Flow-injection spectrophotometric determination of chloramben

Abstract

A method for the dechlorination of PCB mixtures (Aroclor formulations) to biphenyl was extended to soils. The contaminated sample was mixed with magnesium flakes, potassium hexachloropalladiate (K₂PdCl₆), propan-2-ol and water then permitted to react for up to six hours. Biphenyl, recovered by extraction into hexane, was quantified by gas chromatography with flame ionization detection. The reaction was very efficient in propan-2-ol / water (～95%), surfactant emulsion or sand mixture and virtually complete in soil provided that excess magnesium (2 g) and the K₂PdCl₆ were added to the sample prior to the addition of water. Higher PCB loadings were readily determined in field contaminated soils either by direct determination within the matrix or by standard additions. However, analyte concentrations were appreciably over-estimated in Soxhlet or sonication extracts of a certified reference material that contained sub-ppm levels of analyte. The over-estimation is considered to result from the conversion in part of natural organic matter to biphenyl.     

Tuning the mesogenic properties of 5-alkoxy-2-(4-alkoxyphenyl)pyrimidine liquid crystals: the effect of a phenoxy end-group in two sterically equivalent series

Two sterically equivalent series of phenoxy-terminated 5-alkoxy-2-(4-alkoxyphenyl)pyrimidine liquid crystals were synthesised, and their mesogenic properties were characterised by polarised optical microscopy and differential scanning calorimetry (DSC). The phenoxy end-group causes a significant increase in melting point and inhibits – at least partially – the mesomorphism of these materials relative to the parent isomers; in most cases, the broad enantiotropic SmC phase formed by the parent isomers is suppressed by the addition of the phenoxy end-group. However, detailed analyses by small-angle X-ray scattering and monodomain 2D X-ray scattering suggest that these compounds form a SmA phase with a partially intercalated bilayer structure in which the phenoxy end-groups are nanosegregated. Such an intercalated bilayer structure might enable the tuning of smectogenic properties by appropriate substitution of the phenoxy end-groups.     

Facile Synthesis and in Vitro Cytotoxic Evaluation of Novel Thiadiazole,Pyrazole, and Dithiole-Androstane Derivatives

In the aim of identifying new steroidal cytotoxic agents with potential antiproliferative activity against hepatoma cell lines (Hep-G₂), we synthesized modified steroids containing the thiadiazole, pyrazole, or dithiole moiety. Epiandrosterone 1 reacted with carbon disulfide and sodium hydride to furnish α-oxoketene dithio-disodium salt 2. Treatment of 2 with the hydrazonoyl halides 5a–d produced the thiadiazole anellated androstanone 7a–d, respectively. The reaction of 1 with hydrazine hydrate produced the hydrazide adduct 8, which cyclized upon reflux in acetic acid to form the condensed pyrazoloandrostanone derivative 9. Interaction of 8 with carbon disulfide and sodium hydride formed the disodium salt 10, which reacted with ethylchloroacetate to furnish the final adduct, dithioloandrostane derivative, 13. Compounds 7a, 7d, 9, and 13 were examined for their cytotoxicity against a panel of hepatoma cell lines (Hep-G₂) using MTT assay. The results provide that, at incubation time 72 h, in DMSO, compound 7d (50 μ mol/mL) showed the most significant cytotoxic effect at P < 0.05. The higher dose (100 μ mol/mL) of compound 7d, at 48 h incubation, reversed the effect causing resistance and the growth rate return to the control level.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Bigger data,collaborative tools and the future of predictive drug discovery

Over the past decade we have seen a growth in the provision of chemistry data and cheminformatics tools as either free websites or software as a service commercial offerings. These have transformed how we find molecule-related data and use such tools in our research. There have also been efforts to improve collaboration between researchers either openly or through secure transactions using commercial tools. A major challenge in the future will be how such databases and software approaches handle larger amounts of data as it accumulates from high throughput screening and enables the user to draw insights, enable predictions and move projects forward. We now discuss how information from some drug discovery datasets can be made more accessible and how privacy of data should not overwhelm the desire to share it at an appropriate time with collaborators. We also discuss additional software tools that could be made available and provide our thoughts on the future of predictive drug discovery in this age of big data. We use some examples from our own research on neglected diseases, collaborations, mobile apps and algorithm development to illustrate these ideas.     

Structural properties of the trimetallic acetylide complex [{Ru(CO)2(η5C5H5)}3(η1:η1:η2:-CC)]+

The purpose of this Note is the study of the structure and fluxional behavior of the complex [{Ru(CO)₂(η⁵C₅H₅)}₃(η¹:η¹:η²:-CC)]⁺, using density functional methods. The molecular geometry of this complex will be optimized, the transition state (TS) of the fluxional process will be determined and the origin of the energy barrier will be analyzed.     

Synthesis and anticancer activity of some new heterocyclic compounds based on 1-cyanoacetyl-3,5-dimethylpyrazole

Research on Chemical Intermediates - The starting 3-(3,5-dimethyl-1H-pyrazol-1-yl)-3-oxopropanenitrile (1) reacts with phenyl isothiocyanate and ethyl bromoacetate to give the corresponding...     

Strategic analysis of the dairy transportation problem

The dairy transportation problem (DTP) consists of determining the best routes to be performed for collecting milk from farms and delivering it to processing plants. We study the particular case of the province of Quebec, where the Fédération des producteurs de lait du Québec is responsible for negotiating the transportation costs on behalf of producers. Several issues are highlighted in the actual process of designing contracts such as using historical data. We propose an approach based on scenario analysis that consists of revising both the steps and the information used to construct the routes. We develop a generalized tabu search algorithm that integrates the different characteristics of the DTP.     

Catalytic hydrolysis of phosphodiesters by nucleophilic ions in gemini micellar media

The catalytic hydrolysis of bis(4‐nitrophenyl)phosphate (BNPP) and bis(2,4‐dinitrophenyl)phosphate (BDNPP) catalyzed by α‐nucleophiles in gemini micellar media was investigated at 27 °C. The cationic gemini surfactants, i.e., alkanediyl‐α‐ω‐bis(hydroxyethylmethylhexadecylammonium bromide) (16‐s‐16 MEA 2Br^?, where s = 4 and 6) were used. Nucleophilic reactivity of α‐nucleophiles such as hydroperoxide (HOO^?), acetohydroxamate (AHA^?), and butane 2,3‐dione monoximate ions (BDMO^?) were compared. The kinetic rate data were treated by applying the pseudophase model. The cationic gemini surfactants show unusual rate acceleration toward the cleavage of phosphodiesters with nucleophiles. These studies reveal that the hydroperoxide ion shows the highest catalytic activity reported so far with an unprecedented acceleration rate, 10⁷ times faster than that of the uncatalyzed reaction. The possible mechanism for the BNPP and BDNPP cleavage promoted by α‐nucleophiles is proposed on the basis of kinetic analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

Densitometric Kinetic Stability Studies of Some Plant Extracts Using Different Regression Methods

JPC – Journal of Planar Chromatography – Modern TLC -