Streamlined Target Deconvolution Approach Utilizing a Single Photoreactive Chloroalkane Capture Tag.

Identification of physiologically relevant targets for lead compounds emerging from drug discovery screens is often the rate-limiting step toward understanding their mechanism of action and potential for undesired off-target effects. To this end, we developed a streamlined chemical proteomic approach utilizing a single, photoreactive cleavable chloroalkane capture tag, which upon attachment to bioactive compounds facilitates selective isolation of their respective cellular targets for subsequent identification by mass spectrometry. When properly positioned, the tag does not significantly affect compound potency and membrane permeability, allowing for binding interactions with the tethered compound (probe) to be established within intact cells under physiological conditions. Subsequent UV-induced covalent photo-cross-linking "freezes" the interactions between the probe and its cellular targets and prevents their dissociation upon cell lysis. Targets cross-linked to the capture tag are then efficiently enriched through covalent capture onto HaloTag coated beads and subsequent selective chemical release from the solid support. The tag's built-in capability for selective enrichment eliminates the need for ligation of a capture tag, thereby simplifying the workflow and reducing variability introduced through additional operational steps. At the same time, the capacity for adequate cross-linking without structural optimization permits modular assembly of photoreactive chloroalkane probes, which reduces the burden of customized chemistry. Using three model compounds, we demonstrate the capability of this approach to identify known and novel cellular targets, including those with low affinity and/or low abundance as well as membrane targets with several transmembrane domains.

Dechlorination of organochloride waste mixture by microwave irradiation before forming solid recovered fuel.

In order to form a modified solid recovered fuel (SRF) with low chlorine content, high calorific value and well combustion performance, low temperature microwave irradiation was applied to remove the chlorine of the organochloride waste mixture before they were mixed to form SRF. The optimizing conditions of final temperature, microwave absorbents and heating rate were also detected to obtain high dechlorination ratio and high ratio of hydrogen chloride (HCl) to volatiles. In the temperature range of 220-300°C, 280°C would be chose as the optimal low microwave modified temperature concerning at which the dechlorination ratio was high and ratio of HCl to volatiles was relatively high as well; The use of microwave absorbents of graphite and silicon carbide (SiC) had a pronounced effect on the dechlorination of organochloride waste mixture, and the dechlorination ratio was increased significantly which could be reached to 87%, almost 20% higher than absorbent absent sample; The heating rate should set be not too fast nor too slow, and there was no big difference between the heating rate of 13°C/min and 15°C/min; The content of Cl of modified SRF is dramatically decreased and reaches to a low level 0.328%. Hence, the modified SRF can be ascended from the third class to the second class according to the Finland chlorine Classes I-III. Moreover, the combustibility of modified SRF was substantial improved compared to the traditional SRF. The low heating value was almost 20.56MJ/kg which is close to the LHV of lignite coal and bituminous coal in China, and it increased by 60% over that of traditional SRF. Removing chlorine of organochloride waste mixture before they are mixed with other kinds of combustible waste to form a modified SRF which is expected to be an alternative fuel for combustion in the future.

Degradation of multi-DNAPLs by a UV/persulphate/ethanol system with the additional injection of a base solution.

This study was conducted to investigate the inhibited influences on and solution to the degradation of four types of dense non-aqueous phase liquids (DNAPLs) (i.e. perchloroethylene [PCE], trichloroethylene [TCE], chloroform [CF], and carbon tetrachloride [CT]) all at the same instance in groundwater (GW). Degradations of DNAPLs in de-ionized water (DW) and GW were carried out by applying an ultraviolet radiation-activated persulphate (UV/PS) system. PCE and TCE were degraded by over 90% and CT was only degraded by 25% in both DW and GW. However, CF was degraded by over 90% in DW, while it was only degraded by 50% in GW. First of all, degradations with an inorganic anion (either Cl- or HCO3-) indicated that the lower degradation of CF in GW was caused by the existence of the chloride ion. Moreover, the low CF degradation in GW was overcome by the additional injection of a base solution (sodium hydroxide [NaOH]) into the UV/PS system. The results showed that PCE, TCE, and CF were degraded by over 90%, respectively, when a molar ratio of [base]0:[PS]0 was larger than 0.5:1, but CT was still not effectively degraded in the UV/PS system. To achieve effective CT degradation, UV/PS with the ethanol (EtOH) system was evaluated and it was found that it degraded CT over 90%. However, at this time, CF was not effectively degraded in the UV/PS/EtOH system. Finally, degradations of DNAPLs in the UV/PS/EtOH system with the additional injection of a base solution were conducted and it showed that multi-DNAPLs were degraded by over 90%, respectively, when the molar ratio of [PS]0:[EtOH]0:[base]0 was 1:1:3.

