Peroxide stabilizers remarkably increase the longevity of thermally activated peroxydisulfate for enhanced ISCO remediation.

Thermally activated peroxydisulfate In Situ Chemical Oxidation (TAP-ISCO) is often applied for the remediation of soil-sorbed hydrophobic organic contaminants (HOCs) and nonaqueous phase liquids (NAPLs), which act as long-term sources of groundwater contamination. TAP-ISCO benefits from improved desorption/dissolution of organic contaminants into the aqueous phase and efficient activation of peroxydisulfate at elevated temperatures, but the primary limitation of TAP-ISCO is the short lifetime of peroxydisulfate (therefore the availability of reactive radical species). To resolve this problem, coupling of peroxide stabilizers with TAP were tested. The compatibility of seven representative commercial organic and inorganic peroxide stabilizers, including sodium stannate, trisodium phosphate, sodium pyrophosphate, sodium silicate, sodium citrate, ethylene diamine tetra methylene phosphonic acid and ethylenediaminetetraacetic acid disodium salt, with TAP in aqueous solutions and solutions containing goethite or soil particles were first studied. The effects of stabilizers on the formation, distribution and reactivity of reactive oxygen species were then investigated through electron paramagnetic resonance (EPR) spin-trapping experiments using 5,5-dimethyl-1-pyrroline-N-oxide, chemical probe experiments using anisole, nitrobenzene and hexachloroethane, and biphasic trichloroethylene (TCE) dense nonaqueous phase liquids (DNAPLs) TAP-ISCO mimicking experiments. The results indicate that organic stabilizers significantly accelerate peroxydisulfate decomposition at both ambient and elevated temperatures. In contrast, inorganic stabilizers can markedly increase peroxydisulfate longevity by suppressing the acid-catalyzed peroxydisulfate decomposition, quenching radical-chain acceleration, and sequestering transition metal species. In addition, TAP systems containing inorganic stabilizers can effectively generate a variety of reactive radical species, including SO4•-, HO•, and O2•-, and improve the oxidation of anisole and nitrobenzene, though suppressing the reduction of hexachloroethane to some extent. Especially, suitable inorganic stabilizers (e.g., trisodium phosphate) can effectively improve TAP oxidation of TCE DNAPL while suppressing peroxydisulfate decomposition. Overall, this study provides the fundamental basis of coupling TAP-ISCO with peroxide stabilizers.

Critical roles of sulfidation solvent in controlling surface properties and the dechlorination reactivity of S-nZVI.

Sulfidation of nanoscale zero-valent iron (nZVI) has been frequently applied to enhance its reactivity, selectivity, and electron utilization efficiency. However, sulfidation of nZVI is generally carried out in aqueous solution, and formation of passivated iron (hydro)oxide species on the surface of S-nZVI due to the reaction between nZVI and water is inevitable. To mitigate this issue, sulfidation of nZVI with hydrogen sulfide dissolved in absolute ethanol was developed. The properties of the resultant S-nZVI, denoted as S-nZVI-H2S-Ethanol, were compared with S-nZVIs prepared through sulfidation of nZVI with aqueous hydrogen sulfide (S-nZVI-H2S-Water) and aqueous sodium sulfide (S-nZVI-Na2S-Water). S-nZVI-H2S-Ethanol shows increased BET specific surface, reduced susceptibility to incidental oxidation, increased reduction potential, decreased electron-transfer resistance, and improved reactivity toward the reduction of trichloroethylene, compared with S-nZVI-Na2S-Water and S-nZVI-H2S-Water. The results highlight the critical roles of sulfidation solvent in controlling the structure, the physicochemical and electrochemical properties, and the dechlorination reactivity of S-nZVI. In addition, these findings offer fundamental mechanistic insights into the sulfidation processes of nZVI by sulfides, suggesting that solvent-iron (hydro)oxide and sulfide-iron (hydro)oxide interactions at the solvent/nZVI interface play key roles in regulating the sulfidation of nZVI and the properties of S-nZVI.

