Analysis of Efficient Ratiometric Fluorescent Chemodosimeter for detection of Phosgene
 
Satish Kumar1*, Dr. Sunil kumar2
1 Research Scholar, Deptt. of Chemistry, Magadh University Bodhgaya, Bihar (India)
E-mail : s3090khz@gmail.com
2 Assistant Professor, J.J. College, Gaya, Bihar (India)
E-mail : sunilchemu@gmail.com
Abstract - The study has been analysed the “Efficient ratiometric fluorescent chemodosimeter for detection of phosgene”. Nature has provided many outstanding examples of Molecular identification. Molecular recognition that biological situations and is seen in receptor-ligand, sugar-lectin, DNA-protein, antigen-antibody, and RNA-ribosome interactions. In this survey most design strategies for phosgene detection must rely on PET/ICT on mechanisms. Another relevant approach in the area of molecular recognition is the chemiosmotic method. For the replaced A new receptor, 3-oxime-4-hydroxy-1,8-naphthalic-N-butylamide (R1) which has intramolecular protonation within excited state transfer (ESIPT), has been shown to be a suitable radiometric fluorescence sensor or phosgene parameterization will help in the form. Results was described the Design of molecule for detection of phosgene. Further the kinetic study solution of Kinetic Study of R1 in AcCN After solution phase chemodosimetric reactions, fluorescence spectra were measured after mixing R1, ET3N and triphosgene in a 3 mL cubic 4-sided quartz cell. The reaction was carried out with the separation of additional quantities of ordinary triphosgene (between 50.0 equivalents, where the initial concentration was [R1] << [+triphosgene]) at standard ambient temperature, and the reaction conversion and chemical species was 100%.
Keywords: Ratiometric fluorescent, Chemodosimeter, Phosgene R1, Molecular recognition, and Gas chromatograpy.
INTRODUCTION
Molecular recognition and supramolecular chemistry molecular recognition has been molecular recognition and supramolecular chemistry molecular recognition to conceptualized as an approach that aims to systematically incorporate both the binding and selectivity of all substrates for a given receptor molecule, as well as possibly a specific function. This implies broadly defined patterns of intermolecular interactions in structurally well-defined regions. Overview of Language molecular hydrogen bonding, hydrophobic forces, metal coordination, van der waals forces, π–π interactions, halogen bonding between two or more molecules through a specific non-covalent bond Reflects specific interactions. a specific electrostatic effects. Thus the term supramolecular reflects the specialty of chemistry. Supramolecular chemistry is defined as "beyond molecular chemistry" that affects entities organized at high complexities, the molecular chemistry results are two or more chemical bond has species whom with intermolecular chemical force. That said, the scope of this term is extremely broad and includes many other large areas, one of which recognizes host-like molecules.
It is a faith in nature that is highly interdisciplinary, attracting chemists, biologists, environmental scientists, and conservation research persons such as biochemists, stalographers, physicists, theorists, and technologists.
Chemodosimeter: An application is to identifyee of a molecule also identity is an important factor in determining the analytical potency of analytes. So the nature of true meanings lies in molecular identities. In this, the power and concept of making supermolecule is a part of living-non-living systems. Nature has provided many excellent examples of molecular identification. Nature makes to provided lots of examples i.e., molecular recognition and environmental factors. It is recognition play on important role of some biological factors and observed that receptors ligand, Antigen-antibody, DNA on protein, RNA-ribosome, and sugar lectin.1
Supramolecular chemistry is the main tool in the development of nanotechnology. Progress in this field is now applied to medicine using nanotechnology. The distribution system will be used.
