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An investigation into Cu(II) adsorption from contaminated water utilizing a trickle tray column that has been upscaled from batch-scale adsorption was performed to understand the efficacy of the adsorbent when used in a continuous system-which is more common in actual use in an industry. The size of the functionalized fabric adsorbent selected in a pilot-scale is about four times larger than a batch-scale. The continuous Cu(II) adsorption was analyzed using three parameters: initial Cu(II) concentration in solution; inlet solution flow rate and number of adsorbent sheets in the column to estimate the adsorption process's breakthrough curve results. The breakthrough curve results were fitted with three mathematical models by Thomas, Yoon-Nelson and Adams-Bohart to comprehend the mechanisms of the adsorption process. All three mathematical models can be used to reliably describe the continuous adsorption process using diverse conditions applied in this study. Overall results showed that PBMEP-g-PE/PP adsorbent using the trickle tray column demonstrated as high as 97% efficiency of Cu(II) adsorption during the first 6 h. Three-cycle reutilization of the adsorbent through a process of adsorption-desorption revealed that Cu(II) removal efficiency surpassed 70% after 6 h of each cycle, confirming the suitability of this system for practical application., (© 2024. The Author(s).)

In the fields of polymer and material chemistries, strong acid units have mainly included sulfonic acids, which has limited the extension of related material chemistries. Here, a unique carbon acid functionality, namely the bis[(trifluoromethyl)sulfonyl]methyl group, was integrated with polymers via a simple postpolymerization modification with the outstandingly electrophilic 1,1-bis[(trifluoromethyl)sulfonyl]ethylene. The proposed synthesis protocol was verified as an efficient process even for solid-state reactions. The synthesis afforded an organic material with a surface decorated with bis[(trifluoromethyl)sulfonyl]methyl units. The fabricated membranes featuring surface bis[(trifluoromethyl)sulfonyl]methyl units functioned as efficient organocatalysts with high catalytic activity for the Mukaiyama aldol reaction. This study provides a simple method for installing superacidic carbon acid moieties onto the surfaces of materials without tedious chemical treatments., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A chelating fabric was prepared by graft polymerization of glycidyl methacrylate (GMA) onto a nonwoven fabric, followed by attachment reaction of N-methyl-D-glucamine (NMDG) using an organic solvent-free process. The graft polymerization was performed by immersing the gamma-ray pre-irradiated fabric into the GMA emulsion, while the attachment reaction was carried out by immersing the grafted fabric in the NMDG aqueous solution. The chelating capacity of the chelating fabric prepared by reaction in the NMDG aqueous solution without any additives reached 1.74 mmol/g, which further increased to above 2.0 mmol/g when surfactant and acid catalyst were added in the solution. The boron chelation of the chelating fabric was evaluated in a batch mode. Fourier transform infrared spectrophotometer (FTIR) was used to characterize the fabrics. The chelating fabric can quickly chelate boron from water to form a boron ester, and a high boron chelating ability close to 18.3 mg/g was achieved in the concentrated boron solution. The chelated boron can be eluted completely by HCl solution. The regeneration and stability of the chelating fabric were tested by 10 cycles of the chelation-elution operations. Considering the organic solvent-free preparation process and the high boron chelating performance, the chelating fabric is promising for the boron removal from water.

A nonwoven fabric adsorbent loaded with 2-ethylhexyl hydrogen-2-ethylhexylphosphonate (EHEP) was developed for the separation and recovery of dysprosium (Dy) and neodymium (Nd) from an aqueous solution. The adsorbent was prepared by the radiation-induced graft polymerization of a methacrylate monomer with a long alkyl chain onto a nonwoven fabric and the subsequent loading of EHEP by hydrophobic interaction and chain entanglement between the alkyl chains. The adsorbent was evaluated by batch and column tests with a Dy (III) and Nd (III) aqueous solution. In the batch tests, the adsorbent showed high Dy (III) adsorptivity close to 25.0 mg/g but low Nd (III) adsorptivity below 1.0 mg/g, indicating that the adsorbent had high selective adsorption. In particular, the octadecyl methacrylate (OMA)-adsorbent showed adsorption stability in repeated tests. In the column tests, the OMA-adsorbent was also stable and showed high Dy (III) adsorptivity and high selectivity in repeated adsorption-elution circle tests. This result suggested that the OMA-adsorbent may be a promising adsorbent for the separation and recovery of Dy (III) and Nd (III) ions.

