GGCX mutants that impair hemostasis reveal the importance of processivity and full carboxylation to VKD protein function.

γ-Glutamyl carboxylase (GGCX) generates multiple carboxylated Glus (Glas) in vitamin K-dependent (VKD) proteins that are required for their functions. GGCX is processive, remaining bound to VKD proteins throughout multiple Glu carboxylations, and this study reveals the essentiality of processivity to VKD protein function. GGCX mutants (V255M and S300F) whose combined heterozygosity in a patient causes defective clotting and calcification were studied using a novel assay that mimics in vivo carboxylation. Complexes between variant carboxylases and VKD proteins important to hemostasis (factor IX [FIX]) or calcification (matrix Gla protein [MGP]) were reacted in the presence of a challenge VKD protein that could potentially interfere with carboxylation of the VKD protein in the complex. The VKD protein in the complex with wild-type carboxylase was carboxylated before challenge protein carboxylation occurred and became fully carboxylated. In contrast, the V255M mutant carboxylated both forms at the same time and did not completely carboxylate FIX in the complex. S300F carboxylation was poor with both FIX and MGP. Additional studies analyzed FIX- and MGP-derived peptides containing the Gla domain linked to sequences that mediate carboxylase binding. The total amount of carboxylated peptide generated by the V255M mutant was higher than that of wild-type GGCX; however, the individual peptides were partially carboxylated. Analysis of the V255M mutant in FIX HEK293 cells lacking endogenous GGCX revealed poor FIX clotting activity. This study shows that disrupted processivity causes disease and explains the defect in the patient. Kinetic analyses also suggest that disrupted processivity may occur in wild-type carboxylase under some conditions (eg, warfarin therapy or vitamin K deficiency).

Adsorption of methyl orange on low-cost adsorbent natural materials and modified natural materials: a review.

Recently a large number of extensive studies have amassed that describe the removal of dyes from water and wastewater using natural adsorbents and modified materials. Methyl orange dye is found in wastewater streams from various industries that include textiles, plastics, printing and paper among other sources. This article reviews methyl orange adsorption onto natural and modified materials. Despite many techniques available, adsorption stands out for efficient water and wastewater treatment for its ease of operation, flexibility and large-scale removal of colorants. It also has a significant potential for regeneration recovery and recycling of adsorbents in comparison to other water treatment methods. The adsorbents described herein were classified into five categories based on their chemical composition: bio-sorbents, activated carbon, biochar, clays and minerals, and composites. In this review article, we want to demonstrate the capacity of natural and modified materials for dye adsorption which can yield significant improvements to the adsorption capacity of dyes such as methyl orange. In addition, the effect of critical variables including contact time, initial methyl orange concentration, dosage of adsorbent, pH, temperature and mechanism on the adsorption efficiency will be covered as part of this literature review.

The novelty of this review article describes the utility of various natural and modified materials employed to remove methyl orange (MO) from water, wastewater and aqueous solutions. Natural sorbents are very popular adsorbents because the majority of them are affordable and readily accessible in terms of addressing key challenges concerning water security that are relevant to MO adsorption processes.This review is significant since it will be useful in guiding researchers on the selection of an adsorbent that would be suitable for MO adsorption. Furthermore, our findings provide a basis for researchers interested in the design of composite adsorbents based on the selection of constituent components.

High surface area activated carbon from a pineapple (ananas comosus) crown via microwave-ZnCl2 activation for crystal violet and methylene blue dye removal: adsorption optimization and mechanism.