One of the attractive benefits of the science of supramolecular chemistry is the creation of small, well-defined nanostructures preferably from easily accessible molecules. The main unifying theme is the control of matter at the nanoscale (1–100 nm), a means by which the creation of nanomaterial devices will be revolutionary in the near future.2
Additionally, a large number of fluorogenic and chromogenic sensors for nerve gas agents have been developed, i.e. sensors for phosgene, in contrast, but are only a limited edition of the examples focused on. Reported phosgene and nerve gas were examined for mimics and selectivity has yet to be explored. 3 Some phosgene sensors containing reactive groups can be disrupted by formaldehyde, and other triphosgenes by nitric oxide. The amine-catalyzed decomposition of phosgene containing tertiary amines distinguishes phosgene from triphosgene.4
Characterization data of the synthesized probe R1
(È)¬2¯Bŭtył-Sixة-hydrοxy: 1,3-diοxο-2,3-dihydrο-1H, benzο{de)isοquinοline-5-carbaldehydeοxime [Ŗ1]
Yield: 72% (188 mil.gram, 0.86 milimiter). Characteristic: Yellow solid. M.P. 246-248 °C 1H NMR (300 MHz, DMSO-d 6 ): δ11.89 (Brs, 1 H), 8-68 [S:1h], 8,57-52 [m:2h], 8.44/ DJ:6.9hz,ih), 7.76[t,J:7.9hz,h1], 5.76[S:1h], 3.98{t,J:7.6hz,2h}, 1.64/1.54, [m,2h], 1.38:1.28[,m,2h], .91[t,J:7.3hz,3h].13
A nature of solute-solvent interactions. Therefore late increasing interest has been shown in the study of aqueous, pure, non-aqueous, mixed electrolytic and non-electrolytic solution 16/20 Earlier workers in ethanol-nitrobenzene and benzene twenty-six have carried out interaction studies on substituted acetic acids.
A study was reported ultrasound velocity and absorption measurements are under taken of aqueous electrolytic solutions of ammonium chloride, ammonium di hydrogen phosphate and ammonium oxalate having a common NH and anions of different charge densities. There salts show a non-linear increase in the velocity with concentration attributed to the increased cohesion among the water molecular due to the addition of the electrolytes. The observed absorption decrease with increasing concentration of the electrolyte due to the net decrease of non-hydrated water molecules, which mainly contribute for the absorption.
The conductance measurements of N-Bromo. N-Sodio, p-toluene sulphonamide (Bromamine-T. BAT) in water(H₂O). acetonitrile (CH,CN) and dimethyl formamide (DMF), and in various mixtures of these solvent have been carried out at various temperatures. Many workers 2:32 have studied ultrasound velocity, density and related parameters of binary electrolytic solutions ultrasonic relaxation and association with solute-solvent in an aqueous solution of 5-Methoxy 1-Pentanol by Nishikawa³³
A studied the reagent, benzyl (mono-oxime iso-nicotinoyl hydrazone). The maximum coloured intensity is observed in 10-11 pH ranges. This coloured reaction (molar absorptive1. 1.18X10.11 mol ‘cm’ at 405mm) has been used for determination of lead in different water samples.
Various scientist 35/36 calculated the ultrasound velocity in aqueous solution of sulphuric acid and phosphoric acid and pointed out the velocity depended on the temperature and concentration abnormally. They also evaluated all three dissociation constants for phosphoric acid by neutralizing both the acids with acoustic soda, ultrasonically, decrease in molar sound velocity with increasing concentration of Cdl, in Me, Cu, EtOH and ethylene glycol study..
The study was experimented a systematic analysis of experimental data on extraction of organic solutes with organic solvents indicates that non- specific intermolecular interactions are better described by pair wise interaction potentials of London-Debye-Keesom than by the Hilderbrand solubility parameters.
A partial molar volume by ultrasonic studies of aqueous solution of octahedral CO(III) complexes at different temperature. The apparent and partial molar properties based on density measurements have been determined in aqueous solution tris (ethylene diamine) CO(III) chloride, trans-dichlorobis (ethylene diamine) CO(III) bromide at-298.16K, & 303.16K and 313.16L. Ultrasound velocity also measured in aqueous solution of these CO(III) complexes at-303.16K. These results are discussed in the light of ion-solvent interaction.
The adiabatic compressibility, specific accoustic impedance, intermolecular free length, apparent molar compressibility, molar volume, molar sound velocity, solvation number, and relative association of Lil, Nal and KI in ethylene carbonate in order to understand the solute-solvent interaction more precisely. They also observed that ultrasound velocity in the solution of Lil, Nal, and Kl in ethylene carbonate in increases linearly with concentration.