Visualizing the dynamics of cesium (Cs) is desirable to understand the impact of radiocesium when accidentally ingested or inhaled by humans. However, visualization of radiocesium in vivo is currently limited to plants. Herein, we describe a method for the production and purification of 127 Cs and its use in visualizing Cs dynamics in a living animal. The positron-emitting nuclide 127 Cs was produced using the 127 I (α, 4n) 127 Cs reaction, which was induced by irradiation of sodium iodide with a 4 He 2+ beam from a cyclotron. We excluded sodium ions by using a material that specifically adsorbs Cs as a purification column and successfully eluted 127 Cs by flowing a solution of ammonium sulfate into the column. We injected the purified 127 Cs tracer solution into living rats and the dynamics of Cs were visualized using positron emission tomography; the distributional images showed the same tendency as the results of previous studies using disruptive methods. Thus, this method is useful for the non-invasive investigation of radiocesium in a living animal.

A fibrous grafted metal adsorbent with a piperazinyl-dithiocarbamate (PZ-DTC) group was synthesized by radiation-induced emulsion grafting of glycidyl methacrylate onto a polyethylene-coated polypropylene nonwoven fabric (PE/PP-NF) and subsequent three-step chemical modifications consisting of amination with N -( tert -butoxycarbonyl)piperazine ( N -Boc-piperazine, NBPZ), deprotection of the Boc group with HCl, and dithiocarbamation with carbon disulfide (CS 2 ). By using the NBPZ reagent in the amination step, the self-cross-linking of piperazine (PZ) could be completely suppressed, unlike using the PZ reagent. Consequently, the PZ-DTC group density of the fibrous grafted metal adsorbent synthesized through NBPZ attained 2.122 mmol-PZ-DTC/g-adsorbent, which was approximately 6 times higher than that of the metal adsorbent synthesized through PZ. The fibrous grafted metal adsorbent with the PZ-DTC group selectively adsorbed heavy metal ions over light metal ions. Furthermore, it exhibited high adsorption capacity, particularly for Cu 2+ . The Cu 2+ adsorption capacity was determined to be 1.903 mmol-Cu 2+ /g-adsorbent by a batchwise adsorption test using a single-metal-ion aqueous solution at pH 6. The order of metal ion selectivity of the fibrous grafted metal adsorbent with the PZ-DTC group was Na + < Mg 2+ , Ca 2+ , Co 2+ , Cd 2+ < Pb 2+ ≪ Cu 2+ , and Co 2+ ≈ Ni 2+ < Zn 2+ ≪ Cu 2+ . In addition, the fibrous grafted metal adsorbent with the PZ-DTC group did not lose its metal adsorption function even under highly alkaline conditions (pH 15). It could recover Cu 2+ efficiently and selectively from a high-concentration Na + aqueous solution at this pH. The Cu 2+ adsorption capacity of the fibrous grafted metal adsorbent with the PZ-DTC group was 0.754 mmol-Cu 2+ /g-adsorbent under a highly alkaline condition, a 10 M NaOH aqueous solution at pH 15. This value was approximately 2.4 times higher than that of the other grafted adsorbent with an amine-type functional group., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

