6 h), whereas the Liu isotherm was most suitable for the equilibrium data (maximum adsorption capacity = 92.0 mg/g). Adsorption of AAP to the SCs was exothermic at 10-40 °C. The SCs were regenerated and reused for AAP adsorption using a methanol. Multiple-factor-at-once (MFAO) experiments (input variables: pH, temperature, adsorbent dosage, and initial AAP concentration; output: AAP adsorption capacity) were used to develop response surface methodology (RSM, quartic regression) and artificial neural network (ANN, topology 4:11:9:1) models. Analyses using additional MFAO experimental data reveal that the predictive ability of the ANN model (R2 = 0.890) was better than that of the RSM model (R2 = 0.764). Based on the weight values of the ANN model, the relative importance of the input variables on the output was quantified in the order of initial AAP concentration (100%) > adsorbent dosage (92.3%) > temperature (77.6%) > pH (43.6%).

Characterization of ibuprofen removal by calcined spherical hydrochar through adsorption experiments, molecular modeling, and artificial neural network predictions.

Ibuprofen (IPF) is one of the most prescribed nonsteroidal anti-inflammatory drugs in recent times, but it is not readily removed in conventional wastewater treatments. Here, we investigate the adsorption characteristics of IPF onto calcined spherical hydrochar (CSH), which was synthesized through hydrothermal carbonization of sucrose followed by calcination. The adsorption experiments show that the equilibration time for IPF was 360 min, and a pseudo-second-order model was best fitted to the kinetic data. The isotherm data were best described by the Liu model with a theoretical maximum adsorption capacity of 95.6 mg/g. The thermodynamic data indicate the endothermic nature of the adsorption at 10-40 °C. The CSH was favorably regenerated and reused using methanol. In pH experiments, the IPF adsorption capacity declined gradually as pH rose from 2 to 8, dropped rapidly at pH 10, and became negligible at pH 12. The IPF adsorption to the CSH could occur through various adsorption mechanisms. Hydrogen-bond formation, π-π interactions, n-π* interactions, and electrostatic repulsion were explored and visualized with molecular modeling using CHEM3D. The Raman, FTIR, and XPS spectra suggest that π-π interactions could take place between the CSH and IPF. Considering the pKa value of IPF (4.91) and pHiep of the CSH (3.21), electrostatic repulsion between the negatively-charged CSH and anionic IPF could play a negative role in the adsorption. A pore-filling mechanism could contribute to the adsorption in view of the molecular size of IPF (9.43 Å × 7.75 Å × 6.23 Å) and the average pore diameter of the CSH (2.27 nm). In addition, hydrophobic interactions could be involved in the adsorption. Multi-factor adsorption experiments were executed with pH, temperature, CSH dosage, and initial IPF concentrations as input variables and IPF removal rate as an output variable, and an artificial neural network (ANN) model with a topology of 4:9:11:1 was developed to sufficiently describe the adsorption data (R > 0.99). Further analyses with additional experimental data confirm that the ANN model possessed good predictability for multi-factor adsorption.

A Dynamic Substrate Pool Revealed by cryo-EM of a Lipid-Preserved Respiratory Supercomplex.

Aims: Mitochondrial respiratory supercomplexes mediate redox electron transfer, generating a proton gradient for ATP synthesis. To provide structural information on the function of supercomplexes in physiologically relevant conditions, we conducted cryoelectron microscopy studies with supercomplexes in a lipid-preserving state. Results: Here, we present cryoelectron microscopy structures of bovine respiratory supercomplex I1III2IV1 by using a lipid-preserving sample preparation. The preparation greatly enhances the intercomplex quinone transfer activity. The structures reveal large intercomplex motions that result in different shapes and sizes of the intercomplex space between complexes I and III, forming a dynamic substrate pool. Biochemical and structural analyses indicated that intercomplex phospholipids mediate the intercomplex motions. An analysis of the different classes of focus-refined complex I showed that structural switches due to quinone reduction led to the formation of a novel channel that could transfer reduced quinones to the intercomplex substrate pool. Innovation and Conclusion: Our results indicate potential mechanism for the facilitated electron transfer involving a dynamic substrate pool and intercomplex movement by which supercomplexes play an active role in the regulation of metabolic flux and reactive oxygen species.