Crosslinking of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) anion exchange membranes, which can be used for capacitive deionization (CDI), was investigated. PPO Anion exchange polymer was prepared through bromination and amination reaction steps and crosslinked with bisphenol A diglycidylether (BADGE), m-phenylenediamine (m-PDA), and hexamethylenediamine (HMDA). The gelation time by crosslinking was short in the order of HMDA > m-PDA > BADGE. The anion exchange membranes crosslinked at room temperature over a certain amount of crosslinking agent did not dissolve in an aprotic solvent such as 1-methylpyrrolidone (NMP) and the chemical durability of their membranes to organic solvent increased. The ion exchange capacity and water uptake of anion exchange membranes crosslinked with different crosslinker (BADGE) contents were measured and compared. The CDI performance of the crosslinked PPO anion exchange membrane immersed in the HMDA solution was almost the same as that of the non - crosslinked membrane except for the initial stage of the adsorption step.
Kim, Jeong-Ho;Kim, Tae-Hyung;Oh, Jung-Geun;Noh, Seok-Hwan;Lee, Jeong-Soo;Park, Kyu-Ho;Ha, Sam-Chul;Kang, Heon
Bulletin of the Korean Chemical Society
/
v.30
no.11
/
pp.2589-2594
/
2009
Aging phenomena of plasma polymer films were studied by using the surface analysis techniques of contact angle measurement, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOFSIMS), and atomic force microscopy (AFM). The polymer films were grown on an aluminum substrate by using a plasma polymerization method from a gas mixture of acetylene and helium, and the films were subsequently modified to have a hydrophilic surface by oxygen plasma treatment. Aging of the polymer films was examined by exposing the samples to water and air environments. The aging process increased the hydrophobicity of the surface, as revealed by an increase in the advancing contact angle of water. XPS analysis showed that the population of oxygen-containing polar groups increased due to the uptake of oxygen during the aging, whereas TOF-SIMS analysis revealed a decrease in the polar group population in the uppermost surface layer. The results suggest that the change in surface property from hydrophilic to hydrophobic nature results from the restructuring of polymer chains near the surface, rather than compositional change of the surface. Oxidative degradation may enhance the mobility and the restructuring process of polymer chains.
Proton conducting crosslinked membranes were prepared using polymer blends of polystyrene-b-poly(hydroxyethyl acrylate)-b-poly(styrene sulfonic acid) (PS-b-PHEA-b-PSSA) and poly(vinyl alcohol) (PVA). PS-b-PHEA-b-PSSA triblock copolymer at 28:21:51 wt% was synthesized sequentially using atom transfer radical polymerization (ATRP). FT-IR spectroscopy showed that after thermal ($120^{\circ}C$, 2 h) and chemical (sulfosuccinic acid, SA) treatments of the membranes, the middle PHEA block of the triblock copolymer was crosslinked with PVA through an esterification reaction between the -OH group of the membrane and the -COOH group of SA. The ion exchange capacity (IEC) decreased from 1.56 to 0.61 meq/g with increasing amount of PVA. Therefore, the proton conductivity at room temperature decreased from 0.044 to 0.018 S/cm. However, the introduction of PVA resulted in a decrease in water uptake from 87.0 to 44.3%, providing good mechanical properties applicable to the membrane electrode assembly (MEA) of fuel cells. Transmission electron microscopy (TEM) showed that the membrane was microphase-separated with a nanometer range with good connectivity of the $SO_3H$ ionic aggregates. The power density of a single $H_2/O_2$ fuel cell system using the membrane with 50 wt% PVA was $230\;mW/cm^2$ at $70^{\circ}C$ with a relative humidity of 100%. Thermogravimetric analysis (TGA) also showed a decrease in the thermal stability of the membranes with increasing PVA concentration.