Identification and occurrence of analogues of dechlorane 604 in Lake Ontario sediment and their accumulation in fish.

The dechlorane family of flame retardants, which includes Mirex (also known as Dechlorane), Dechlorane Plus (DP), and Dechloranes (Dec) 602, 603, and 604, were manufactured at a facility along the Niagara River, upstream of Lake Ontario. Some of these compounds remain in use. In a previous study, we found Mirex and Dec602 to have greater bioaccumulation potentials than Dec604 and DP based on calculated biota-sediment accumulation factors (BSAFs). In this study, analogues of Dec604, containing fewer bromines and mixed substitutions of bromine and chlorine, were identified in Lake Ontario sediment and fish using high and ultrahigh resolution mass spectrometric techniques. The tribromo-Dec604 (Br3Dec604) analogue, known as Dechlorane 604 Component B (Dec604 CB), was present in lake trout and whitefish at concentrations of 10-60 ng/g lipid weight, approximately 50-200 times greater than concentrations measured for Dec604. In addition, BrDec604 and Br2Dec604 analogues, and mixed Br2Cl2Dec604, Br3ClDec604, Br2ClDec604, and BrCl2Dec604 analogues were also present. We have shown that solutions of Dec604 and Dec604 CB exposed to UV-light undergo photodebromination and give rise to the analogues found in sediment and fish. Dec604 CB and other lesser halogenated analogues of Dec604 show greater bioaccumulation potentials than Dec604, Dec602 and DP, based on BSAFs, which highlight the need to consider likely impurities and degradation products in the assessment of persistent, bioaccumulative, and toxic compounds.

Effects of combined UV and chlorine treatment on the formation of trichloronitromethane from amine precursors.

The objective of this study was to investigate the effects of combined low-pressure ultraviolet (LPUV) irradiation and free chlorination on the formation of trichloronitromethane (TCNM) byproduct from amine precursors, including a commonly used polyamine coagulant aid (poly(epichlorohydrin dimethylamine)) and simple alkylamines dimethylamine (DMA) and methylamine (MA). Results showed that TCNM formation can increase up to 15 fold by combined UV/chlorine under disinfection to advanced oxidation conditions. The enhancement effect is influenced by UV irradiance, chlorine dose, and water pH. Extended reaction time leads to the decay of TCNM by direct photolysis. The combined UV/chlorine conditions significantly promoted degradation of polyamine to generate intermediates, including DMA and MA, which are better TCNM precursors than polyamine, and also facilitated transformation of these amine precursors to TCNM. Under combined UV/chlorine, polyamine degradation was likely promoted by radical oxidation, photodecay of chlorinated polyamine, and chlorine oxidation/substitution. Promoted TCNM formation from primary amine MA was primarily due to radicals' involvement. Promoted TCNM formation from secondary amine DMA likely involved a combination of radical oxidation, photoenhanced chlorination reactions, and other unknown mechanisms. Insights obtained in this study are useful for reducing TCNM formation during water treatment when both UV and chlorine will be encountered.

Mechanical behavior of facial prosthetic elastomers after outdoor weathering.