In this investigation, microwave irradiation assisted by ZnCl2 was used to transform pineapple crown (PN) waste into mesoporous activated carbon (PNAC). Complementary techniques were employed to examine the physicochemical characteristics of PNAC, including BET, FTIR, SEM-EDX, XRD, and pH at the point-of-zero-charge (pHpzc). PNAC is mesoporous adsorbent with a surface area of 1070 m2/g. The statistical optimization for the adsorption process of two model cationic dyes (methylene blue: MB and, crystal violet: CV) was conducted using the response surface methodology-Box-Behnken design (RSM-BBD). The parameters include solution pH (4-10), contact time (2-12) min, and PNAC dosage (0.02-0.1 g/100 mL). The Freundlich and Langmuir models adequately described the dye adsorption isotherm results for the MB and CV systems, whereas the pseudo-second order kinetic model accounted for the time dependent adsorption results. The maximum adsorption capacity (qmax) for PNAC with the two tested dyes are listed: 263.9 mg/g for CV and 274.8 mg/g for MB. The unique adsorption mechanism of MB and CV dyes by PNAC implicates multiple contributions to the adsorption process such as pore filling, electrostatic forces, H-bonding, and π-π interactions. This study illustrates the possibility of transforming PN into activated carbon (PNAC) with the potential to remove two cationic dyes from aqueous media.

The novelty of this research work stems from the conversion of pineapple (Ananas comosus) crown wastes with no monetary value into an efficient activated carbon adsorbent with relatively high surface area. Furthermore, a fast and convenient microwave assisted ZnCl₂ activation method was applied for producing the activated carbon (AC). The effectiveness of the produced AC was tested for the removal of two different cationic dyes: crystal violet (CV) and methylene blue (MB). A statistical optimization that employs a response surface methodology with the Box-Behnken design was employed to optimize the adsorption variables for the optimal dye removal. Moreover, the dye adsorption kinetics and thermodynamics, equilibrium isotherms, and the details of the adsorption process were reported herein.

Optimization and mechanistic approach for removal of crystal violet and methylene blue dyes via activated carbon from pyrolyzed-ZnCl2 bamboo waste.

In this study, bamboo waste (BW) was subjected to pyrolysis-assisted ZnCl2 activation to produce mesoporous activated carbon (BW-AC), which was then evaluated for its ability to remove cationic dyes, specifically methylene blue (MB) and crystal violet (CV), from aqueous environments. The properties of BW-AC were characterized using various techniques, including potentiometric-based point of zero charge (pHpzc), scanning electron microscopy with energy dispersive X-rays (SEM-EDX), X-ray diffraction (XRD), gas adsorption with Brunauer-Emmett-Teller (BET) analysis, infrared (IR) spectroscopy. To optimize the adsorption characteristics (BW-AC dosage, pH, and contact time) of PBW, a Box-Behnken design (BBD) was employed. The BW-AC dose of 0.05 g, solution pH of 10, and time of 8 min are identified as optimal operational conditions for achieving maximum CV (89.8%) and MB (96.3%) adsorption according to the BBD model. The dye removal kinetics for CV and MB are described by the pseudo-second-order model. The dye adsorption isotherms revealed that adsorption of CV and MB onto BW-AC follow the Freundlich model. The maximum dye adsorption capacities (qmax) of BW-AC for CV (530 mg/g) and MB (520 mg/g) are favorable, along with the thermodynamics of the adsorption process, which is characterized as endothermic and spontaneous. The adsorption mechanism of CV and MB dyes by BW-AC was attributed to multiple contributions: hydrogen bonding, electrostatic forces, π-π attraction, and pore filling. The findings of this study highlight the potential of BW-AC as an effective adsorbent in wastewater treatment applications, contributing to the overall goal of mitigating the environmental impact of cationic dyes and ensuring the quality of water resources.

The novelty of this research work comes from the conversion of the bamboo waste (BW) into mesoporous activated carbon (BW-AC) via pyrolysis-assisted ZnCl₂ activation for the removal of cationic dyes such as methylene blue (MB) and crystal violet (CV) from aqueous media. The effectiveness of the obtained activated carbon was tested toward removal of two structurally different cationic dyes (CV and MB), where a statistical optimization employing a response surface methodology with Box-Behnken design was applied to optimize dye removal. In addition to determination of the working parameters for dye removal, the adsorption kinetics and thermodynamic parameters for the adsorption process were determined to provide molecular-level insight.

Production of activated carbon from food wastes (chicken bones and rice waste) by microwave assisted ZnCl2 activation: an optimized process for crystal violet dye removal.