Magnetite was chosen as a typical adsorbent to study its phosphate adsorption capacity in water body with low concentration of phosphorus (below $2mg\;PL^{-1}$). Magnetite was collected from Luoyang City, Henan Province, China. In this research, three factors have been studied to describe the adsorption of phosphate on magnetite, which was solution concentration (concentration ranging from 0.1 to $2.5mg\;PL^{-1}$), suspension pH (1 to 13) and temperature (ranging from $10^{\circ}C$ to $40^{\circ}C$). In addition, the modified samples had been characterized with XRD and FE-SEM image. The results show that iron ions contains in magnetite were the main factors of phosphorus removal. The behavior of phosphorus adsorption to substrates could be fitted to both Langmuir and Freundlich isothermal adsorption equations in the low concentration phosphorus water. The theoretical saturated adsorption quantity of magnetite is 0.158 mg/g. pH has great influence on the phosphorus removal of magnetite ore by adsorption. And pH of 3 can receive the best results. While temperature has little effect on it. Magnetite was greatly effective for phosphorus removal in the column experiments, which is a more practical reflection of phosphorous removal combing the adsorption isotherm model and the breakthrough curves. According to the analysis of heavy metals release, the release of heavy metals was very low, they didn't produce the secondary pollution. The mechanism of uptake phosphate is in virtue of chemisorption between phosphate and ferric ion released by magnetite oxidation. The combined investigation of the magnetite showed that it was better substrate for water body with low concentration of phosphorus.
To adapt to environmental changes and to maintain cellular homeostasis, microorganisms adjust the intracellular concentrations of biochemical compounds, including metal ions; these are essential for the catalytic function of many enzymes in cells, but excessive amounts of essential metals and heavy metals cause cellular damage. Metal-responsive transcriptional regulators play pivotal roles in metal uptake, pumping out, sequestration, and oxidation or reduction to a less toxic status via regulating the expression of the detoxification-related genes. The sensory and regulatory functions of the metalloregulators have made them as attractive biological parts for synthetic biology, and the exceptional sensitivity and selectivity of metalloregulators toward metal ions have been used in heavy metal biosensors to cope with prevalent heavy metal contamination. Due to their importance, substantial efforts have been made to characterize heavy metal-responsive transcriptional regulators and to develop heavy metal-sensing biosensors. In this review, we summarize the biochemical data for the two major metalloregulator families, SmtB/ArsR and MerR, to describe their metal-binding sites, specific chelating chemistry, and conformational changes. Based on our understanding of the regulatory mechanisms, previously developed metal biosensors are examined to point out their limitations, such as high background noise and a lack of well-characterized biological parts. We discuss several strategies to improve the functionality of the metal biosensors, such as reducing the background noise and amplifying the output signal. From the perspective of making heavy metal biosensors, we suggest that the characterization of novel metalloregulators and the fabrication of exquisitely designed genetic circuits will be required.
A simple solvothermal reaction was used to prepare a 3-aminopropyl-functionalized silica-gel-based adsorbent for adsorbing Pd(II) from the nitric acid solution. Scanning electron microscopy, fourier transform infrared spectroscopy, and thermogravimetry analysis were performed on the as-synthesized adsorbent to demonstrate the successful introduction of Schiff base groups. Batch experiments were used to investigate the effects of contact time, nitric acid concentration, solution temperature, and adsorption capacity. It is worth noting that the prepared adsorbent exhibited a higher affinity toward Pd(II) with the uptake approximately 100% even in a 2 M HNO3 solution. At an equilibrium time of 5 h, the maximum adsorption capacity of Pd(II) was estimated to be 0.452 mmol/g. The adsorbed Pd(II) could be completely eluted by dissolving 0.2 M thiourea solution in 0.1 M HNO3. Using a combination of particle-induced X-ray emission analysis and an X-ray photoelectron spectrometer, the adsorbed Pd was found to be uniformly distributed on the surface of the prepared adsorbent and the existing species were Pd(II) and zero-valent Pd(0). Due to the desirable performances, facile preparation method, and abundant raw material source, the prepared adsorbent demonstrated a high application potential in the recovery of Pd(II) from simulated high-level liquid waste treatment.