Multifunctional nano-cellulose composite films with grape seed extracts and immobilized silver nanoparticles.

Nowadays, traditional packaging films with weak activity or single function cannot satisfy the active packaging requirements. In this paper, novel multifunctional films (TNC/GSE/AgNPs) based on TEMPO-oxidized nano-cellulose (TNC), grape seed extract (GSE) and TNC immobilized silver nanoparticles (TNC@AgNPs) are reported. The results showed that transparent TNC/GSE/AgNPs films exhibited better mechanical properties, lower water vapor permeability and oxygen permeability compared to pure TNC films. Moreover, due to the effect of TNC immobilization on AgNPs, only 5.77%, 3.62% and 3.11% of AgNPs were released from TNC/GSE/AgNPs films under the pH 4.0, 6.9 and 9.2, respectively. Nevertheless, the films had good antimicrobial activity against E. coli and S. aureus. Moreover, TNC/GSE/AgNPs films showed strong antioxidant activity which has been evaluated by DPPH (6.87 µg Vc/mg d.w.) and TRAP (82.67 µg Trolox/mg d.w.) methods. The prepared films will exhibit multifunction as food packaging to extend storage period.

Functional and proteomic comparison of different techniques to produce equine anti-tetanus immunoglobulin F(ab')2 fragments.

Tetanus is still a major cause of human deaths in several developing countries. In particular, the neonatal form remains a significant public health problem. According to the World Health Organization, administration of tetanus toxoid is recommended for neonatal tetanus patients. Furthermore, tetanus antitoxin or anti-tetanus immunoglobulin (Ig) are used for mild case or intensive care. This paper discusses a novel purification technique for improving equine anti-tetanus Ig production. First, equine plasma dealt with two steps salting out with ammonium sulfate; second, ultrafiltration concentration liquid purified by one successive protein G based affinity chromatography steps; finally, the purified F(ab')2 fragments was characterized using biochemical and proteomic methods and shown to be pure and homogeneous. Compared with the original technique product, specific activity increased by 80% (about 90,000 IU/g) and recovery of F(ab')2 is approximately equal 75%. Furthermore, Proteomic profiling of total technique process is demonstrated by nano-HPLC-MS and bioinformatics analysis. New technique to produce equine anti-tetanus immunoglobulin F(ab')2 fragments from crude plasma in high quality and yield. And it also could be used for industrial amplification.

Compatibility of Surfactants and Thermally Activated Persulfate for Enhanced Subsurface Remediation.

Limited aqueous availability of hydrophobic organic contaminants and nonaqueous phase liquids in subsurface environment may seriously impair the effectiveness of traditional in situ chemical oxidation (ISCO). To tackle the issue, a combination of surfactants and thermally activated persulfate was proposed to enhance the aqueous availability and consequent oxidation of organic contaminants. The compatibility of eight representative nonionic, monovalent anionic, and divalent anionic surfactants with persulfate at various temperatures was first studied, to identify suitable surfactants that have high aqueous stability and low oxidant demands to couple with thermally activated persulfate. C12-MADS (sodium dodecyl diphenyl ether disulfonate, a representative divalent anionic surfactant) stands out as the most compatible surfactant. Batch treatability study with coal tar, an example of challenging scenarios for traditional ISCO, was then conducted. The results show that C12-MADS can significantly enhance not only the oxidation of polyaromatic hydrocarbons contained in coal tar but also oxidant utilization efficiency, indicating the potential of the proposed coupling process for the treatment of organic contaminants with low aqueous availability.

Ultrasound assisted, thermally activated persulfate oxidation of coal tar DNAPLs.

