Analysis of Organophosphorus Compounds. 1. Application of Iodine-Azide Reaction for Detection of Thiophosphoorganic Compounds in Thin-Layer Chromatography

Wydrukowano z dostarczonych Wydawnictwu UŁ gotowych materiałówZadanie pt. Digitalizacja i udostępnienie w Cyfrowym Repozytorium Uniwersytetu Łódzkiego kolekcji czasopism naukowych wydawanych przez Uniwersytet Łódzki nr 885/P-DUN/2014 zostało dofinansowane ze środków MNiSW w ramach działalności upowszechniającej naukę

Some bis(dialkylphosphinyl) methanes as solvent extractants

An extensive review of some of the more important neutral organophosphorus compounds as solvent extractants was given. The compounds included were tri-n-butyl phosphate, TBP, tri-n-octylphosphine oxide, TOPO, tris (2 -ethylhexyl)phosphine oxide, TEHPO, and bis (di-n-hexylphosphinyl) methane, HDPM. A review was also given on the effects of structure on the extracting power of neutral organophosphorus compounds

Studies of organophosphorus compounds by nuclear magnetic resonance spectroscopy with two frequency dimensions

A range of organophosphorus compounds with bicyclic and tricyclic cage structures has been prepared and studied by n.m.r. spectroscopy

Organofosforni spojevi i esteraze: stanje sadašnjih istraživanja toksičnosti i zaštite od organofosfata

This brief review describes the reactions of organophosphorus compounds with cholinesterases, neuropathy target esterase, and phosphoric triester hydrolases with respect to their toxicity. It also describes antidotes, protectors, and decontaminating agents against organophosphates.U ovom prikazu opisane su reakcije organofosfornih (OP) spojeva s kolinesterazama, hidrolazama fosfornih triestera (PTH) i esterazom koja je povezana s neuropatskim djelovanjem OP spojeva (NTE). Kolinesteraze i NTE su serinske esteraze. Organofosforni spojevi inhibiraju te enzime zato što fosforiliraju serin u aktivnom mjestu enzima. Inhibicija acetilkolinesteraze (AChE) je glavni uzrok akutne toksičnosti OP spojeva. Suprotno serinskim esterazama, PTH enzimi hidroliziraju OP spojeve i time ih detoksiciraju. Oksimi su antidoti kod akutnog otrovanja OP spojevima zato što defosforiliraju inhibiranu AChE. Oksimi dodatno štite slobodnu AChE od fosforiliranja. Hidrolaze fosfornih triestera, kao i butirilkolinesteraza (BChE), služe i za dekontaminaciju od OP spojeva, a oba enzima istražuju se i kao mogući protektori protiv otrovanja OP spojevima. U prikazu su opisane i molekulske strukture AChE i PTH

A Nanoparticle/enzyme System For The Simultaneous Detection And Decontamination Of Organophosphates

The need for a direct visual response system for the detection of organophosphorus compounds stems from the continued threat and use of these toxic agents in military and terrorist conflicts. The development of an enzyme-inhibitor triggered release system allows for direct visual detection with high specificity. Mesoporous silica nanoparticles (MSNs) have physical features that make them attractive as scaffolds for the construction of these systems, such as pore diameters (20-500 Á) that can be synthetically controlled, large surface areas (300-1500 m2g-1), large pore volumes, chemical inertness, stability at elevated temperatures, and surfaces that can be easily functionalized. In our studies, the dye Congo Red was loaded into the pores of MSNs, which were then capped by tethering an enzyme (organophosphorus hydrolase (OPH) or acetylcholinesterase (AChE)) to the external surfaces of MSNs through a competitive inhibitor (diethyl 4-aminobenzyl phosphonate (DEABP) or tacrine, respectively). OPH has been extensively studied for its ability to hydrolyze a wide range of organophosphorus compounds, rendering them non-toxic. AChE has been commonly used for organophosphate detection resulting from its sensitivity to phosphorylation. Upon addition of organophosphorus compounds to suspensions of the modified MSNs, the enzymes detached from the MSN surface, releasing the dye and providing a visual confirmation of organophosphate presence. Enzyme kinetics were studied using 31P NMR or UV-Visible spectroscopy; Congo Red release was also monitored by UV-Visible spectroscopy. The system was sensitive and specific for organophosphorus compounds both in phosphate-buffered saline and in human serum. The rate of dye release directly correlated with the rate of organophosphorus conversion for OPH and the rate of phosphorylation for AChE

