Synthesis and Spectral Study of a New Family of 2,5-Diaryltriazoles Having Restricted Rotation of the 5-Aryl Substituent.

Efficient synthesis of 2,5-diaryl substituted 4-azido-1,2,3-triazoles by the reaction of sodium azide with dichlorosubstituted diazadienes was demonstrated. The optical properties of the prepared azidotriazoles were studied to reveal a luminescence maximum in the 360-420 nm region. To improve the luminescence quantum yields a family of 4-azido-1,2,3-triazoles bearing ortho-propargyloxy substituents in the 5 position was prepared. Subsequent intramolecular thermal cyclization permits to construct additional triazole fragment and obtain unique benzoxazocine derivatives condensed with two triazole rings. This new family of condensed heterocycles has a flattened heterocyclic system structure to provide more conjugation of the 5-aryl fragment with the triazole core. As a result, a new type of UV/"blue light-emitting" materials with better photophysical properties was obtained.

A colorimetric and fluorescent lighting-up sensor based on ICT coupled with PET for rapid, specific and sensitive detection of nitrite in food.

An anthracene carboxyimide derivative was synthesized as a colorimetric and fluorogenic sensor to determine NO2- with a rapid response (<4 min), excellent selectivity and a low detection limit (84 nM). Paper strips containing the sensor were applied to visually determine the NO2- content in food.

A water soluble donor-acceptor-donor conjugated oligomer as a photosensitizer for mitochondria-targeted photodynamic therapy.

We designed a water soluble benzotriazole-cored donor-acceptor-donor molecule bearing four triphenylphosphonium moieties for mitochondria targeting. The organic molecule showed strong singlet oxygen sensitizing capability (ΦΔ 0.64), minimal dark cytotoxicity and high photocytotoxicity. The molecule is efficient in photodynamic killing of tumour cells under normal and hypoxia conditions using a very low light flux, and has potential in near-infrared two-photon imaging and photodynamic therapy.

The increased toxicity of UV-degraded nitroguanidine and IMX-101 to zebrafish larvae: Evidence implicating oxidative stress.

Insensitive munitions (IMs) improve soldier safety by decreasing sympathetic detonation during training and use in theatre. IMs are being increasingly deployed, although the environmental effects of IM constituents such as nitroguanidine (NQ) and IM mixture formulations such as IMX-101 remain largely unknown. In the present study, we investigated the acute (96h) toxicity of NQ and IMX-101 to zebrafish larvae (21d post-fertilization), both in the parent materials and after the materials had been irradiated with environmentally-relevant levels of ultraviolet (UV) light. The UV-treatment increased the toxicity of NQ by 17-fold (LC50 decreased from 1323mg/L to 77.2mg/L). Similarly, UV-treatment increased the toxicity of IMX-101 by nearly two fold (LC50 decreased from 131.3 to 67.6mg/L). To gain insight into the cause(s) of the observed UV-enhanced toxicity of the IMs, comparative molecular responses to parent and UV-treated IMs were assessed using microarray-based global transcript expression assays. Both gene set enrichment analysis (GSEA) and differential transcript expression analysis coupled with pathway and annotation cluster enrichment were conducted to provide functional interpretations of expression results and hypothetical modes of toxicity. The parent NQ exposure caused significant enrichment of functions related to immune responses and proteasome-mediated protein metabolism occurring primarily at low, sublethal exposure levels (5.5 and 45.6mg/L). Enriched functions in the IMX-101 exposure were indicative of increased xenobiotic metabolism, oxidative stress mitigation, protein degradation, and anti-inflammatory responses, each of which displayed predominantly positive concentration-response relationships. UV-treated NQ had a fundamentally different transcriptomic expression profile relative to parent NQ causing positive concentration-response relationships for genes involved in oxidative-stress mitigation pathways and inhibited expression of multiple cadherins that facilitate zebrafish neurological and retinal development. Transcriptomic profiles were similar between UV-treated versus parent IMX-101 exposures. However, more significant and diverse enrichment as well as greater magnitudes of differential expression for oxidative stress responses were observed in UV-treated IMX-101 exposures. Further, transcriptomics indicated potential for cytokine signaling suppression providing potential connections between oxidative stress and anti-inflammatory responses. Given the overall results, we hypothesize that the increased toxicity of UV-irradiated NQ and the IMX-101 mixture result from breakdown products with elevated potential to elicit oxidative stress.