Adsorption behavior of Cu onto Hwangto, from Pankok-ri, Kosung-gun, suspension was studied using Cu batch adsorftion experiment and computer program MINTEQA2 and FITEQL 3.2. The sorption of copper was investigated as a function of pH, copper concentration and $NaNO_3$ background concentration (0.01 and 0.1 M). The concentration of copper was analyzed using ICP-AES. The sorption of copper onto Hwangto suspension increased with increasing pH and copper concentration. The adsorption percentage of copper drastically increased from pH 5.5 to 6.5, and reached nearly 100% at pH 7.5. Because the amount of copper solution and the ionic strength of background electrolyte may not affect the sorption of copper onto Hwangto, the copper ion may be combined at the surface of Hwangto as an inner-sphere complex. Using the MINTEQA2 program, the speciation of copper was calculated as a function of pH and copper concentration. The concentration of $Cu^{2+}$ decreased and that of $Cu(OH)_2$ increased with increasing pH. The uptake of copper in the Hwangto suspension was simulated by FITEQL3.2 program using two sites-three pKas model, which is composed of silicate reaction site and Fe oxide reaction site. The copper absorption reaction constants were calculated in the case of 2~6 mL of copper solution. The Fe oxide reaction site rapidly adsorbs copper ion between pH 4.5~6.5. Silicate reaction site adsorbs little copper ion at low copper concentration but much at high copper concentration. The removal amount of copper by precipitation was negligible in comparison with that of adsorption. The Fe oxide reaction site may has higher adsorption affinity of copper ion than silicate reaction site.
Park, Young-Il;Kim, Hee-Guen;Kim, Yoo-Young;Kim, In-Soo
Applied Biological Chemistry
/
v.39
no.6
/
pp.494-500
/
1996
Uptake of hen metal ions by water dropwort (Oenanthe stolonifera DC.) and its cadmium-binding protein were studied to probe for good method to remove heavy metal contaminants from environments. The plant was cultured in the culture medium (pH 7.0) containing the various concentrations of $Cd^{2+}$, $Cr^{3+}$ or $Pb^{2+}$, for 3 and 7 days. The residual heavy metals deposited in roots linearly increased as the metal ions concentration increased up to 17 ppm for $Cd^{2+}$, 20 ppm for $Cr^{3+}$ and 50 ppm for $Pb^{2+}$. Above these concentrations, the plant growth was inhibited and the uptake rates of the metal ions decreased. The heavy metals absorbed by the plant were mostly deposited in roots. In particular, the residual concentration of lead in roots was about four times higher than those of cadmium and chromium. When cultured in the medium containing 20 ppm of each metal ion, 80% of cadmium, 90% of cromium and 96% of lead were deposited in roots out of the total residual metal ions in the plant. These values correspond to 6.1 mg of cadmium, 5.2 mg of chromium and 23.6 mg of lead per one gram of roots tissue on a dry weight basis. A cadmium-binding protein was partially purified by extraction, gel filtration and DEAE-Cellulose chromatography from water dropworts that was grown in the medium containing 20 ppm $Cd^{2+}$. The purified protein was a single band on SDS- and non-denaturing- polyacrylamide gel electrophoresis. Its molecular mass was estimated to be ca. 5,000 dalton by gel filteration. Analysis of amino acid composition of the protein indicated that it had a typical amino acid composition of heavy metal-binding protein in that it contained 27% of acidic amino acids and 9.9% of cysteine. However, it is likely that the protein is a new plant metal-binding protein, since its amino acid composition is somewhat different from those of phytochelatins that have been known so far.