The feasibility of ultrasound assisted, thermally activated persulfate for effective oxidation of twenty 2-6 ringed coal tar PAHs in a biphasic tar/water system and a triphasic tar/soil/water system were investigated and established. The results indicate that ultrasonic assistance, persulfate and elevated reaction temperature are all required to achieve effective oxidation of coal tar PAHs, while the heating needed can be provided by ultrasonic induced heating as well. Further kinetic analysis reveals that the oxidation of individual PAH in the biphasic tar/water system follows the first-order kinetics, and individual PAH oxidation rate is primary determined by the mass transfer coefficients, tar/water interfacial areas, the aqueous solubility of individual PAH and its concentration in coal tar. Based on the kinetic analysis and experimental results, the contributions of ultrasound, persulfate and elevated reaction temperature to PAHs oxidation were characterized, and the effects of ultrasonic intensity and oxidant dosage on PAHs oxidation efficiency were investigated. In addition, the results indicate that individual PAH degradability is closely related to its reactivity as well, and the high reactivity of 4-6 ringed PAHs substantially improves their degradability.

In situ detection of salicylic acid binding sites in plant tissues.

The determination of hormone-binding sites in plants is essential in understanding the mechanisms behind hormone function. Salicylic acid (SA) is an important plant hormone that regulates responses to biotic and abiotic stresses. In order to label SA-binding sites in plant tissues, a quantum dots (QDs) probe functionalized with a SA moiety was successfully synthesized by coupling CdSe QDs capped with 3-mercaptopropionic acid (MPA) to 4-amino-2-hydroxybenzoic acid (PAS), using 1-ethyl-3-(3-dimethyllaminopropyl) carbodiimide (EDC) as the coupling agent. The probe was then characterized by dynamic light scattering and transmission electron microscopy, as well as UV/vis and fluorescence spectrophotometry. The results confirmed the successful conjugation of PAS to CdSe QDs and revealed that the conjugates maintained the properties of the original QDs, with small core diameters and adequate dispersal in solution. The PAS-CdSe QDs were used to detect SA-binding sites in mung bean and Arabidopsis thaliana seedlings in vitro and in vivo. The PAS-CdSe QDs were effectively transported into plant tissues and specifically bound to SA receptors in vivo. In addition, the effects of the PAS-CdSe QDs on cytosolic Ca(2+) levels in the tips of A. thaliana seedlings were investigated. Both SA and PAS-CdSe QDs had similar effects on the trend in cytosolic-free Ca(2+) concentrations, suggesting that the PAS-CdSe QDs maintained the bioactivity of SA. To summarize, PAS-CdSe QDs have high potential as a fluorescent probe for the in vitro/in vivo labeling and imaging of SA receptors in plants.

Degradation of dimethyl phthalate in solutions and soil slurries by persulfate at ambient temperature.

The degradation of dimethyl phthalate (DMP) by persulfate at ambient temperature (T=20-40°C) was investigated in aqueous solutions and soil slurries to assess the feasibility of using persulfate to remediate DMP contaminated soil and groundwater. First, the effects of temperature, initial oxidant concentration, initial DMP concentration and initial solution pH on the removal of DMP and TOC were studied in aqueous solutions. The results show that persulfate at 40°C can effectively mineralize DMP. Furthermore, dimethyl 4-hydroxyl phthalate, maleic acid and oxalic acid were identified as the degradation intermediates, and degradation pathways were proposed. Lastly, persulfate at 40°C was applied to remediate soil spiked with DMP at ∼ 600 mg/kg. The results show that persulfate at 40°C is highly effective for the remediation of DMP contaminated soil. Overall, this study provides fundamental and practical knowledge for the treatment of emerging phthalate esters (PAEs) contaminated soil and groundwater, as well as PAEs contaminated industrial wastewater, with persulfate at ambient temperature.

Impact of activation methods on persulfate oxidation of methyl tert-butyl ether.