Aquatic toxicity of photo-degraded insensitive munition 101 (IMX-101) constituents.

Insensitive munitions are desirable alternatives to historically used formulations, such as 2,4,6-trinitrotoluene (TNT), because of their so-called insensitivity to unintended detonation. The insensitive munition IMX-101 is a mixture of 2,4-dinitroanisole (DNAN), 3-nitro-1,2,4-triazol-5-one (NTO), and nitroguanidine (NQ). Environmental releases of munitions may be from production wastewaters or training; these munitions may be exposed to ultraviolet (UV) light. Therefore, it is useful to understand the relative toxicity of IMX-101 and its constituents both before and after photodegradation. The intent of the present study was to generate relative hazard information by exposing the standard ecotoxicological model Ceriodaphnia dubia to each insensitive munition constituent individually and to IMX-101 before and after the exposure solution was irradiated in a UV photoreactor. Without photodegradation, DNAN was more toxic (median lethal concentration [LC50] = 43 mg/L) than the other 2 constituents and it contributed predominantly to the toxicity of IMX-101 (LC50 = 206 mg/L) based on toxic units. Toxicity was observed only at high levels of NQ (LC50 = 1174 mg/L) and pH-adjusted NTO (LC50 = 799 mg/L). The toxicity of IMX-101 is lower than literature-reported TNT toxicity. Photodegradation efficiency was greater at lower insensitive munition concentrations. The observed degradation was greatest for NQ (42-99%), which in turn corresponded to the greatest relative increase in toxicity (100-1000-fold). Modest percent of degradation (4-18%) and increases in phototoxicity (2-100-fold) were observed for NTO and DNAN. Photodegraded NQ products were the predominant source of toxicity of photodegraded IMX-101. Future work involves research to enable analytical and computational confirmation of the specific degradation compounds inducing the observed photoenhanced toxicity. Environ Toxicol Chem 2017;36:2050-2057. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Benzotriazole UV 328 and UV-P showed distinct antiandrogenic activity upon human CYP3A4-mediated biotransformation.

Benzotriazole ultraviolet stabilizers (BUVSs) are prominent chemicals widely used in industrial and consumer products to protect against ultraviolet radiation. They are becoming contaminants of emerging concern since their residues are frequently detected in multiple environmental matrices and their toxicological implications are increasingly reported. We herein investigated the antiandrogenic activities of eight BUVSs prior to and after human CYP3A4-mediated metabolic activation/deactivation by the two-hybrid recombinant human androgen receptor yeast bioassay and the in vitro metabolism assay. More potent antiandrogenic activity was observed for the metabolized UV-328 in comparison with UV-328 at 0.25 µM ((40.73 ± 4.90)% vs. (17.12 ± 3.00)%), showing a significant metabolic activation. In contrast, the metabolized UV-P at 0.25 µM resulted in a decreased antiandrogenic activity rate from (16.08 ± 0.95)% to (6.91 ± 2.64)%, indicating a metabolic deactivation. Three mono-hydroxylated (OH) and three di-OH metabolites of UV-328 were identified by ultra-performance liquid chromatography quadrupole time of flight mass spectrometry (UPLC-Q-TOF-MS/MS), which were not reported previously. We further surmised that the hydroxylation of UV-328 occurs mainly at the alicyclic hydrocarbon atoms based on the in silico prediction of the lowest activation energies of hydrogen abstraction from C-H bond. Our results for the first time relate antiandrogenic activity to human CYP3A4 enzyme-mediated hydroxylated metabolites of BUVSs. The biotransformation through hydroxylation should be fully considered during the health risk assessment of structurally similar analogs of BUVSs and other emerging contaminants.