OBJECTIVES: The degradation of maxillofacial prosthetic elastomers that occurs during physical weathering is usually responsible for the replacement of prostheses. In this study the mechanical behavior of 4 non-pigmented facial prosthetic elastomers, exposed to outdoor weathering for 1 year, was investigated. The hypothesis investigated was that irradiation time did not affect the properties measured. METHODS: The samples were exposed to solar radiation for 1 year in Thessaloniki (Greece). Three different types of polydimethyl siloxane (PDMS) and chlorinated polyethylene (CPE) samples were tested in this study. Mechanical tests (compressive-tensile) were performed using a universal type testing machine. Hardness tests were evaluated using a durometer tester. Simple mathematical models were developed to correlate the measured properties with irradiation time. The stress-strain data of compression and tensile tests were modeled using parameters such as maximum stress (sigma(max)), maximum strain (epsilon(max)), elasticity parameter (E), and non-linearity parameter (p), while the mathematical model used for hardness data involves initial hardness of materials (H(0)). RESULTS: Two of the silicone prosthetics (Elastomer 42, TechSil 25) seem to become harder and more brittle contrary to the other silicone (M 511) and chlorinated polyethylene (CPE) samples that become softer and more ductile. Duration of exposure increases these phenomena. CONCLUSION: The effect of irradiation time on the mechanical behavior was introduced through its effect on the models' parameters. The hypothesis was rejected since changes were observed in the model parameters.

The effect of artificial accelerated weathering on the mechanical properties of maxillofacial polymers PDMS and CPE.

The effect of UVA-UVB irradiation on the mechanical properties of three different industrial types of polydimethylsiloxane and chlorinated polyethylene samples, used in maxillofacial prostheses, was investigated in this study. Mechanical properties and thermal analysis are commonly used to determine the structural changes and mechanical strength. An aging chamber was used in order to simulate the solar radiation and assess natural aging. Compression and tensile tests were conducted on a Zwick testing machine. Durometer Shore A hardness measurements were carried out in a CV digital Shore A durometer according to ASTM D 2240. Glass transition temperature was evaluated with a differential scanning calorimeter. Simple mathematical models were developed to correlate the measured properties with irradiation time. The effect of UVA-UVB irradiation on compressive behavior affected model parameters. Significant deterioration seems to occur due to irradiation in samples.

A study on radiation technological degradation of organic chloride wastewater--exemplified by TCE and PCE.

This paper describes the potential of using gamma radiation technology to degrade trichloroethylene (TCE) and perchloroethylene (PCE) wastewater. The experimental method is divided into two parts: (1) using the gamma-ray to irradiate the TCE and PCE solution, the dose-rate is 10Gy/minute, the irradiation dosage is 0-2.5kGy and (2) self-making the UV irradiation system, the tube specification is 254nm and 6W, and turning on 8 tubes at the same time to make the irradiation. The efficiency of degradation ratio for gamma-ray is better than UV in the range of 0.1-250ppm; for example, as for the concentration of 0.1ppm, when TCE is degraded to D(90) and T(90), the gamma-ray only needed 46.7Gy and took about 4.67 minutes, but UV needed to take about 28.1 minutes. The dose-concentration equations of TCE and PCE are: TCE: y=44.58+8.832x, R(2)=0.999; and PCE: y=81.33+12.81x, R(2)=0.997. We verified that the radiation technology is able to effectively degrade the organic chlorine wastewater without yielding the secondary pollution, and the TCE and PCE that degraded by using gamma-ray will be reached US-EPA and Taiwan Effluent Standard (5ppb).

Photoprocesses of chloro-substituted p-benzoquinones.