To provide guidance on the selection of proper persulfate processes for the remediation of MTBE contaminated groundwater, MTBE aqueous solutions were treated with three common field persulfate processes including heat activated persulfate, Fe(III)-EDTA activated persulfate and alkaline persulfate, respectively. The results were compared with MTBE oxidation by Fenton's reagent and persulfate alone at 25°C. The impact of the activating conditions on the fate of MTBE and its daughter products was investigated. Heat activation at 40°C offered the most rapid removal of MTBE and its daughter products, while Fe(III)-EDTA activation showed higher efficiency of MTBE removal but low removal efficiency of its daughter products. On the other hand, alkaline persulfate showed slower kinetics for the removal of MTBE and less accumulation of the daughter products. Furthermore, tert-butyl alcohol and acetone were observed as the main purgeable daughter products along with a small amount of tert-butyl formate in persulfate oxidation of MTBE, while tert-butyl formate, tert-butyl alcohol and acetone were the main products in Fenton oxidation. Mechanistic analysis suggests that degradation of MTBE by persulfate most likely happens via non-oxygen demand pathways, different from the dominant oxygen demand degradation pathways observed in Fenton oxidation.

Decolourization of the azo dye Orange G in aqueous solution via a heterogeneous Fenton-like reaction catalysed by goethite.

Decolourization of the azo dye Orange G (OG) was investigated by using goethite/H2O2 as a heterogeneous Fenton-like reagent. Five principle operational parameters, namely pH, ion strength, concentrations ofgoethite (alpha-FeOOH) and hydrogen peroxide (H2O2), and reaction temperature, were taken into account to investigate how these controlling factors mediated OG decolourization. Goethite surfaces catalysed a Fenton-like reaction responsible for decolourizing OG following pseudo-first-order kinetics (R2 > 0.964). This process was effective but seriously impacted by the medium pH and the dosages of both alpha-FeOOH and H2O2. The decolourization efficiencies of OG increased with the decrease of solution pH and NaCl (chloride ion) concentration and/or the increase of H2O2. The acidic aqueous medium conditions were likely favourable due to the surface adsorption of the negatively charged OG leading to the promotion of decolourizing OG. The apparent activation energy (E) for this reaction was 42.18 kJ mol(-1), a relatively low value. This is consistent with the OG decolourization being enhanced with the reaction temperature increase.

Application of NaClO-treated multiwalled carbon nanotubes as solid phase extraction sorbents for preconcentration of trace 2,4-dichlorophenoxyacetic acid in aqueous samples.

Multiwalled carbon nanotubes functionalized by oxidation of original multiwalled carbon nanotubes with NaClO were prepared and their application as solid phase extraction sorbent for 2,4-dichlorophenoxyacetic acid (2,4-D) was investigated systemically, and a new method was developed for the determination of trace 2,4-D in water samples based on extraction and preconcentration of 2,4-D with solid phase extraction columns packed with NaClO-treated multiwalled carbon nanotubes prior to its determination by HPLC. The optimum experimental parameters for preconcentration of 2,4-D, including the column activating conditions, the amount of the sorbent, pH of the sample, elution composition, and elution volume, were investigated. The results indicated 2,4-D could be quantitatively retained by 100 mg NaClO-treated multiwalled carbon nanotubes at pH 5, and then eluted completely with 10 mL 3:1 (v/v) methanol-ammonium acetate solution (0.3 mol/L). The detection limit of this method for 2,4-D was 0.15 µg/L, and the relative standard deviation was 2.3% for fortified tap water samples and 2.5% for fortified riverine water sample at the 10 µg/L level. The method was validated using fortified tap water and riverine water samples with known amount of 2,4-D at the 0.4, 10, and 30 µg/L levels, respectively.

[Assessment of external methods of traditional Chinese medicine in patients with chronic ulcer of the lower extremities: study protocol of a multicenter, randomized, parallel-group, prospective trial].