Sunlight photolysis of benzotriazoles - Identification of transformation products and pathways.

Benzotriazoles (BTs) are widely used corrosion inhibitors, incompletely removed in municipal wastewater treatment. The photochemical fate of the three BTs 1H-benzotriazole (1H-BT), 4-methyl-1H-benzotriazole (4Me-BT) and 5-methyl-1H-benzotriazole (5Me-BT) and of three microbial metabolites, was studied under simulated sunlight (290-800 nm) at neutral pH in aqueous solution for 24 h. The half-life, the quantum yield and the reaction rate were determined and a total of 36 photolysis products were detected and identified using liquid chromatography-high resolution-mass spectrometry. The half-lives of all six BTs were in the range of 6-24 h under the experimental conditions. Though the quantum yields were comparatively low (0.0007-0.0021), the environmental half-lives ranged from 2.4 to 8 d, suggesting that sunlight photolysis is still a relevant degradation process of BTs in surface waters. The photolysis pathway of 1H-BT under simulated sunlight differed from that suggested for UV-radiation, in that aminophenol is formed directly rather than via aniline. Similar pathways were found for the other BTs, except for 4-hydroxy-1H-benzotriazole (4OH-BT). Most identified transformation products of the BTs showed a high reactivity and appear not to persist in the environment. Upon co-photolysis of BTs with dissolved organic matter (DOM), however, series of reaction products were determined by Fourier transform - ion cyclotron resonance - mass spectrometry (FTICR-MS) which are formed by reaction of photolysis intermediates of the BTs with DOM.

Degradation rates of benzotriazoles and benzothiazoles under UV-C irradiation and the advanced oxidation process UV/H2O2.

Benzotriazoles (BTs) and benzothiazoles (BTHs) are extensively used chemicals found in a wide range of household and industrial products. They are chemically stable and are therefore ubiquitous in the aquatic environment. The present study focuses on the potential of ultraviolet (UV) irradiation, alone or in combination with hydrogen peroxide (H2O2), to remove BTs and BTHs from contaminated waters. Six compounds, three out of each chemical class, were investigated using a low-pressure mercury lamp (main emission at 254 nm) as the radiation source. Initially, the direct phototransformation kinetics and quantum yield in dilute aqueous solution was studied over the pH range of 4-12. All BTs and BTHs, except for benzothiazole, exhibited pH-dependent direct phototransformation rate constants and quantum yields in accordance to their acid-base speciation (7.1 < pKa < 8.9). The direct phototransformation quantum yields (9.0 × 10(-4)-3.0 × 10(-2) mol einstein(-1)), as well as the photon fluence-based rate constants (1.2-48 m(2) einstein(-1)) were quite low. This suggests that UV irradiation alone is not an efficient method to remove BTs and BTHs from impacted waters. The second-order rate constants for the reaction of selected BTs and BTHs with the hydroxyl radical were also determined, and found to fall in the range of 5.1-10.8 × 10(9) M(-1) s(-1), which is typical for aromatic contaminants. Finally, the removal of BTs and BTHs was measured in wastewater and river water during application of UV irradiation or the advanced oxidation process UV/H2O2. The latter process provided an efficient removal, mostly due to the effect of the hydroxyl radical, that was comparable to other aromatic aquatic contaminants, in terms of energy requirement or treatment costs.

Adsorption and desorption behavior of selected pesticides as influenced by decomposition of maize mulch.