Solvent extraction properties of some BIS(DI-n-hexylphosphinyl) alkanes

A general comparison of the solvent extraction properties of some bidentate organophosphorus compounds with the structure 0 0 C6Hl3 P-(CH2)n -P (n-1, 2, 3, 4) C6Hl3 C6Hl3 is reported. The partition of mineral acids and the solvent extraction of uraniurn(VI), praseodymium, neodymium, samarium and thulium from nitrate, chloride and perchlorate media are considered. The cornplexing (in solution) of uraniurn(VI) nitrate by these bidentate ligands and tri-n-octyl phosphine oxide (TOPO) was investigated by means of infrared - spectral data, partition studies and molar conductivity and viscosity measurements. Chemical analyses and nuclear magnetic resonance proton spectral data for water-saturated solutions of these organophosphorus compounds in an inert diluent are presented

Probing Coherent Vibrations of Organic Phosphonate Radical Cations with Femtosecond Time-Resolved Mass Spectrometry

Organic phosphates and phosphonates are present in a number of cellular components that can be damaged by exposure to ionizing radiation. This work reports femtosecond time-resolved mass spectrometry (FTRMS) studies of three organic phosphonate radical cations that model the DNA sugar-phosphate backbone: dimethyl methylphosphonate (DMMP), diethyl methylphosphonate (DEMP), and diisopropyl methylphosphonate (DIMP). Upon ionization, each molecular radical cation exhibits unique oscillatory dynamics in its ion yields resulting from coherent vibrational excitation. DMMP has particularly well-resolved 45 fs (732 ± 28 cm−1) oscillations with a weak feature at 610–650 cm−1, while DIMP exhibits bimodal oscillations with a period of ∼55 fs and two frequency features at 554 ± 28 and 670–720 cm−1. In contrast, the oscillations in DEMP decay too rapidly for effective resolution. The low- and high-frequency oscillations in DMMP and DIMP are assigned to coherent excitation of the symmetric O–P–O bend and P–C stretch, respectively. The observation of the same ionization-induced coherently excited vibrations in related molecules suggests a possible common excitation pathway in ionized organophosphorus compounds of biological relevance, while the distinct oscillatory dynamics in each molecule points to the potential use of FTRMS to distinguish among fragment ions produced by related molecules

Probing Coherent Vibrations of Organic Phosphonate Radical Cations with Femtosecond Time-Resolved Mass Spectrometry

Organic phosphates and phosphonates are present in a number of cellular components that can be damaged by exposure to ionizing radiation. This work reports femtosecond time-resolved mass spectrometry (FTRMS) studies of three organic phosphonate radical cations that model the DNA sugar-phosphate backbone: dimethyl methylphosphonate (DMMP), diethyl methylphosphonate (DEMP), and diisopropyl methylphosphonate (DIMP). Upon ionization, each molecular radical cation exhibits unique oscillatory dynamics in its ion yields resulting from coherent vibrational excitation. DMMP has particularly well-resolved 45 fs (732 ± 28 cm−1) oscillations with a weak feature at 610–650 cm−1, while DIMP exhibits bimodal oscillations with a period of ∼55 fs and two frequency features at 554 ± 28 and 670–720 cm−1. In contrast, the oscillations in DEMP decay too rapidly for effective resolution. The low- and high-frequency oscillations in DMMP and DIMP are assigned to coherent excitation of the symmetric O–P–O bend and P–C stretch, respectively. The observation of the same ionization-induced coherently excited vibrations in related molecules suggests a possible common excitation pathway in ionized organophosphorus compounds of biological relevance, while the distinct oscillatory dynamics in each molecule points to the potential use of FTRMS to distinguish among fragment ions produced by related molecules

Fluorinated Epoxy Resins-based Sorbent Coating Materials for Quartz Piezoelectric Crystal Detector

Fluorinated epoxy resins were synthesised and evaluated as sorbent coating materials for the detection of organophosphorus compounds using quartz piezoelectric crystal detector. These resins were prepared by reacting excess of epichlorohydrin with each of or in combination of fluorinated diols, ie, a, a, a', a' tetrakis (trifluoromethyl) 1,3 benzene dimethanol (TTFMBD), 4,4'bis-2-hydroxy hexafluoro isopropyl) biphenyl (BHHFIBP), 4,4'dihydroxyocta fluorodiphenyl (DHOFDP) and 2,2,3,3,4,4 hexafluoro 1,5 pentanediol (HFPD) in the presence of sodium hydroxide at reflux temperature. These polymers were extracted in organic solvents and dried. Each of these fluoroepoxy resins were coated over quartz piezoelectric crystal by solution-casting method and tested using dimethylmethyl phosphonate (DMMP) as model compound. Change in the  frequency (AF) of quartz piezoelectric crystal oscillator was recorded. Sensitive and potential fluorinated epoxy resins, ie, diglycidylethers (DGE) of HFPD-TTFMBD (in the molar ratio 6:4) and DGE (HFPD-BHHFIBP in the molar ratio 4:6) were characterised by viscosity, number average molecular weight (Mn), epoxy equivalent, infrared spectroscopy, and thermal stability