Removal of copper from sulfate solutions using biochar derived from crab processing by-product.

Increasing metal demand is accelerating the mining and processing of minerals, however to ensure sustainable growth innovative approaches are required to better manage associated effluents. Biochar from the fast pyrolysis of residues from fishery and forestry operations has been studied as a low-cost, environmentally and economically friendly method for treating mine tailings and processing effluents. However, the bulk of the studies focus on terrestrial biomass (e.g. wood) and do not include potential inhibition/enhancement of adsorption due to pH controlling compounds. In this work biochar generated from snow crab (Chionoecetes Opilio) processing was studied as an adsorbent for copper solutions containing sulfate (a key compound in sulfide ore mining waters) with the objective of assessing adsorption capacity and the impact of sulfate on copper adsorption. The biochar, a porous structure comprised of calcite (CaCO3), was alkaline and has a negative zeta potential under neutral and basic conditions. The crab biochar removed over 99% of Cu2+ from a 100 mg/L solution (sourced as CuSO4) at a dosage of 5 g/L, which was higher than lignocellulosic biochar at the same biochar dosage. While metal adsorption can often be impacted at acidic conditions, Cu2+ adsorption was not impacted by initial acidic pH due to the biochar's buffering capacity. The Pseudo-Second Order (PSO) model fit the adsorption rate with maximum adsorption achieved in approximately 2 h. The maximum adsorption isotherm capacity was 184.8 ± 10.2 mg/g for Cu2+, much higher than existing commercial activated carbons and previously studied lignocellulosic biochars and followed the Freundlich isotherm. The adsorption mechanism responsible for removal of Cu2+ was found to be precipitation, in the form of the mineral posnjakite (Cu4[(OH)6SO4]·H2O). These results indicate for the first time that crab-based biochars are capable of adsorbing large quantities of Cu2+ from sulfate-rich solution, while also buffering solution pH, demonstrating promise as an acid mine drainage treatment for removal of harmful metals and reduction of acidity.

Adsorption of Oligo-DNA on Magnesium Aluminum-Layered Double-Hydroxide Nanoparticle Surfaces: Mechanistic Implication in Gene Delivery.

Magnesium aluminum-layered double-hydroxide nanoparticles (LDH NPs) are promising drug-delivery vehicles for gene therapy, particularly for siRNA interference; however, the interactions between oligo-DNA and LDH surfaces have not been adequately elucidated. Through a mechanistic study, oligo-DNA initially appears to rapidly bind strongly to the LDH outer surfaces through interactions with their phosphate backbones via ligand exchange with OH- on Mg2+ centers and electrostatic forces with Al3+. These initial interactions might precede diffusion into interlayer spaces, and this knowledge can be used to design better gene therapy delivery systems.

Application of biochar for acid gas removal: experimental and statistical analysis using CO2.

Acid gases such as carbon dioxide and hydrogen sulfide are common contaminants in oil and gas operations, landfill gases, and exhaust stacks from power plants. While there are processes currently used to treat these effluents (e.g., amine absorption and adsorption using zeolite), many of these processes require high energy, space, and hazardous chemicals. Removal using biochar derived from the fast pyrolysis of forestry residues represents a more sustainable option. In this study, adsorption using CO2 as a surrogate for acid gases was investigated using various biochars produced from fast pyrolysis of sawmill residues. Response surface methodology was used to determine operating conditions for maximum adsorption and assess interaction of the adsorption parameters, i.e., temperature, inlet feed flow rate, and CO2 concentration, on biochar adsorption capacity. The Freundlich isotherm best represented the equilibrium adsorption, and the kinetic model was pseudo first-order. Thermodynamic analysis indicated the adsorption process was spontaneous and exothermic. The biochar had better adsorption capacity relative to commercial zeolite. Our results suggested that biochar could be used as a sustainable and cost-effective option for contaminant removal from acid gases produced in landfill gas treatment, fossil fuel extraction, and/or combustion.

Chiral periodic mesoporous organosilicates based on axially chiral monomers: transmission of chirality in the solid state.

Chiral mesoporous materials have been prepared with purely organic monomers employing an enantiomerically pure biphenyl bis-siloxane as a dopant along with simple 4,4'-bis(triethoxysilyl)biphenyl as the bulk material. Analysis of these materials by CD spectroscopy indicates the formation of new chiral aggregates in the solid state consistent with charge delocalization from adjacent aryl rings in close contact. These aggregates are only observed when the biphenyl and enantiomerically pure biaryl are both present. The red-shift resulting of the CD signal resulting from these interactions is modeled computationally using time-dependent DFT calculations.

Optimizing Reductive Degradation of PAHs Using Anhydrous Ethanol with Magnesium Catalyzed by Glacial Acetic Acid.

Targeted degradation of individual polycyclic aromatic hydrocarbon (PAH) constituents like anthracene, may offer cost effective and efficient cleaning of coal tar-contaminated sites. Thus, a reductive degradation procedure of anthracene using activated magnesium with anhydrous ethanol at room temperature was developed and optimized. To determine the optimum conditions for anthracene, such as effective magnesium concentrations, glacial acetic acid volumes, and exposure time for the anthracene reduction, the experiments were designed using the response surface methodology based on the central composite design. The design also minimized the number of experiments. The main product from anthracene reduction is 9,10-dihyrdoanthracene. Optimum conditions for 98% degradation capacity of anthracene (2.80 × 10-3 mmol) were 30 mg of Mg powder (1.20 mmol), 60 µL of glacial acetic acid (1.05 mmol), and 30 min exposure time. When the optimized method was tested on the coal tar specimen, twice as many reagents (i.e., Mg and glacial acetic acid) were required to obtain a 90% degradation of anthracene and fluoranthene from the coal tar. This method of using activated Mg and anhydrous ethanol selectively reduces PAHs in coal tar; in particular anthracene and fluoranthene are most efficiently removed.

Adsorption of doxorubicin on citrate-capped gold nanoparticles: insights into engineering potent chemotherapeutic delivery systems.

Gold nanomaterials have received great interest for their use in cancer theranostic applications over the past two decades. Many gold nanoparticle-based drug delivery system designs rely on adsorbed ligands such as DNA or cleavable linkers to load therapeutic cargo. The heightened research interest was recently demonstrated in the simple design of nanoparticle-drug conjugates wherein drug molecules are directly adsorbed onto the as-synthesized nanoparticle surface. The potent chemotherapeutic, doxorubicin often serves as a model drug for gold nanoparticle-based delivery platforms; however, the specific interaction facilitating adsorption in this system remains understudied. Here, for the first time, we propose empirical and theoretical evidence suggestive of the main adsorption process where (1) hydrophobic forces drive doxorubicin towards the gold nanoparticle surface before (2) cation-π interactions and gold-carbonyl coordination between the drug molecule and the cations on AuNP surface facilitate DOX adsorption. In addition, biologically relevant compounds, such as serum albumin and glutathione, were shown to enhance desorption of loaded drug molecules from AuNP at physiologically relevant concentrations, providing insight into the drug release and in vivo stability of such drug conjugates.