A major worldwide challenge that presents significant economic, environmental, and social concerns is the rising generation of food waste. The current work used chicken bones (CB) and rice (R) food waste as alternate precursors for the production of activated carbon (CBRAC) by microwave radiation-assisted ZnCl2 activation. The adsorption characteristics of CBRAC were investigated in depth by removing an organic dye (crystal violet, CV) from an aquatic environment. To establish ideal conditions from the significant adsorption factors (A: CBRAC dosage (0.02-0.12 g/100 mL); B: pH (4-10); and C: duration (30-420), a numerical desirability function of Box-Behnken design (BBD) was utilized. The highest CV decolorization by CBRAC was reported to be 90.06% when the following conditions were met: dose = 0.118 g/100 mL, pH = 9.0, and time = 408 min. Adsorption kinetics revealed that the pseudo-first order (PFO) model best matches the data, whereas the Langmuir model was characterized by equilibrium adsorption, where the adsorption capacity of CBRAC for CV dye was calculated to be 57.9 mg/g. CV adsorption is accomplished by several processes, including electrostatic forces, pore diffusion, π-π stacking, and H-bonding. This study demonstrates the use of CB and R as biomass precursors for the efficient creation of CBRAC and their use in wastewater treatment, resulting in a greener environment.

The novelty of this research work relates to converting food wastes (mixture of chicken bones and rice waste) into activated carbon via microwave assisted ZnCl₂ activation. Moreover, the produced activated carbon was successfully applied as a potential adsorbent for removal of a toxic cationic dye; namely, crystal violet (CV) from aqueous environment.

Response surface methodology for optimizing methylene blue dye removal by mesoporous activated carbon derived from renewable woody Bambusoideae waste.

In this study, the focus was on utilizing tropical plant biomass waste, specifically bamboo (BB), as a sustainable precursor for the production of activated carbon (BBAC) via pyrolysis-induced K2CO3 activation. The potential application of BBAC as an effective adsorbent for the removal of methylene blue (MB) dye from aqueous solutions was investigated. Response surface methodology (RSM) was employed to evaluate key adsorption characteristics, which included BBAC dosage (A: 0.02-0.08 g/L), pH (B: 4-10), and time (C: 2-8 min). The adsorption isotherm analysis revealed that the adsorption of MB followed the Freundlich model. Moreover, the kinetic data were well-described by the pseudo-second-order model, suggesting the role of a chemisorption process. The BBAC demonstrated a notable MB adsorption capacity of 195.8 mg/g, highlighting its effectiveness as an adsorbent. Multiple mechanisms were identified as controlling factors in MB adsorption by BBAC, including electrostatic forces, π-π stacking, and H-bonding interactions. The findings of this study indicate that BBAC derived from bamboo has the potential to be a promising adsorbent for the treatment of wastewater containing organic dyes. The employment of sustainable precursors like bamboo for activated carbon production contributes to environmentally friendly waste management practices and offers a solution for the remediation of dye-contaminated wastewater.

This works introduces a renewable and woody Bambusoideae waste as promising and low-cost precursor for producing mesoporous activated carbon via microwave assisted K₂CO₃ activation. The effectiveness of the prepared activated carbon was tested toward removal of a toxic cationic dye, namely; methylene blue from aqueous environment.

Food-grade algae modified Schiff base-chitosan benzaldehyde composite for cationic methyl violet 2B dye removal: RSM statistical parametric optimization.

This work aims to apply the use of food-grade algae (FGA) composited with chitosan-benzaldehyde Schiff base biopolymer (CHA-BD) as a new adsorbent (CHA-BA/FGA) for methyl violet 2B (MV 2B) dye removal from aqueous solutions. The effect of three processing variables, including CHA-BA/FGA dosage (0.02-0.1 g/100 mL), pH solution (4-10), and contact duration (10-120 min) on the removal of MV 2B was investigated using the Box-Behnken design (BBD) model. Kinetic and equilibrium dye adsorption profiles reveal that the uptake of MV 2B dye by CHA-BA/FGA is described by the pseudo-second kinetics and the Langmuir models. The thermodynamics of the adsorption process (ΔG°, ΔH°, and ΔS°) reveal spontaneous and favorable adsorption parameters of MV 2B dye onto the CHA-BA/FGA biocomposite at ambient conditions. The CHA-BA/FGA exhibited the maximum ability to absorb MV 2B of 126.51 mg/g (operating conditions: CHA-BA/FGA dose = 0.09 g/100 mL, solution pH = 8.68, and temperature = 25 °C). Various interactions, including H-bonding, electrostatic forces, π-π stacking, and n-π stacking provide an account of the hypothesized mechanism of MV 2B adsorption onto the surface of CHA-BA/FGA. This research reveals that CHA-BA/FGA with its unique biocomposite structure and favorable adsorption properties can be used to remove harmful cationic dyes from wastewater.