This paper investigates the selectivity of GMA-based-non-woven fabrics adsorbent towards copper ion (Cu) functionalized with several aliphatic amines. The aliphatic amines used in this study were ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA). The non-woven polyethylene/polypropylene fabrics (NWF) were grafted with glycidyl methacrylate (GMA) via pre-radiation grafting technique, followed by chemical functionalization with the aliphatic amine. To prepare the ion recognition polymer (IRP), the functionalized amine GMA-grafted-NWF sample was subjected to radiation crosslinking process along with the crosslinking agent, divinylbenzene (DVB), in the presence of Cu ion as a template in the matrix of the adsorbent. Functionalization with different aliphatic amine was carried out at different amine concentrations, grafting yield, reaction temperature, and reaction time to study the effect of different aliphatic amine onto amine density yield. At a concentration of 50% of amine and 50% of isopropanol, EDA, DETA, TETA, and TEPA had attained amine density around 5.12, 4.06, 3.04, and 2.56 mmol/g-ad, respectively. The amine density yield decreases further as the aliphatic amine chain grows longer. The experimental condition for amine functionalization process was fixed at 70% amine, 30% isopropanol, 60 °C for grafting temperature, and 2 h of grafting time for attaining 100% of grafting yield (Dg). The prepared adsorbents were characterized comprehensively in terms of structural and morphology with multiple analytical tools. An adsorptive removal and selectivity of Cu ion by the prepared adsorbent was investigated in a binary metal ion system. The IRP samples with a functional precursor of EDA, the smallest aliphatic amine had given the higher adsorption capacity and selectivity towards Cu ion. The selectivity of IRP samples reduces as the aliphatic amine chain grows longer, EDA to TEPA. However, IRP samples still exhibited remarkably higher selectivity in comparison to the amine immobilized GMA- g -NWF at similar adsorption experimental conditions. This observation indicates that IRP samples possess higher selectivity after incorporation of the ion recognition imprint technique via the radiation crosslinking process., Competing Interests: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

A simplified radiation-induced emulsion graft polymerization (SREG) method is proposed. This method involves a convenient and easy degassing process of a monomer solution using a commercially available sealed glass jar. A loaded weight on the lid of the jar was used to control the jar's internal pressure as the degassing of the monomer solution took place using a vacuum pump. The degassing method was highly reproducible, resulting from no bumping of the monomer solution. The initial grafting velocity was proportional to the absorbed doses of pre-irradiation between 5 and 20 kGy. This result indicates that dissolved oxygen was sufficiently eliminated from the monomer solution at such a level where the remaining oxygen had little effect on the grafting reaction at a dose of 5 kGy. The method was then applied to the fabrication of a heavy metal adsorbent that possessed a sufficient adsorption capacity of Co(II) ions. The SREG method is applicable to the fabrication of a wide variety of functional graft polymers because high-dose-rate gamma-ray radiation and expensive experimental equipment are not necessary.

In this manuscript, we present the successful attachment of crown ether moieties onto fluoropolymer surfaces, via the combination of radiation-induced graft polymerization and a subsequent surface Kabachnik-Fields three-component reaction. The obtained crown ether-tethered fluoropolymer films exhibited an ammonium cation capturing ability, owing to the host-guest interactions (i.e., hydrogen bonding) between the surface-anchored crown ethers and the guest ammonium cations., Competing Interests: The authors declare no conflict of interest.

To determine the molecular weight of graft chains in grafted films, the polystyrene graft chains of PVDF- g -St films synthesized by a pre-irradiation graft method are cleaved and separated by boiling xylene extraction. The analysis of the extracted material and the residual films by FTIR, nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC) analyses indicates that most graft chains are removed from the PVDF- g -St films within 72 h of extraction time. Furthermore, the molecular weight of the residual films decreases quickly within 8 h of extraction and then remains virtually unchanged up to 72 h after extraction time. The degradation is due to the cleavage of graft bonds, which is mainly driven by the thermal degradation and the swelling of graft chains in solution. This allows determination of the molecular weight of graft chains by GPC analysis of the extracted material. The results indicate that the PVDF- g -St prepared in this study has the structure where one or two graft chains hang from each PVDF backbone., Competing Interests: The authors declare no conflict of interest.