The photochemistry of chloro-(ClBQ), dichloro-(2,5- and 2,6-Cl 2BQ), and trichloro-1,4-benzoquinone (Cl 3BQ) was studied in aqueous solution and/or in mixtures with acetonitrile. Final products are the corresponding hydroquinones (QH 2s) and 2-hydroxy-1,4-benzoquinones (QOHs). Three transients were detected by UV-vis absorption spectroscopy. The triplet state appears within the 20 ns 248 nm pulse and is converted within 0.1-1 micros into a photohydrate (HI aq). HI aq which is spectroscopically and kinetically separated from the triplet state decays within 5 ms, whereas the anion of the hydroxyquinone (QO (-)) grows in at ca. 500 nm in the 0.1-1 s time range. The proton formation and decay kinetics within 0.1-10 micros were observed by transient conductivity in the course of the reaction of the triplet state with water en route to HI aq at pH 4-9. Formation of QO (-) results in a permanent conductance. The efficient photoconversion of Cl n BQs at low concentrations (<0.2 mM) into QH 2s and HOQs is due to a redox reaction of Q with rearranged HI aq. The quantum yield of photoconversion at lambda irr = 254 nm is 0.8-1.2 for ClBQ or Cl 2BQs in aqueous acetonitrile and smaller (0.4) for Cl 3BQ. The yield of semiquinone radical ( (*)QH/Q (*-)) of Cl n BQs ( n = 1-4) in acetonitrile-water (1:1) is low (<20%) at low substrate concentration but is significantly increased upon addition of an H-atom donor, for example, 2-propanol. Other mechanisms involving (*)QH/Q (*-) radicals, such as quenching of the triplet state at enhanced Cl n BQ concentrations and H-atom abstraction from an organic solvent in mixtures with water, have also to be considered.

Development of an analytical method based on microwave-assisted extraction and solid phase extraction cleanup for the determination of organochlorine pesticides in animal feed.

A method to determine 21 organochlorine pesticides in animal feed samples using microwave assisted extraction and solid phase extraction cleanup was optimised regarding its main parameters. After extraction with hexane-acetone (50:50), three different sorbents (alumina/ENVI-Florisil, ENVI-Carb and ENVI-Carb II/PSA) were assayed for the cleanup step. Analytes were eluted with hexane-ethyl acetate (80:20) and determined by gas chromatography and electron capture detection followed by gas chromatography-mass spectrometry. ENVI-Carb and ENVI-Carb II/PSA provided colourless eluates but fewer interferent compounds were found in ENVI-Carb II/PSA chromatograms, so this system was selected to carry out the purification of the extracts. The analytical recoveries obtained with this method were close to 100% in most cases with relative standard deviations lower than 10%. These percentages were similar to those obtained with the Soxhlet extraction procedure, which shows the method suitable for the determination of organochlorine pesticides in animal feed material. The method was also validated with the analysis of a certified reference material (CRM-115 BCR), and the results obtained were in good accordance with the certified values.

Behavior and prediction of photochemical degradation of chlorinated polycyclic aromatic hydrocarbons in cyclohexane.

The photochemical degradation of 11 chlorinated polycyclic aromatic hydrocarbons (ClPAHs) and the corresponding 5 parent PAHs was examined to simulate the compound's fate on aerosol surfaces. All the ClPAHs and PAHs decayed according to the first-order reaction rate kinetics. The photolysis rates of ClPAHs varied greatly according to the skeleton of PAHs; the rates of chlorophenanthrenes (ClPhes) and 1-chloropyrene were higher than those of corresponding parent PAHs, whereas chlorofluoranthenes, 7-chlorobenz[a]anthracene and 6-chlorobenzo[a]pyrene were more stable under irradiation compared to respective parent PAH. Considering the photoproducts of ClPhes detected, the oxidation could occur immediately at positions of the highest frontier electron density. Finally, the quantitative structure-property relationship models were developed for direct photolysis half-lives and average quantum yields of the ClPAHs and parent PAHs, in which the significant factors affecting photolysis were E(LUMO+1), total energy and surface area, and E(LUMO), E(LUMO)-E(HOMO) and total energy, respectively.

Sonolysis of chlorinated compounds in aqueous solution.

To examine the reaction rates of sonochemical degradation of aqueous phase carbon tetrachloride, trichloroethylene and 1,2,3-trichloropropane at various temperatures, power intensities, and saturating gases, the batch tests were carried out. The degradations of chlorinated hydrocarbons were analyzed as pseudo first order reactions and their reaction rate constants were in the range of 10(-1)-10(-3)/min. The reaction was fast at the low temperature with higher power intensity. Also, the reaction went fast with the saturating gas with high specific heat ratio, high solubility and low thermal conductivity. The main mechanism of destruction of chemicals was believed the thermal combustion in the bubble.

Direct VUV photolysis of chlorinated methanes and their mixtures in a nitrogen stream.