The first novel aspect of this research work comes from the utilization of food-grade algae which contains various types of negative functional groups hydroxyl, carboxyl, and phosphate to modify a cationic biopolymer (Chitosan) to improve its adsorptive property toward removal of a cationic dye such as methyl violet 2B. The second novel aspect of this research work is to use the hydrothermal process to assist the grafting of an aromatic ring of benzaldehyde into the polymer matrix of the chitosan-food grade algae composite via a Schiff base linkage to improve its chemical stability and functionality.

A Novel Size-Based Centrifugal Microfluidic Design to Enrich and Magnetically Isolate Circulating Tumor Cells from Blood Cells through Biocompatible Magnetite-Arginine Nanoparticles.

This paper presents a novel centrifugal microfluidic approach (so-called lab-on-a-CD) for magnetic circulating tumor cell (CTC) separation from the other healthy cells according to their physical and acquired chemical properties. This study enhances the efficiency of CTC isolation, crucial for cancer diagnosis, prognosis, and therapy. CTCs are cells that break away from primary tumors and travel through the bloodstream; however, isolating CTCs from blood cells is difficult due to their low numbers and diverse characteristics. The proposed microfluidic device consists of two sections: a passive section that uses inertial force and bifurcation law to sort CTCs into different streamlines based on size and shape and an active section that uses magnetic forces along with Dean drag, inertial, and centrifugal forces to capture magnetized CTCs at the downstream of the microchannel. The authors designed, simulated, fabricated, and tested the device with cultured cancer cells and human cells. We also proposed a cost-effective method to mitigate the surface roughness and smooth surfaces created by micromachines and a unique pulsatile technique for flow control to improve separation efficiency. The possibility of a device with fewer layers to improve the leaks and alignment concerns was also demonstrated. The fabricated device could quickly handle a large volume of samples and achieve a high separation efficiency (93%) of CTCs at an optimal angular velocity. The paper shows the feasibility and potential of the proposed centrifugal microfluidic approach to satisfy the pumping, cell sorting, and separating functions for CTC separation.

A Highly Sensitive Chitosan-Based SERS Sensor for the Trace Detection of a Model Cationic Dye.

The rapid detection of contaminants in water resources is vital for safeguarding the environment, where the use of eco-friendly materials for water monitoring technologies has become increasingly prioritized. In this context, the role of biocomposites in the development of a SERS sensor is reported in this study. Grafted chitosan was employed as a matrix support for Ag nanoparticles (NPs) for the surface-enhanced Raman spectroscopy (SERS). Chitosan (CS) was decorated with thiol and carboxylic acid groups by incorporating S-acetyl mercaptosuccinic anhydride (SAMSA) to yield CS-SAMSA. Then, Ag NPs were immobilized onto the CS-SAMSA (Ag@CS-SAMSA) and characterized by spectral methods (IR, Raman, NIR, solid state 13C NMR with CP-MAS, XPS, and TEM). Ag@CS-SAMSA was evaluated as a substrate for SERS, where methylene blue (MB) was used as a model dye adsorbate. The Ag@CS-SAMSA sensor demonstrated a high sensitivity (with an enhancement factor ca. 108) and reusability over three cycles, with acceptable reproducibility and storage stability. The Raman imaging revealed a large SERS effect, whereas the MB detection varied from 1-100 µM. The limits of detection (LOD) and quantitation (LOQ) of the biocomposite sensor were characterized, revealing properties that rival current state-of-the-art systems. The dye adsorption profiles were studied via SERS by fitting the isotherm results with the Hill model to yield the ΔG°ads for the adsorption process. This research demonstrates a sustainable dual-function biocomposite with tailored adsorption and sensing properties suitable for potential utility in advanced water treatment technology and environmental monitoring applications.