Assessing pesticide fate in conservation agricultural systems requires a detailed understanding of their interaction with decomposing surface crop residues (mulch). Adsorption and desorption behavior of glyphosate, s-metolachlor and epoxiconazole was investigated on maize mulch residues decomposed under laboratory and field conditions. Our conceptual approach included characterization of chemical composition and hydrophobicity of mulch residues in order to generate parameters to predict sorption behavior. Adsorption of s-metolachlor and epoxiconazole greatly increased with mulch decomposition, whereas glyphosate adsorption was less affected but its desorption was increased. Mulch characteristics including aromaticity, hydrophobicity and polarity indices were strongly correlated to Koc of the non-ionic pesticides. A predictive model based on compositional data (CoDa) analysis revealed that the sorption capacity of decomposing mulch can be predicted from descriptors such as aromatic and alkyl C corresponding respectively to lignin and NDF biochemical fractions. The decomposition degree of mulch residues should be taken into account while predicting the fate of pesticides.

Photocatalytic degradation of pesticides in pure water and a commercial agricultural solution on TiO2 coated media.

Heterogeneous photocatalysis of pesticides is an effective process for removing pesticides from pure water. With a view to treating real agricultural effluents, this paper deals with the degradation of the chlortoluron and cyproconazole pesticides in pure water and the treatment of commercial solutions by photocatalysis on TiO2 coated media. The process was effective in degrading and mineralizing the pesticides. The changes of the fate of heteroatoms showed that during irradiation of the chlortoluron and cyproconazole, NH4+ and NO3(-) ions were produced. A release of chloride ions was observed from the beginning of the irradiation and stoichiometry was achieved. The photodegradation of chlortoluton and cyproconazole in commercial solutions was studied. For the degradation of chlortoluton in a commercial solution, the mineralization was completely achieved whereas in the case of the commercial cyproconazole solution, the degradation kinetic was lower. These results highlight the fact that the chemical nature of the additives in the commercial pesticide solutions does significantly affect the degradation yield of the target compound by photocatalysis.

Titanium dioxide photoinduced degradation of some pesticide/fungicide precursors.

Five-membered nitrogen heterocycles (pyrrole, imidazole and 1,2,4-triazole) have been degraded using titanium dioxide and simulated solar radiation at pH = 8. The degradations followed a simple Langmuir-Hinshelwood mechanism. Accordingly, the adsorption equilibrium constants K of the heterocycles on the titanium dioxide surface and the rate constants k of degradation of the heterocycle-catalyst adduct have been obtained experimentally. While the K values decrease with heterocycle pKa, the k values increase with increasing pKa. Therefore, apparently, the rate constant depends on the availability of the electron pair on nitrogen, but at the same time the electron pair repulsion induced by the negatively charged titanium dioxide surface at pH = 8 causes a reverse effect in the adsorption equilibrium constant. Only in the case of imidazole, where the adsorption equilibrium constant is low enough (K = 0.013 M(-1)), can the rate constant be approximated to a pseudo-first-order rate expression: k(obs) = Kk. In all other cases, k(obs) = Kk/(1 + K(heterocycle)).

Photocatalytic degradation of triazophos in aqueous titanium dioxide suspension: identification of intermediates and degradation pathways.

The photocatalytic degradation of triazophos in aqueous TiO2 suspension has been studied in a photoreactor operating with simulated solar radiation. The decrease in triazophos concentration followed first-order kinetics with a half-life of 4.76+/-0.42 h at a TiO2 suspension concentration of 10 mg/L. Seventeen degradation products were identified using HPLC-UV, HPLC/MS/MS, GC/MS/MS and IC, and by comparing retention times and spectra with commercially available authentic standards. On the basis of the observed transformation products, two routes were proposed, one based on the initial oxidative cleavage of PS bond to PO bond, and the other on initial cleavage of the ester P-O bonds. Photocatalysis holds promise for the solar treatment of pesticide-contaminated waters.

Microwave-assisted synthesis of N-alkylated benzotriazole derivatives: antimicrobial studies.