BACKGROUND: Chronic ulcer of the lower extremities amounts for a grave and serious problem for public health. Western medicine focuses on controlling infection, improving blood circulation, surgical debridement, skin grafting, etc, but there are bottlenecks in the treatment. Traditional Chinese medicine (TCM) has a long history and a legacy of sound clinical efficacy in this area. TCM has developed a unique, effective external theory, and a large number of topical prescriptions and external technology. Through this research, a safe and effective treatment protocol of TCM for chronic ulcer of the lower extremities can be formed. To this end, during China's "Eleventh Five-Year" Plan, special research committees and projects on TCM external treatments and external technologies were established. This study on ulcer of the lower extremities constitutes one of the major research topics. METHODS AND DESIGN: Clinical information of patients with chronic ulcer of the lower extremities will be first collected in a large, multicenter, epidemiological survey. Concurrently, a large multicenter, randomized, parallel-group, prospective study will be launched based on evidence-based medical principles to evaluate the efficacy and safety of external methods for removing carrion, dissolving stasis, reinforcing deficiency and promoting tissue regeneration. The evaluated indexes will include the wound healing percentage for primary outcome, wound healing time, wound healing rate, time and rate of removal of necrotic tissue, and TCM syndromes for secondary outcomes and routine blood test, routine urine test, liver and kidney function, blood mercury content and finally urine mercury content for adverse events. DISCUSSION: In this trial, the authors will evaluate the efficacy and safety of external methods for removing carrion, dissolving stasis, reinforcing deficiency and promoting tissue regeneration in cases of chronic ulcer of the lower extremities for standardizing external therapy of TCM for treatment of this condition, and establishing the clinical assessment system for TCM. TRIAL REGISTRATION NUMBER: The research program was registered in the Chinese Clinical Trial Registry in both English and Chinese in June 2011. REGISTRATION NUMBER: ChiCTR-TRC-11001365.

Tridentate lysine-based fluorescent sensor for Hg(II) in aqueous solution.

A novel homoplastic podand fluorescent sensor based on flexible hydrophilic lysine was prepared. Lysine with two dansyl groups-appended at both ends supplied a possibility for a tridentate binding toward Hg(II) and finally resulted in a unique selectivity to Hg(II) over other transition-metal ions with a hypersensitivity (detection limit 2.0 nM) in neutral buffered aqueous solutions. Notably, the coordination of chloride ion to the complex of sensor-Hg(II) brought forth that the trend in the NMR chemical shift for hydrogen and carbon atoms of the sensor was contrary to the findings in the former reports, which shows upfield shifts for the hydrogens and the alkane carbons but downfield shifts for the dansyl carbons, respectively.

Degradation mechanisms of phoxim in river water.

Degradation of phoxim in river water was fully explored in this paper. Effects of pH, temperature, and photoirradiation on the degradation were investigated in detail. The results indicated that the degradation was characterized by a first-order process; UV irradiation and the increase of pH and temperature substantially accelerated the degradation. To fully characterize the degradation mechanism, HPLC-MS/MS was utilized to identify the degradation intermediates. Five intermediates were identified as phoxom, phoxom dimer, O,O,O',O'-tetraethyldithiopyrophosphate, O,O,O'-triethyl-O'-2-hydroxyethyldisulfinylpyrophosphate, and O,O,O'-triethyl-O'-2-hydroxyethyldithiopyrophosphate. On the basis of the results of the intermediate analysis, the degradation pathways of phoxim under the present experimental conditions were proposed. Through conversion of a thiophosphoryl into a phosphoryl group, some phoxim was converted to phoxom, most of which further formed dimer. Another portion of phoxim transformed to O,O,O',O'-tetraethyldithiopyrophosphate via nucleophilic substitution and photolysis. Thereafter, O,O,O',O'-tetraethyldithiopyrophosphate underwent hydroxylation to form O,O,O'-triethyl-O'-2-hydroxyethyldithiopyrophosphate or sulfur oxidation first and then hydroxylation to produce O,O,O'-triethyl-O'-2-hydroxyethyldisulfinylpyrophosphate. The understanding of phoxim's degradation mechanism in this study will be critical to its safety assessment and increase the understanding of the fate of phoxim in environment water.

Profiling mechanisms of alkane hydroxylase activity in vivo using the diagnostic substrate norcarane.