Chitosan Biocomposites with Variable Cross-Linking and Copper-Doping for Enhanced Phosphate Removal.

The fabrication of chitosan (CH) biocomposite beads with variable copper (Cu2+) ion doping was achieved with a glutaraldehyde cross-linker (CL) through three distinct methods: (1) formation of CH beads was followed by imbibition of Cu(II) ions (CH-b-Cu) without CL; (2) cross-linking of the CH beads, followed by imbibition of Cu(II) ions (CH-b-CL-Cu); and (3) cross-linking of pristine CH, followed by bead formation with Cu(II) imbibing onto the beads (CH-CL-b-Cu). The biocomposites (CH-b-Cu, CH-b-CL-Cu, and CH-CL-b-Cu) were characterized via spectroscopy (FTIR, 13C solid NMR, XPS), SEM, TGA, equilibrium solvent swelling methods, and phosphate adsorption isotherms. The results reveal variable cross-linking and Cu(II) doping of the CH beads, in accordance with the step-wise design strategy. CH-CL-b-Cu exhibited the greatest pillaring of chitosan fibrils with greater cross-linking, along with low Cu(II) loading, reduced solvent swelling, and attenuated uptake of phosphate dianions. Equilibrium and kinetic uptake results at pH 8.5 and 295 K reveal that the non-CL Cu-imbibed beads (CH-b-Cu) display the highest affinity for phosphate (Qm = 133 ± 45 mg/g), in agreement with the highest loading of Cu(II) and enhanced water swelling. Regeneration studies demonstrated the sustainability and cost-effectiveness of Cu-imbibed chitosan beads for controlled phosphate removal, whilst maintaining over 80% regenerability across several adsorption-desorption cycles. This study offers a facile synthetic approach for controlled Cu2+ ion doping onto chitosan-based beads, enabling tailored phosphate oxyanion uptake from aqueous media by employing a sustainable polysaccharide biocomposite adsorbent for water remediation by mitigation of eutrophication.

Mesoporous activated carbon derived from fruit by-product by pyrolysis induced chemical activation: optimization and mechanism for fuchsin basic dye removal.

In this study, pineapple crown (PC) feedstock residues were utilized as a potential precursor toward producing activated carbon (PCAC) via pyrolysis induced with ZnCl2 activation. The PCAC has a surface area (457.8 m2/g) and a mesoporous structure with an average pore diameter of 3.35 nm, according to the Brunauer-Emmett-Teller estimate. The removal of cationic dye (Fuchsin basic; FB) was used for investigating the adsorption parameters of PCAC. The optimization of significant adsorption variables (A: PCAC dose (0.02-0.1 g/100 mL); B: pH (4-10); C: time (10-90); and D: initial FB concentration (10-50 mg/L) was conducted using the Box-Behnken design (BBD). The pseudo-second-order (PSO) model characterized the dye adsorption kinetic profile, whereas the Freundlich model reflected the equilibrium adsorption profile. The maximum adsorption capacity (qmax) of PCAC for FB dye was determined to be 171.5 mg/g. Numerous factors contribute to the FB dye adsorption mechanism onto the surface of PCAC, which include electrostatic attraction, H-bonding, pore diffusion, and π-π stacking. This study illustrates the utilization of PC biomass feedstock for the fabrication of PCAC and its successful application in wastewater remediation.

Box-Behnken design with desirability function for methylene blue dye adsorption by microporous activated carbon from pomegranate peel using microwave assisted K2CO3 activation.