Synthesis and characterization of N-alkylated benzotriazole derivatives 2(a-g) bearing pharmaceutically important bioactive substituents and their antimicrobial studies in vitro are described. The syntheses of the compounds were achieved by N-alkylation of the benzotriazole with different bioactive alkyl halides in presence of powdered K2CO3 in DMF solution and by microwave irradiation method with good yield compared to conventional method. The crystal structure analysis shows that compound 4'-benzotriazol-1-yl-methyl-biphenyl-2-carbonitrile 2a crystallizes in the space group P1 with cell parameters a = 8.526 (3) A, b = 12.706 (3) A, c = 7.966 (2) A, alpha = 100.89 (2) degrees , beta = 101.63 (3) degrees , gamma = 102.20(2) degrees, Volume = 801.7(4) A degrees , Z = 2 and the final R factor is 0.0559 for 6130 reflections with 218 parameters and zero restraint. This structure exhibits intermolecular hydrogen bonding. Compounds 2e, 2a showed significant antimicrobial activity.

Efficient microwave enhanced regioselective synthesis of a series of benzimidazolyl/triazolyl spiro [indole-thiazolidinones] as potent antifungal agents and crystal structure of spiro[3H-indole-3,2'-thiazolidine]-3'(1,2,4-triazol-3-yl)-2,4'(1H)-dione.

A microwave-assisted three-component, regioselective one-pot cyclocondensation method has been developed for the synthesis of a series of novel spiro[indole-thiazolidinones] (6a-l) using an environmentally benign procedure at atmospheric pressure in open vessel. This rapid method produces pure products in high yields within few minutes in comparison to a conventional two-step procedure. The crystal structure of one representative compound has been determined by X-ray diffraction. The synthesized compounds have been screened 'in vitro' for antifungal activity against Rhizoctonia solani, Fusarium oxysporum and Collectotrichum capsici. All compounds have shown good activity against these pathogens.

In vitro evaluation of color change in maxillofacial elastomer through the use of an ultraviolet light absorber and a hindered amine light stabilizer.

STATEMENT OF PROBLEM: External prostheses composed of silicone elastomers exhibit an unwanted color change over time. PURPOSE: This study evaluated color stability when an ultraviolet light absorber and hindered amine light stabilizer were mixed in the maxillofacial elastomer containing either organic or inorganic pigments. MATERIAL AND METHODS: The materials used were an RTV silicone elastomer, 1 natural inorganic dry-earth pigment (burnt sienna) and 2 synthesized organic pigments (hansa yellow and alizarin red), ultraviolet light absorber (UVA) and hindered amine light stabilizer (HALS). Specimens (n=160) were fabricated in a custom mold and randomly assigned and exposed to weathering sites in Miami and Phoenix for approximately 3 months. Eight test groups (2 of each 4 material types with or without additives) of 10 specimens each were assigned to each site. L*, a*, b* readings were obtained before and after weathering from a spectrocolorimeter. Nonpigmented elastomers served as the control. Three-factor ANOVA was conducted to examine interaction effects between weathering sites, specimen type, and the presence of additive (alpha=.05). Overall color change (Delta E) and change in color coordinates (Delta L*, Delta a*, Delta b*) of specimen groups with and without additive were analyzed with independent sample t tests. RESULTS: In specimen groups with the additives (UVA and HALS), color change decreased significantly (P<.05) in burnt sienna and hansa yellow in Phoenix and in the control and hansa yellow in Miami. Additives did not affect color change in the alizarin red group. CONCLUSION: UVA and HALS were shown to be effective in retarding color change in some circumstances.

Environmental transformation of triadimefon in water and on plant leaf surface.

Phototransformation of triadimefon was studied in aqueous solution and on plant leaf surface under natural and simulated conditions. Photoproducts such as 4-chlorophenol, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazole-1-yl)-butan-2-ol and 1-phenoxy-3,3-dimethyl-but-2-one were identified on leaf as well as in aqueous solution. A new photoproduct product 1-(4-chlorophenoxymethyl)-1,2,4-triazole was identified only on the leaf surface. The rate of degradation was more in tap water as compared to rain and distilled water.