Attenuation correction is important in producing quantitative positron emission tomography (PET) images. Conventionally, photon attenuation effects are corrected using transmission measurements performed before tracer administration. The pre-injection transmission measurement approach may require a time delay between transmission and emission scans for the tracer studies requiring a long uptake period, about 45 minutes for F-18 deoxyglucose study. The time delay will limit patient throughput and increase the likelihood of patient motion. A technique lot performing simultaneous transmission and emission scans (T+E method) after the tracer injection has been validated. The T+E method substracts the emission counts contaminating the transmission measurements to produce accurate attenuation correction coefficients. This method has been evaluated in experiments using a cylindrical phantom filled with background water (5750 cc) containing $0.4{\mu}Ci/cc$ of F-18 fluoride ion and one insert cylinder (276 cc) containing $4.3{\mu}Ci/cc$. GE $Advance^{TM}$ PET scanner and Ge-68 rotating pin sources for transmission scanning were used for this investigation. Post-injection transmission scan and emission scan were peformed alternatively over time. The error in emission images corrected using post-infection transmission scan to emission images corrected transmission scan was 2.6% at the concentration of $1.0{\mu}Ci/cc$. No obvious differences in image quality and noise were apparent between the two images. The attenuation correction can be accomplished with post-injection transmission measurement using rotating pin sources and this method can significantly shorten the time between transmission and omission scans and thereby reduce the likelihood of patient motion and increase scanning throughput in PET.
The physiological and biochemical role of potassium for upland crops according to recent research reports and the nutritional status of potassium in Korea were reviewed. Since physical and chemical characteristics of potassium ion are different from those of sodium, potassium can not completely be replaced by sodium and replacement must be limited to minimum possible functional area. Specific roles of potassium seem to keep fine structure of biological membranes such as thylacoid membrane of chloroplast in the most efficient form and to be allosteric effector and conformation controller of various enzymes principally in carbohydrate and protein metabolism. Potassium is essential to improve the efficiency of phoro- and oxidative- phosphorylation and involve deeply in all energy required metabolisms especially synthesis of organic matter and their translocation. Potassium has many important, physiological functions such as maintenance of osmotic pressure and optimum hydration of cell colloids, consequently uptake and translocation of water resulting in higher water use efficiency and of better subcellular environment for various physiological and biochemical activities. Potassium affects uptake and translocation of mineral nutrients and quality of products. potassium itself in products may become a quality criteria due to potassium essentiality for human beings. Potassium uptake is greatly decreased by low temperature and controlled by unknown feed back mechanism of potassium in plants. Thus the luxury absorption should be reconsidered. Total potassium content of upland soil in Korea is about 3% but the exchangeable one is about 0.3 me/100g soil. All upland crops require much potassium probably due to freezing and cold weather and also due to wet damage and drought caused by uneven rainfall pattern. In barley, potassium should be high at just before freezing and just after thawing and move into grain from heading for higher yield. Use efficiency of potassium was 27% for barley and 58% in old uplands, 46% in newly opened hilly lands for soybean. Soybean plant showed potassium deficiency symptom in various fields especially in newly opened hilly lands. Potassium criteria for normal growth appear 2% $K_2O$ and 1.0 K/(Ca+Mg) (content ratio) at flower bud initiation stage for soybean. Potassium requirement in plant was high in carrot, egg plant, chinese cabbage, red pepper, raddish and tomato. Potassium content in leaves was significantly correlated with yield in chinese cabbage. Sweet potato. greatly absorbed potassium subsequently affected potassium nutrition of the following crop. In the case of potassium deficiency, root showed the greatest difference in potassium content from that of normal indicating that deficiency damages root first. Potatoes and corn showed much higher potassium content in comparison with calcium and magnesium. Forage crops from ranges showed relatively high potassium content which was significantly and positively correlated with nitrogen, phosphorus and calcium content. Percentage of orchards (apple, pear, peach, grape, and orange) insufficient in potassium ranged from 16 to 25. The leaves and soils from the good apple and pear orchards showed higher potassium content than those from the poor ones. Critical ratio of $K_2O/(CaO+MgO)$ in mulberry leaves to escape from winter death of branch tip was 0.95. In the multiple croping system, exchangeable potassium in soils after one crop was affected by the previous crops and potassium uptake seemed to be related with soil organic matter providing soil moisture and aeration. Thus, the long term and quantitative investigation of various forms of potassium including total one are needed in relation to soil, weather and croping system. Potassium uptake and efficiency may be increased by topdressing, deep placement, slow-releasing or granular fertilizer application with the consideration of rainfall pattern. In all researches for nutritional explanation including potassium of crop yield reasonable and practicable nutritional indices will most easily be obtained through multifactor analysis.
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