In an effort to elucidate the deposition pathway of Pd in river sediments, we analyzed the amount of Pd in the river water and sediments of the Yukawa and Yazawa rivers, as well as in the sediments of the Shinaki dam-lake of the Kusatsu hot-spring area, which is located northwest in Gunma Prefecture of Japan. The crystal structures and elemental compositions of the river sediment samples differed significantly before and after neutralization. This was attributed to the lime input, which also affected the Pd abundance ratio obtained by the sequential extraction procedure. Additionally, the low leachability of Pd in the sediment suggested possible difficulties in its recovery. Considering the analysis of the Pd variation in the environments, it was concluded that the Pd content in the sediment of the Shinaki dam-lake was mainly supplied by the Yukawa river water inflowing the surrounding tributary rivers and hot-spring waters before neutralization, rather than the lime input.

To remove chromium from wastewater effectively, two types of nitrogen-containing fabric adsorbents, having amidoxime ligand groups and quaternary ammonium anion exchange groups, respectively, were prepared by radiation grafting. In brief, the amidoxime adsorbent is obtained by grafting of acrylonitrile (AN)/methacrylic acid (MAA) onto a nonwoven fabric and subsequent amidoximation with hydroxylamine, while the ammonium adsorbent is obtained by grafting of chloromethylstyrene (CMS) followed by quaternization with trimethylamine. The AN/MAA-grafting reaches a high degree of grafting more than 100%, and the resulting amidoxime adsorbent reaches a high amidoxime density of 4.53 mmol/g. On the other hand, the CMS-grafting reaches a much higher degree of grafting above 200%, and the resulting ammonium adsorbent reaches a high ammonium density of 3.51 mmol/g. FTIR/ATR and TGA/DTA are used for the characterization of the grafted fabrics as well as the relevant fabric adsorbents. Furthermore, the chromium removal of the prepared fabric adsorbent is tested in both batch and column modes. It has been confirmed that the chromium removal was largely dependent on the pH of the solution. At pH 5.0, the amidoxime adsorbent shows a high Cr(III) adsorption capacity of 31.68 mg/g, while the ammonium adsorbent shows a much higher Cr(VI) adsorption capacity of 130.65 mg/g.

Reversible addition-fragmentation chain transfer (RAFT) agent was added into a simultaneous radiation grafting system and its effects on graft polymerization and homopolymerization were investigated. Chloromethylstyrene (CMS) was graft polymerized onto ethylene-tetrafluoroethylene copolymer (ETFE) films under γ-ray sources via simultaneous irradiation. The non-grafted poly(CMS) in the grafted films were extracted by xylene at 120 °C. The poly(CMS) was characterized by NMR and GPC instruments. Addition of the RAFT agent suppressed both graft polymerization and homopolymerization. However, under a high concentration of RAFT agent, the homopolymerization in the monomer solution could occur through a typical RAFT polymerization while polymerization in the ETFE films proceeded via RAFT and conventional radical polymerization, resulting in poly(CMS) in the ETFE films with molecular weight dispersity higher than 1.0 but lower than that without RAFT agent. Furthermore, it was found that the molecular weight of the poly(CMS) in the ETFE films was several times higher than that of the poly(CMS) in the monomer solution., Competing Interests: The authors declare no conflict of interest.