The gas-phase decomposition of CCl(4), CHCl(3) and CH(2)Cl(2) and their binary mixtures was studied in a flow-type reactor in a nitrogen gas stream, using a low-pressure mercury vapour lamp covered with a high-purity silica quartz sleeve. The 184.9 nm vacuum-ultraviolet (VUV) light emitted is able to rupture the C-Cl bond in these target substances. For H-containing compounds, the decomposition takes place not only by direct photolysis, but also by H abstraction by .Cl formed during the direct photolysis of the target substances. The relative contributions of direct photolysis and .Cl-sensitized reactions to the decomposition were estimated at different initial concentrations. The addition of CCl(4) to CHCl(3) or CH(2)Cl(2) increased their decomposition rates via increase of the .Cl concentration, whereas the addition of CH(2)Cl(2) to CHCl(3) decreased its degradation rate, suggesting that CH(2)Cl(2) acts as a .Cl radical scavenger. The variation of the product distribution confirms the effect of the composition of the irradiated gas mixtures on the relative contributions of .Cl-sensitized reactions and direct photolysis.

Direct VUV photolysis of chlorinated methanes and their mixtures in an oxygen stream using an ozone producing low-pressure mercury vapour lamp.

The gas-phase photooxidations of CCl(4), CHCl(3), CH(2)Cl(2) and their binary mixtures in an O(2) stream were studied in a flow reactor under various experimental conditions using a low-pressure mercury lamp as light source covered with a high-purity silica sleeve being used. The 184.9 nm VUV irradiation emitted is responsible for the Cl-C bond rupture in the chlorinated methanes and for the formation of O(3) from O(2). The rate of degradation of H-containing chlorinated methanes increased sharply on increase of their initial concentrations, most probably of a (*)Cl chain reaction, as indicated by the increase in the molar ratio of the amount of HCl formed to the amount of H-containing target substance decomposed. The experimental results suggested that the further transformations of the radicals and products formed play an important role as (*)Cl sources, causing a considerably higher rate of decomposition of the H-containing target substances. In a humidified O(2) stream, the (*)OH formed opens up another route for oxidation of the target substances. Thus, the rates of degradation of CH(2)Cl(2) and CHCl(3) increased on increase of the relative humidity, whereas the water vapour had no effect at all on the decomposition of CCl(4). At the same time, competition occurs between (*)Cl or (*)OH for reactions with the target substance. The photooxidation of binary mixtures was investigated too. The addition of CCl(4) or CHCl(3) to CH(2)Cl(2) strongly increased its degradation rate. The addition of CH(2)Cl(2) did not have a considerable effect on the rate of degradation of CHCl(3).

Efficient and selective hydrocarbon oxidation with sodium periodate under ultrasonic irradiation catalyzed by polystyrene-bound Mn (TPyP).

Rapid, efficient and selective alkene epoxidation and alkane hydroxylation with sodium periodate catalyzed by Mn (TPyP) supported on chloromethylated polystyrene, [Mn(TPyP)-CMP], under ultrasonic irradiation were reported. This catalytic system showed high selectivity in epoxidation of stilbenes and R-(+)-limonene and exhibits a particular ability to epoxidize linear alkenes such as 1-heptene. This supported catalyst can catalyze the oxidation of very inert saturated hydrocarbons as well as alkylbenzene derivatives with NaIO4 under ultrasonic irradiation. Under mild reaction conditions, this catalyst was consecutive reused five times without detectable catalyst leaching and gave over 95% epoxide yield in the epoxidation of styrene.

Development and validation of a novel method for the analysis of chlorinated pesticides in soils using microwave-assisted extraction-headspace solid phase microextraction and gas chromatography-tandem mass spectrometry.