Worked put interactions in dioxane-water co-solvent ultrasonic volumetric and viscometric studies on 2-hydroxy-5- Methylacetophenone and 2,4 dihydroxy acetophenone, Various thermodynamic parameters such as apparent molar volume, apparent molar compressibility and their limiting values have been determined.
The data collection results & discussed with light of research it will be solute/solvent interaction. Marks6 concluded by studying sound velocity in aqueous solution if Li, Na, and K sulphates which increase on increasing ionic radius (Li:.06Amp, Na .095A, K-1.33A) while compressibility of sulphate decrease.
It is computed sound velocity, density and viscosity of aqueous solutions of Polytetro fluoro ethylene at different concentration and 303.16, and 313.16K. Ultrasound velocity also measured in aqueous solution of these CO(III) complexes at-303.16K. These results are discussed in the light of ion-solvent interaction.
Some others observation the adiabatic compressibility, specific accoustic impedance, intermolecular free length, apparent molar compressibility, molar volume, molar sound velocity, solvation number, and relative association of Lil, Nal and KI in ethylene carbonate in order to understand the solute-solvent interaction more precisely. They also observed that ultrasound velocity in the solution of Lil, Nal, and Kl in ethylene carbonate in increases linearly with concentration limiting values have been determined.
AIM OF THIS WORK
The aims of the studies would be to analysed the solute-solvent interactions studying sound velocity in aqueous solution if Li, Na, and K sulphates which increase on increasing ionic radius (Li .06A, Na’.095A, K -1.33A) while compressibility of sulphate decrease.
MATERIALS AND METHODS
A method was developed to identify phosgene molecules (R1) via anhydride (1) (2), CuSO4-catalyzed O-C coupling (3) and HI-mediated O-C cleavage to phenolic compounds (4). Including formylation with HMTA TFA (5) and finally prepare the probe (R1) via oxime (Scheme 4.2.2). Compounds (1-5) 31 and probe R1 were purified by column chromatography and fully characterized by spectroscopic analysis.
RESULTS
Molecular design for detection of phosgene molecules (R1) by anhydride (1) (2), CuSO4 catalyzed O-C coupling (3), HI mediated O-C cleavage to phenolic compounds (4), simulation of HMTA to form TFA (5) is synthesized in six steps including acylation and finally probe (R1) is prepared from oxime (Scheme 4.2.2). Compounds (1-5) 31 and probe R1 were purified by column chromatography and fully characterized by spectroscopic analysis.
Synthesis of probe R1
Detection of phosgene in solution:
Phosgene is weak and highly toxic, and its precursor triphosgene is a non-volatile, easy to control, low toxic substance. In the presence of tertiary amines, triphosgene is converted to phosgene. Therefore, we decided that the recommended amount of Et3N is 0.5% triphosgene. In the presence of large amounts of triphosgene, it is seen as UV-vis absorption and fluorescence emission spectral analysis of R1/AcCN/Et3N (0.5%) samples.
It can be seen that R1 in AcCN (10.0 µM) appears red-brown in the presence of Et3N and shows a strong absorption band at 498 nm. With the addition of triphosgene (0.1 µM), the intensity of the absorption of R1 at 498 nm decreases, while the intensity of new peaks at 328 nm and 254 nm increases and the color of the solution turns yellow-green.