Mechanistically informative chemical probes are used to characterize the activity of functional alkane hydroxylases in whole cells. Norcarane is a substrate used to reveal the lifetime of radical intermediates formed during alkane oxidation. Results from oxidations of this probe with organisms that contain the two most prevalent medium-chain-length alkane-oxidizing metalloenzymes, alkane omega-monooxygenase (AlkB) and cytochrome P450 (CYP), are reported. The results--radical lifetimes of 1-7 ns for AlkB and less than 100 ps for CYP--indicate that these two classes of enzymes are mechanistically distinguishable and that whole-cell mechanistic assays can identify the active hydroxylase. The oxidation of norcarane by several recently isolated strains (Hydrocarboniphaga effusa AP103, rJ4, and rJ5, whose alkane-oxidizing enzymes have not yet been identified) is also reported. Radical lifetimes of 1-3 ns are observed, consistent with these organisms containing an AlkB-like enzyme and inconsistent with their employing a CYP-like enzyme for growth on hydrocarbons.

Remarkable aliphatic hydroxylation by the diiron enzyme toluene 4-monooxygenase in reactions with radical or cation diagnostic probes norcarane, 1,1-dimethylcyclopropane, and 1,1-diethylcyclopropane.

Toluene 4-monooxygenase (T4MO) catalyzes the hydroxylation of toluene to yield 96% p-cresol. This diiron enzyme complex was used to oxidize norcarane (bicyclo[4.1.0]heptane), 1,1-dimethylcyclopropane, and 1,1-diethylcyclopropane, substrate analogues that can undergo diagnostic reactions upon the production of transient radical or cationic intermediates. Norcarane closely matches the shape and volume of the natural substrate toluene. Reaction of isoforms of the hydroxylase component of T4MO (T4moH) with different regiospecificities for toluene hydroxylation (k(cat) approximately 1.9-2.3 s(-)(1) and coupling efficiency approximately 81-96%) revealed similar catalytic parameters for norcarane oxidation (k(cat) approximately 0.3-0.5 s(-)(1) and coupling efficiency approximately 72%). The products included variable amounts of the un-rearranged isomeric norcaranols and cyclohex-2-enyl methanol, a product attributed to rearrangement of a radical oxidation intermediate. A ring-expansion product derived from the norcaranyl C-2 cation, cyclohept-3-enol, was not produced by either the natural enzyme or any of the T4moH isoforms tested. Comparative studies of 1,1-dimethylcyclopropane and 1,1-diethylcyclopropane, diagnostic substrates with differences in size and with approximately 50-fold slower k(cat) values, gave products consistent with both radical rearrangement and cation ring expansion. Examination of the isotopic enrichment of the incorporated O-atoms for all products revealed high-fidelity incorporation of an O-atom from O(2) in the un-rearranged and radical-rearranged products, while the O-atom found in the cation ring-expansion products was predominantly obtained by reaction with H(2)O. The results show a divergence of radical and cation pathways for T4moH-mediated hydroxylation that can be dissected by diagnostic substrate probe rearrangements and by changes in the source of oxygen used for substrate oxygenation.

Electron impact mass spectral fragmentation of chiral bisbenzoxazole, bisbenzothiazole and biscarbamide derivatives of 2,2-dimethyl-1,3-dioxolane.

The mass spectrometric fragmentation behaviour of five pairs of (R,R)- and (S,S)-4,5-bis(benzoxazol-2-yl)-2,2-dimethyl-1,3-dioxolane derivatives, one pair of (R,R)- and (S,S)-4,5-bis(benzothiazol-2-yl)-2,2-dimethyl-1,3-dioxolanes, and three pairs of (R,R)- and (S,S)-N,N'-bis(2-hydroxyaryl)-2,2-dimethyl-1,3-dioxolane-4,5-dicarbamides, all important compounds for asymmetric catalysis (P. Jiao et al., Tetrahedron Asymmetry 2001; 12: 3081), has been studied with the aid of mass-analyzed ion kinetic energy spectrometry and accurate mass measurements under electron impact ionization conditions. The spectral observations have been rationalized in terms of fragment ion structures and fragmentation mechanisms that will provide an aid to spectral interpretation for new compounds of this type.