This research aims to convert pomegranate peel (PP) into microporous activated carbon (PPAC) using a microwave assisted K2CO3 activation method. The optimum activation conditions were carried out with a 1:2 PP/K2CO3 impregnation ratio, radiation power 800 W, and 15 min irradiation time. The statistical Box-Behnken design (BBD) was employed as an effective tool for optimizing the factors that influence the adsorption performance and removal of methylene blue (MB) dye. The output data of BBD with a desirability function indicate a 94.8% removal of 100 mg/L MB at the following experimental conditions: PPAC dose of 0.08 g, solution pH of 7.45, process temperature of 32.1 °C, and a time of 30 min. The pseudo-second order (PSO) kinetic model accounted for the contact time for the adsorption of MB. At equilibrium conditions, the Freundlich adsorption isotherm describes the adsorption results, where the maximum adsorption capacity of PPAC for MB dye was 291.5 mg g-1. This study supports the utilization of biomass waste from pomegranate peels and conversion into renewable and sustainable adsorbent materials. As well, this work contributes to the management of waste biomass and water pollutant sequestration.

The novelty of this research work comes from the conversion of the biomass waste, namely; the conversion of pomegranate peel (PP) into microporous activated carbon (PPAC) via a microwave assisted K₂CO₃ activation process. The applicability of the PPAC toward the removal of methylene blue dye (MB) was statistically optimized using Box Behnken design in the response surface methodology (BBD-RSM).

An Overview of Modified Chitosan Adsorbents for the Removal of Precious Metals Species from Aqueous Media.

This mini-review provides coverage of chitosan-based adsorbents and their modified forms as sustainable solid-phase extraction (SPE) materials for precious metal ions, such as gold species, and their complexes in aqueous media. Modified forms of chitosan-based adsorbents range from surface-functionalized systems to biomaterial composites that contain inorganic or other nanomaterial components. An overview of the SPE conditions such as pH, temperature, contact time, and adsorbent dosage was carried out to outline how these factors affect the efficiency of the sorption process, with an emphasis on gold species. This review provides insight into the structure-property relationships for chitinaceous adsorbents and their metal-ion removal mechanism in aqueous media. Cross-linked chitosan sorbents showed a maximum for Au(III) uptake capacity (600 mg/g), while S-containing cross-linked chitosan display favourable selectivity and uptake capacity with Au(III) species. Compared to industrial adsorbents such as activated carbon, modified chitosan sorbents display favourable uptake of Au(III) species, especially in aqueous media at low pH. In turn, this contribution is intended to catalyze further research directed at the rational design of tailored SPE materials that employ biopolymer scaffolds to yield improved uptake properties of precious metal species in aqueous systems. The controlled removal of gold and precious metal species from aqueous media is highly relevant to sustainable industrial processes and environmental remediation.

Adsorption Studies of Waterborne Trihalomethanes Using Modified Polysaccharide Adsorbents.

The adsorptive removal of trihalomethanes (THMs) from spiked water samples was evaluated with a series of modified polysaccharide adsorbents that contain ß-cylodextrin or chitosan. The uptake properties of these biodegradable polymer adsorbents were evaluated with a mixture of THMs in aqueous solution. Gas chromatography employing a direct aqueous injection (DAI) method with electrolytic conductivity detection enabled quantification of THMs in water at 295 K and at pH 6.5. The adsorption isotherms for the polymer-THMs was evaluated using the Sips model, where the monolayer adsorption capacities ranged between 0.04 and 1.07 mmol THMs/g for respective component THMs. Unique adsorption characteristics were observed that vary according to the polymer structure, composition, and surface chemical properties. The modified polysaccharide adsorbents display variable molecular recognition and selectivity toward component THMs in the mixed systems according to the molecular size and polarizability of the adsorbates.

Coating Cellulosic Material with Ag Nanowires to Fabricate Wearable IR-Reflective Device for Personal Thermal Management: The Role of Coating Method and Loading Level.