A new procedure for determining eleven organochlorine pesticides in soils using microwave-assisted extraction (MAE) and headspace solid phase microextraction (HS-SPME) is described. The studied pesticides consisted of mirex, alpha- and gamma-chlordane, p,p'-DDT, heptachlor, heptachlor epoxide isomer A, gamma-hexachlorocyclohexane, dieldrin, endrin, aldrine and hexachlorobenzene. The HS-SPME was optimized for the most important parameters such as extraction time, sample volume and temperature. The present analytical procedure requires a reduced volume of organic solvents and avoids the need for extract clean-up steps. For optimized conditions the limits of detection for the method ranged from 0.02 to 3.6 ng/g, intermediate precision ranged from 14 to 36% (as CV%), and the recovery from 8 up to 51%. The proposed methodology can be used in the rapid screening of soil for the presence of the selected pesticides, and was applied to landfill soil samples.

Effects of medium-pressure UV lamps radiation on water quality in a chlorinated indoor swimming pool.

The aim of our study was to determine the impact of medium-pressure UV lamps radiation on water quality in a chlorinated indoor swimming pool. An indoor swimming pool was equipped with two medium-pressure UV lamps. We collected eight samples of water daily over a four-weeks period and measured total and free chlorine, pH, water temperature, bacteriological parameters, total organic carbon and trihalomethanes. During the first week, which served as control, medium-pressure UV lamps were turned off. During the next three weeks, medium-pressure UV lamps were kept on 24 h per day. The third week, we reduced the level of the injected chlorine into water, and the last week we also reduced the water renewal volume by 27%. Our results showed that bacteriological parameters remained within allowable french limits. When medium-pressure UV lamps were kept on, total, free and active chlorine levels were significantly increased (P<0.001), whereas combined chlorine level were significantly decreased (P<0.001 and P<0.05, respectively). The levels of chloroform and bromodichloromethane were significantly increased when medium-pressure UV lamps were kept on (P<0.001), whereas chlorodibromomethane and bromoform levels significantly decreased (P<0.05 and P<0.001, respectively). The additional formation of chloroform and bromodichloromethane may be explained by the increase in active chlorine and by radicalizing mechanisms initiated by UV radiation.

Effect of electron beam irradiation on the degradation of monochlorophenols in aqueous solution.

Electron beam was successfully used for the degradation of 2-chlorophenol (2-CP) and 4-chlorophenol (4-CP) in aqueous solutions in this research. The effect of radiation dose on substrate degradation and dechlorination of solutions with concentration of 50 mg/L was investigated. The effect of initial concentration, pH and presence of oxygen was also investigated. The concentration of 2-CP and 4-CP remaining in solution after irradiation were measured by HPLC. The results showed that increased radiation dose led to increased degradation of the chlorophenols and increased Cl- yield. Deaeration was also found to significantly increase the rate of degradation of chlorophenols in water while degradation and dechlorination under alkaline condition was lower than at low to neutral pH.

Photolytic clean-up of biological samples for gas chromatographic analysis of chlorinated paraffins.

A method based on gas chromatography electron capture detection (GC-ECD) for the analysis of chlorinated paraffins (CPs) in biological samples has been investigated. The method includes photolytic destruction of halogenated aromatic compounds, such as PCBs, to eliminate some of the interferences in the analysis of CPs in environmental samples. Gel permeation chromatography was used to isolate CPs from the interfering components of Toxaphene and chlordane after the photolysis. GC-ECD gave a detection limit of 20 ng CPs/g fresh muscle tissue. The recovery of CPs from a spiked moose liver sample was estimated to 94%.

UV-light induced mineralization of organic matter bound chlorine in Lake Bjän, Sweden--a laboratory study.

Surface water and aqueous solutions of isolated organic matter from a humic rich lake in southern Sweden were exposed to artificial UV radiation to investigate the UV light induced influence on organic matter bound chlorine in natural systems. It was found that the photodegradation of organic matter bound chlorine was more pronounced than the photodegradation of organic carbon. After 120 h of irradiation of the isolated organic matter, only 35% of the initial organochlorine was still in the solution compared to about 70% of the dissolved organic carbon (DOC). A similar result was obtained for unfractionated surface water. Furthermore, our results indicate that the loss of organic chlorine was mainly due to a mineralization of organic chlorine into chloride ions. The total decrease of organic chlorine after 120 h was 32 microg Cl(org) l(-1), of which the major part disappeared in the initial irradiation phase. A similar increase was observed in the chloride concentration (34 microg Cl(-) l(-1)).