UV−Vis absorption (a) and (b) Triphosgene (0.1 µM) was slowly added to a solution of R1/AcCN (10 µM) in the presence of Et3N (30 nM) until saturation (0.5 equiv). Legend: (a) Change in the human eye color of R1/AcCN/Et3N in the presence of triphosgene. (b) Fluorescence color change of R1/AcCN/Et3N at different triphosgene concentrations. 9
A sharp isoabsorbance point at 382 nm indicates the formation of a new compound, isoxazole. Initially, intramolecular charge transfer (ICT) occurs from the naphthalenedicarboxylic acid-OH and oxime-N-OH to the naphthalimide moiety in the R1 probe, resulting in a red color of the solution and corresponding to the absorbance peak at 498 nm. The blue shift of the absorption spectrum after reaction with phosgene is due to the closure of the ICT process initiated by the cyclization of R1 to isoxazoline derivative. Under excitation at 382 nm, the sample R1 (10.0 µM)/AcCN/Et3N (0.5%) emits orange fluorescence in the 577 nm region with a quantum yield of ïβ = 0.31. After gradual addition of triphosgene, a new emission band appeared in the green region of 495 nm and gradually became the main emission band of the orange band until 0.5 equal triphosgene was added, the used green fluorescence reached saturation and the orange quantum yield disappeared. ïβ = 0.26. The first band at 577 nm is due to the ESIPT (excited intramolecular proton transfer) process from naphthyl-OH to oxime nitrogen. Phase chemical dose response. The reaction was carried out in an excess of triphosgene (50.0 equiv, where the initial concentration [R1]<<[triphosgene]) at ambient temperature, and the reaction conversion rate was 100%. Separate solutions of R1 and triphosgene at different concentrations in AcCN in the presence of Et3N were prepared and mixed to study the kinetics. The excitation wavelength is 382 nm and in all cases the concentrations are low enough to keep the UV absorption at <0.5. The reaction rate is determined by fitting the fluorescence intensity of the sample solution at 495 nm to the quasi-first order equation (1): ln(Fmax -Ft)/Fmax = - kÕt âââ…(1 ) where, F(t), F(max) is the fluorescence intensity at the wavelength measured at time t and the maximum value is the final fluorescence intensity when the R1 change value reaches 100%. kÕ is the apparent constant (Fig. 4.3.1), which is a pseudo-first order plot of R1 against 10.0 equivalents of triphosgene. The negative slope of this plot indicates the apparent constant = 1.07016 S-1. The same experiment was performed for R1/filter paper, R1/PCL film and R1/PCL nanocomposite. In all cases the phosgene concentration was 0.5 ppm.
suede-first rate plot of R1 (10 μM) in AcCN in the presence of triphosgene (5 equiv). [Rate constant (k/ = 1.07016 s-1)].
The time-dependent fluorescence intensity of R1/AcCN/Et3N before and after the addition of tri-phosgene is shown. It was noted that the fluorescence intensity ratio (F496/F577) did not improve up to 1 min with the addition of Et3N alone, while the emission rate increased rapidly with the addition of tri-phosgene and reached saturation in approximately 2.0 s.
(a). The fluorescence intensity ratio (F495/F577) of R1 (10 μM)/Et3N (30 nM) before and after the addition of triphosgene (0.50 equiv) reveals the reaction of R1 to phosgene. (b) Kinetic curve of R1 (10 μM) in the presence of 50.0 equiv of triphosgene for the pseudo first-order rate constant.
The pseudo first cutoff constant value is assumed to be 1.07 s ± 1. The rapid increase in fluorescence is due to Et3N causing the decomposition of triphosgene to phosgene, but the reaction is very slow in the presence of triphosgene alone10. A review of emerging candidates for the use of phosgene.
CONCLUSION
This study describes the development of sensor R1 for phosgene colorimetry and fluorescence detection by taking advantage of the ESIPT technique. The reactive oxime functionality first forms the oxime-N-O-oxychloride and then undergoes O-N combined intramolecular cyclization, i.e. intramolecular cyclization of the ortho-hydroxyl group of the oxime to form the isoxazoline compound.
These are accompanied by changes in absorption and fluorescence spectra and can be detected by the naked eye. Sensor R1 selectively detects phosgene better than other competing analytes, including nerve cells. Furthermore, R1 embedded polymer fibers were prepared using electrospinning technique, which showed distinct color and fluorescence changes upon short-term (approximately 5 s) exposure to phosgene. All kinds of laws have been accepted for the determination of the limit and it has been found that phosgene is far below the recommended safe level for human civilization. However, for the first time we have prepared polymer-based films and nanofibers of R1 and compared its role with phosgene gas and found that the latter has higher performance. SEM images of films and nanofibers after adsorption of phosgene gas give a partial deformation on the surface due to the reaction of phosgene with small organic molecules (R1 as isoxazoline compounds). with we have found a simple, low-cost nanomaterial platform for rapid detection of negative gaseous environment of phosgene. Innovation in hearing technology for sexual health.
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