Textiles coated with silver nanowires (AgNWs) are effective at suppressing radiative heat loss without sacrificing breathability. Many reports present the applicability of AgNWs as IR-reflective wearable textiles, where such studies partially evaluate the parameters for practical usage for large-scale production. In this study, the effect of the two industrial coating methods and the loading value of AgNWs on the performance of AgNWs-coated fabric (AgNWs-CF) is reported. The AgNWs were synthesized by the polyol process and applied onto the surface of cotton fabric using either dip- or spray-coating methods with variable loading levels of AgNWs. X-ray diffraction, scanning electron microscopy (SEM), infrared (IR) reflectance, water vapor permeability (WVP), and electrical resistance properties were characterized. The results report the successful synthesis of AgNWs with a 30 µm length. The results also show that the spray coating method has a better performance for reflecting the IR radiation to the body, which increases with a greater loading level of the AgNWs. The antibacterial results show a good inhibition zone for cotton fabric coated by both methods, where the spray-coated fabric has a better performance overall. The results also show the coated fabric with AgNWs maintains the level of fabric breathability similar to control samples. AgNWs-CFs have potential utility for cold weather protective clothing in which heat dissipation is attenuated, along with applications such as wound dressing materials that provide antibacterial protection.

Floating ZnO QDs-Modified TiO2/LLDPE Hybrid Polymer Film for the Effective Photodegradation of Tetracycline under Fluorescent Light Irradiation: Synthesis and Characterisation.

In this work, mesoporous TiO2-modified ZnO quantum dots (QDs) were immobilised on a linear low-density polyethylene (LLDPE) polymer using a solution casting method for the photodegradation of tetracycline (TC) antibiotics under fluorescent light irradiation. Various spectroscopic and microscopic techniques were used to investigate the physicochemical properties of the floating hybrid polymer film catalyst (8%-ZT@LLDPE). The highest removal (89.5%) of TC (40 mg/L) was achieved within 90 min at pH 9 due to enhanced water uptake by the LDDPE film and the surface roughness of the hybrid film. The formation of heterojunctions increased the separation of photogenerated electron-hole pairs. The QDs size-dependent quantum confinement effect leads to the displacement of the conduction band potential of ZnO QDs to more negative energy values than TiO2. The displacement generates more reactive species with higher oxidation ability. The highly stable film photocatalyst can be separated easily and can be repeatedly used up to 8 cycles without significant loss in the photocatalytic ability. The scavenging test indicates that the main species responsible for the photodegradation was O2●-. The proposed photodegradation mechanism of TC was demonstrated in further detail based on the intermediates detected by LC-time-of-flight/mass spectrometry (LC/TOF-MS).

Warfarin alters vitamin K metabolism: a surprising mechanism of VKORC1 uncoupling necessitates an additional reductase.

The anticoagulant warfarin inhibits the vitamin K oxidoreductase (VKORC1), which generates vitamin K hydroquinone (KH2) required for the carboxylation and consequent activation of vitamin K-dependent (VKD) proteins. VKORC1 produces KH2 in 2 reactions: reduction of vitamin K epoxide (KO) to quinone (K), and then KH2 Our dissection of full reduction vs the individual reactions revealed a surprising mechanism of warfarin inhibition. Warfarin inhibition of KO to K reduction and carboxylation that requires full reduction were compared in wild-type VKORC1 or mutants (Y139H, Y139F) that cause warfarin resistance. Carboxylation was much more strongly inhibited (∼400-fold) than KO reduction (two- to threefold). The K to KH2 reaction was analyzed using low K concentrations that result from inhibition of KO to K. Carboxylation that required only K to KH2 reduction was inhibited much less than observed with the KO substrate that requires full VKORC1 reduction (eg, 2.5-fold vs 70-fold, respectively, in cells expressing wild-type VKORC1 and factor IX). The results indicate that warfarin uncouples the 2 reactions that fully reduce KO. Uncoupling was revealed because a second activity, a warfarin-resistant quinone reductase, was not present. In contrast, 293 cells expressing factor IX and this reductase activity showed much less inhibition of carboxylation. This activity therefore appears to cooperate with VKORC1 to accomplish full KO reduction. Cooperation during warfarin therapy would have significant consequences, as VKD proteins function in numerous physiologies in many tissues, but may be poorly carboxylated and dysfunctional if the second activity is not ubiquitously expressed similar to VKORC1.

Modular Chitosan-Based Adsorbents for Tunable Uptake of Sulfate from Water.