Background: Omalizumab is effective and well-tolerated in children with moderate to severe allergic asthma. However, the effects of long-term treatment with omalizumab in this population haven't been well investigated. The objective of this study is to evaluate the long-term safety, efficacy, pharmacokinetics and pharmacodynamics of omalizumab in children with uncontrolled severe asthma., Methods: Thirty-eight Japanese children (aged 7-16 years) who completed the 24-week treatment core study were included in an uncontrolled extension study, in which treatment with omalizumab continued until the pediatric indication was approved in Japan (ClinicalTrials.gov number: NCT01328886)., Results: Thirty-five patients (92.1%) completed the extension study. The median exposure throughout the core and extension studies was 116.6 weeks (range, 46.9-151.1 weeks). The most common adverse events were nasopharyngitis, influenza, upper respiratory tract infection, and asthma. Serious adverse events developed in 10 patients (26.3%), but resolved completely with additional treatments. Incidence of adverse events didn't increase with extended exposure with omalizumab. Twenty-nine patients (76.3%) achieved completely- or well-controlled asthma compared with 9 patients (23.7%) at the start of the extension study. QOL scores, the rates (per year) of hospitalizations and ER visits were significantly improved compared with the baseline of the core study [39.0 vs 48.0 (median), p < 0.001 for QOL, 1.33 vs 0.16, p < 0.001 for hospitalization, 0.68 vs 0.15, p = 0.002 for ER visits]. Remarkably, the mean total IgE level showed a decreasing trend while exposure to omalizumab remained at steady-state., Conclusions: Long-term treatment with omalizumab is well-tolerated and effective in children with uncontrolled severe allergic asthma. No new safety findings were identified., (Copyright © 2017 Japanese Society of Allergology. Production and hosting by Elsevier B.V. All rights reserved.)

Lysosomal trapping was investigated in the retinal capillary endothelial cells that are responsible for the inner blood-retinal barrier (BRB) using LysoTracker(®) Red (LTR). Using confocal microscopy on TR-iBRB2 cells, an in vitro model of the inner BRB, the presence of lysosomal trapping in retinal capillary endothelial cells was suggested since TR-iBRB2 cells exhibited punctuate intracellular localization of LTR that was attenuated by NH4Cl treatment. The study confirmed that LTR uptake by retinal capillary endothelial cells took place in a time- and temperature-dependent manner, and exhibited the 1.58-fold greater uptake at pH 8.4 than that at pH 7.4 while there was no change in uptake between pH 6.4 and pH 7.4, suggesting that passive diffusion is not enough to explain LTR uptake. The inhibition study showed the possible influence of lysosomal trapping on cationic drug transport by retinal capillary endothelial cells since LTR uptake was significantly inhibited by cationic amphiphilic drugs. Inhibition profiling and the estimation of IC50 suggested the influence of lysosomal trapping on propranolol and low-affinity pyrilamine transport while lysosomal trapping had only a partial effect on verapamil, clonidine, nicotine and high-affinity pyrilamine transport in retinal capillary endothelial cells.

Background: Omalizumab has demonstrated clinical benefits in children with moderate to severe allergic asthma. However, no studies have been performed in Japanese asthmatic children. The aim of this study was to evaluate the efficacy including free IgE suppression and safety of omalizumab in Japanese children with severe allergic asthma. The primary objective was to examine whether omalizumab decreases serum free IgE levels to less than 25 ng/ml (target level of suppression)., Methods: Thirty-eight Japanese children (6-15 years) with uncontrolled severe allergic asthma despite inhaled corticosteroids (>200 μg/day fluticasone propionate or equivalent) and two or more controller therapies received add-on treatment with omalizumab in a 24-week, multicenter, uncontrolled, open-label study., Results: The geometric mean serum free IgE level at 24 weeks was 15.6 ng/mL. Compared with baseline, total asthma symptom scores, daily activity scores and nocturnal sleep scores at 24 weeks were significantly improved. The rates of asthma exacerbation and hospitalization due to asthma were reduced by 69.2% and 78.2%, respectively (p < 0.001), versus baseline. Quality-of-life scores were also significantly improved (p < 0.001). In addition, 11 (28.9%) patients reduced the dose of any asthma controller medications. Thirty-six (94.7%) patients experienced at least one adverse event during the treatment period. All adverse events were mild or moderate in severity and no new safety concerns were detected. No patients discontinued the study., Conclusions: In Japanese children with severe allergic asthma, omalizumab decreased free IgE levels to less than 25 ng/mL. Omalizumab improved asthma control and was well-tolerated, as well., (Copyright © 2015 Japanese Society of Allergology. Production and hosting by Elsevier B.V. All rights reserved.)