Photoreduction of the chloropropionic acid of carfentrazone-ethyl in sodium sulfide [corrected].

The purpose of this study was to determine whether the conversion of carfentrazone-chloropropionic acid to carfentrazone-propionic acid in sunlit rice paddies is attributed to photoreduction. Model solutions (Na2S with quinoids) irradiated by laboratory ultraviolet light dechlorinated carfentrazone-chloropropionic acid (1.6-28.4% yield of carfentrazone-propionic acid), though Na2S alone was also reactive. Minor conversion (0-2.5%) occurred in the dark, along with dehydrochlorination to carfentrazone-cinnamic acid. Carfentrazone-propionic acid formed proportionally to the Na2S concentration (0-50.7% at 1.3-91 mM), whereas acidic pH inhibited reactivity. Photoreduction with Na2S was verified with 2-chloropropionic acid conversion to propionic acid (53.5%) and by minor 4-chlorophenoxyacetic acid dechlorination. Dissolved Na2S was the primary photoreductant, whereas reduced quinones degraded carfentrazone-chloropropionic acid by an alternate reaction. A survey of ambient rice field conditions indicates that carfentrazone-chloropropionic acid photoreduction is not directly attributed to H2S/HS- in this environment, though reduced quinones may be involved to an unknown extent.

High-performance liquid chromatographic/tandem mass spectrometric identification of the phototransformation products of tebuconazole on titanium dioxide.

Tebuconazole is a widely used fungicide. The formation of by-products on irradiated titanium dioxide as a photocatalyst was evaluated. Several species derived from tebuconazole degradation were identified and characterized by HPLC/MS(n). A pattern of reactions accounting for the observed intermediates is proposed. Different parallel pathways are operating (and through these pathways the transformation of the molecule proceeds), leading to a wide range of intermediate compounds. All these molecules are more hydrophylic than tebuconazole. The main steps involved are (1) the hydroxylation of the molecule with the formation of three species having [M + H](+) 324; the hydroxylation occurs on the C-1 carbon and on the aromatic ring in the two ortho-positions; (2) the cleavage of a C--C bond with the release of the tert-butyl moiety and the formation of a species having m/z 250; analogously to step 1, also on this species a further hydroxylation reaction occurs; (3) through the loss of the triazole moiety with the formation of a structure with m/z 257.

A molecular logic gate.

We propose a scheme for molecule-based information processing by combining well-studied spectroscopic techniques and recent results from chemical dynamics. Specifically it is discussed how optical transitions in single molecules can be used to rapidly perform classical (Boolean) logical operations. In the proposed way, a restricted number of states in a single molecule can act as a logical gate equivalent to at least two switches. It is argued that the four-level scheme can also be used to produce gain, because it allows an inversion, and not only a switching ability. The proposed scheme is quantum mechanical in that it takes advantage of the discrete nature of the energy levels but, we here discuss the temporal evolution, with the use of the populations only. On a longer time range we suggest that the same scheme could be extended to perform quantum logic, and a tentative suggestion, based on an available experiment, is discussed. We believe that the pumping can provide a partial proof of principle, although this and similar experiments were not interpreted thus far in our terms.

Pyrazolo-triazoles as light activable DNA cleaving agents.

In view of the continuous interest in new DNA cleaving compounds, both for the development of new therapeutic agents and for the possible use as reagents in nucleic acids research, a few pyrazolo[3,4-d][1,2,3]triazole derivatives have been obtained and investigated for their antiproliferative activity and capability to cleave DNA, after light-activation. A possible in situ activation, i.e. in neoplastic tissues, of less cytotoxic derivatives, may lead to potential antitumor compounds endowed with high therapeutic indexes.