The context of this study responds to the need for sorbent technology development to address the controlled removal of inorganic sulfate (SO42-) from saline water and the promising potential of chitosan as a carrier system for organosulfates in pharmaceutical and nutraceutical applications. This study aims to address the controlled removal of sulfate using chitosan as a sustainable biopolymer platform, where a modular synthetic approach was used for chitosan bead preparation that displays tunable sulfate uptake. The beads were prepared via phase-inversion synthesis, followed by cross-linking with glutaraldehyde, and impregnation of Ca2+ ions. The sulfate adsorption properties of the beads were studied at pH 5 and variable sulfate levels (50-1000 ppm), where beads with low cross-linking showed moderate sulfate uptake (35 mg/g), while cross-linked beads imbibed with Ca2+ had greater sulfate adsorption (140 mg/g). Bead stability, adsorption properties, and the point-of-zero charge (PZC) from 6.5 to 6.8 were found to depend on the cross-linking ratio and the presence of Ca2+. The beads were regenerated over multiple adsorption-desorption cycles to demonstrate the favorable uptake properties and bead stability. This study contributes to the development of chitosan-based adsorbent technology via a modular materials design strategy for the controlled removal of sulfate. The results of this study are relevant to diverse pharmaceutical and nutraceutical applications that range from the controlled removal of dextran sulfate from water to the controlled release of chondroitin sulfate.

Cu(II) Ion Adsorption by Aniline Grafted Chitosan and Its Responsive Fluorescence Properties.

The detection and removal of heavy metal species in aquatic environments is of continued interest to address ongoing efforts in water security. This study was focused on the preparation and characterization of aniline grafted chitosan (CS-Ac-An), and evaluation of its adsorption properties with Cu(II) under variable conditions. Materials characterization provides support for the grafting of aniline onto chitosan, where the kinetic and thermodynamic adsorption properties reveal a notably greater uptake (>20-fold) of Cu(II) relative to chitosan, where the adsorption capacity (Qm) of CS-Ac-An was 106.6 mg/g. Adsorbent regeneration was demonstrated over multiple adsorption-desorption cycles with good uptake efficiency. CS-Ac-An has a strong fluorescence emission that undergoes prominent quenching at part per billion levels in aqueous solution. The quenching process displays a linear response over variable Cu(II) concentration (0.05-5 mM) that affords reliable detection of low level Cu(II) levels by an in situ "turn-off" process. The tweezer-like chelation properties of CS-Ac-An with Cu(II) was characterized by complementary spectroscopic methods: IR, NMR, X-ray photoelectron (XPS), and scanning electron microscopy (SEM). The role of synergistic effects are inferred among two types of active adsorption sites: electron rich arene rings and amine groups of chitosan with Cu(II) species to afford a tweezer-like binding modality.

Simultaneous adsorption of lanthanum and yttrium from aqueous solution by durian rind biosorbent.

This paper presents the adsorption capacity of a biosorbent derived from the inner part of durian (Durio zibethinus) rinds, which are a low-cost and abundant agro-waste material. The durian rind sorbent has been successfully utilized to remove lanthanum (La) and yttrium (Y) ions from their binary aqueous solution. The effects of several adsorption parameters including contact time, pH, concentrations of La and Y, and temperature on the removal of La and Y ions were investigated. The adsorption isotherm and kinetics of the metal ions were also evaluated in detail. Both La and Y ions were efficiently adsorbed by the biosorbent with optimum adsorption capacity as high as 71 mg La and 35 mg Y per gram biosorbent, respectively. The simultaneous adsorption of La and Y ions follows Langmuir isotherm model, due to the favorable chelation and strong chemical interactions between the functional groups on the surface of the biosorbent and the metal ions. The addition of oxygen content after adsorption offers an interpretation that the rare-earth metal ions are chelated and incorporated most probably in the form of metal oxides. With such high adsorption capacity of La and Y ions, the durian rind sorbent could potentially be used to treat contaminated wastewater containing La and Y metal ions, as well as for separating and extracting rare-earth metal ions from crude minerals.