Colorectal cancer (CRC) is one of the leading causes of cancer-related deaths worldwide. We previously performed Serial Analysis of Gene Expression (SAGE) on four primary gastric cancer samples and identified several gastric cancer-specific genes. Of these genes, olfactomedin 4 (OLFM4, also known as GW112 or hGC-1) is a candidate gene for cancer-specific expression. In the present study, we examined the expression and distribution of olfactomedin 4 in CRC by immunohistochemistry. Of the 176 CRC cases, 59 (34%) were positive for cytoplasmic staining of olfactomedin 4. Olfactomedin 4-positive CRC cases showed earlier T classification (P=0.0180), N classification (P=0.0149) and stage (P=0.0144) than olfactomedin 4-negative CRC cases. In the 176 CRC patients, those with olfactomedin 4-positive CRC had a better survival rate than patients with olfactomedin 4-negative CRC (P=0.0092). Multivariate analysis indicated that T classification, M classification and negative olfactomedin 4 expression were independent predictors of survival in patients with CRC. In addition to cytoplasmic staining of olfactomedin 4, stromal staining at the invasive front was observed. In total, 29 (16%) of the 176 CRC cases were positive for stromal olfactomedin 4; however, stromal olfactomedin 4 staining was not correlated with any clinicopathologic characteristic or with patient survival. These results indicate that olfactomedin 4 is a valuable marker for long-term survival in patients with CRC.

The effect of cutaneous metabolism on the skin penetration of drugs was analyzed based on a two-layer skin diffusion/metabolism model. In vitro permeation studies of propylparaben and butylparaben with or without an esterase inhibitor, diisopropyl fluorophosphate (DFP), were performed. Pretreatment of the skin with DFP prolonged the lag time for the penetration of intact parabens. Additionally, DFP significantly decreased the total flux of butylparaben, but not that of propylparaben. Model analysis of the penetration profiles revealed that DFP inhibits the cutaneous metabolism without affecting any other processes. To comprehensively understand the relationships among lipophilicity, metabolic rate, and skin permeation of drugs, simulation studies were performed with newly derived equations concerning the permeability coefficient and the lag time for the penetration of both intact and metabolite forms. The analysis revealed that the lag time for the penetration of both intact and metabolite forms becomes shorter with increasing metabolic rate. As the metabolic rate of the drug increases, skin penetration of the intact form decreases whereas that of the metabolite increases. The total flux of intact and metabolite forms increases with increasing metabolic rate, being more obvious for highly lipophilic drugs. This indicates that the permeation of lipophilic compounds such as butylparaben is more highly affected by cutaneous metabolism in the viable layer because these compounds easily penetrate the stratum corneum layer. Consequently, the balance between the permeability of drug across the stratum corneum and the dermis has been implicated to impose a significant influence on the percutaneous absorption of drugs subjected to cutaneous metabolism.

Diphenylimidazole and diphenylthiazole derivatives were synthesized and tested as inhibitors of platelet aggregation in in vitro experiments with the rabbit. Diphenylthiazole derivatives (10) were more potent than diphenylimidazole derivatives (4) in inhibiting arachidonic acid-induced platelet aggregation of rabbit platelet-rich plasma. Two diphenylimidazole and eight diphenylthiazole derivatives were evaluated for ex vivo arachidonic acid and collagen-induced platelet aggregation inhibitory activity using guinea pigs. In these compounds, 4,5-bis(4-methoxyphenyl)-2-(1,5-dimethyl-2-pyrrolyl)thiazole (10n) showed strong activity in vitro and ex vivo. The ex vivo activity of 10n was 200 times stronger than that of aspirin. The mechanism of the activity of 10n was the inhibition of cyclo-oxygenase.