A Fluorescent Sensor for Dual-Channel Discrimination between Phosgene and a Nerve-Gas Mimic
TL;DR: A o-phenylenediamine-pyronin linked dye that is capable of both fluorogenic and colorimetric discrimination between phosgene and the prototypical nerve-agent mimic, diethyl chlorophosphate (DCP) in the solution or gas phase is designed.
Abstract: The ability to analyze highly toxic chemical warfare agents (CWAs) and related chemicals in a rapid and precise manner is essential in order to alleviate serious threats to humankind and public security caused by unexpected terrorist attacks and industrial accidents. In this investigation, we designed a o-phenylenediamine-pyronin linked dye that is capable of both fluorogenic and colorimetric discrimination between phosgene and the prototypical nerve-agent mimic, diethyl chlorophosphate (DCP) in the solution or gas phase. Moreover, this dye has been used to construct a portable kit that can be employed for real-time monitoring of DCP and phosgene in the field, both in a discriminatory manner, and in a simple and safe way.
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TL;DR: This review focuses on recent innovations in probe design, detection mechanisms and the investigation of biological processes and the ongoing development of fluorescent probes to enable deeper insight into the physiology of bioactive analytes.
Abstract: In contrast to the classical design of a probe with one binding site to target one specific analyte, probes with multiple interaction sites or, alternatively, with single sites promoting tandem reactions to target one or multiple analytes, have been developed. They have been used in addressing the inherent challenges of selective targeting in the presence of structurally similar compounds and in complex matrices, as well as the visualization of the in vivo interaction or crosstalk between the analytes. Examples of analytes include reactive sulfur species, reactive oxygen species, nucleotides and enzymes. This review focuses on recent innovations in probe design, detection mechanisms and the investigation of biological processes. The vision is to promote the ongoing development of fluorescent probes to enable deeper insight into the physiology of bioactive analytes.
223 citations
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TL;DR: This review describes in a comprehensive manner recent progress that has been made on the development of chromophore-based chemosensors for detecting nerve agents (mimic) and phosgene.
Abstract: The extreme toxicity and ready accessibility of nerve agents and phosgene has caused an increase in the demand to develop effective systems for the detection of these substances. Among the traditional platforms utilized for this purpose, chemosensors including surface acoustic wave (SAW) sensors, enzymes, carbon nanotubes, nanoparticles, and chromophore based sensors have attracted increasing attention. In this review, we describe in a comprehensive manner recent progress that has been made on the development of chromophore-based chemosensors for detecting nerve agents (mimic) and phosgene. This review comprises two sections focusing on studies of the development of chemosensors for nerve agents (mimic) and phosgene. In each of the sections, the discussion follows a format which concentrates on different reaction sites/mechanisms involved in the sensing processes. Finally, chemosensors uncovered in these efforts are compared with those based on other sensing methods and challenges facing the design of mor...
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TL;DR: In this paper, the most significant developments in fluorescent probes for the detection of the carbonyl species formaldehyde, carbon monoxide and phosgene in recent years, with a special emphasis on their mechanisms and applications.
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TL;DR: Three o-phenylendiamine derivatives, containing 4-chloro-7-nitrobenzo[c][1,2,5]oxadiazole, rhodamine, and 1,8-naphthalimide moieties, were prepared and tested as phosgene chemosensors and display distinct color and fluorescence changes upon exposure to phosGene even in the solid state.
Abstract: Three o-phenylendiamine (OPD) derivatives, containing 4-chloro-7-nitrobenzo[c][1,2,5]oxadiazole (NBD-OPD), rhodamine (RB-OPD), and 1,8-naphthalimide (NAP-OPD) moieties, were prepared and tested as phosgene chemosensors. Unlike previously described methods to sense this toxic agent, which rely on chemical processes that transform alcohols and amines to respective phosphate esters and phosphoramides, the new sensors operate through a benzimidazolone-forming reaction between their OPD groups and phosgene. These processes promote either naked eye visible color changes and/or fluorescence intensity enhancements in conjunction with detection limits that range from 0.7 to 2.8 ppb. NBD-OPD and RB-OPD-embedded polymer fibers, prepared using the electrospinning technique, display distinct color and fluorescence changes upon exposure to phosgene even in the solid state.
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TL;DR: A highly selective fluorescent sensor o-Pab for phosgene with a BODIPY unit as a fluorophore and o-phenylenediamine as a reactive site is constructed and excellent discrimination of o- Pab has been demonstrated to be due to the difference in highly reactive and bifunctional phosGene relative to its substitutes.
Abstract: As a highly toxic and widely used chemical, phosgene has become a serious threat to humankind and public security because of its potential use by terrorists and unexpected release during industrial accidents. For this reason, it is an urgent need to develop facile, fast, and selective detection methods of phosgene. In this Article, we have constructed a highly selective fluorescent sensor o-Pab for phosgene with a BODIPY unit as a fluorophore and o-phenylenediamine as a reactive site. The sensor o-Pab exhibits rapid response (∼15 s) in both colorimetric and turn-on fluorescence modes, high selectivity for phosgene over nerve agent mimics and various acyl chlorides and a low detection limit (2.7 nM) in solutions. In contrast to most undistinguishable sensors reported, o-Pab can react with phosgene but not with its substitutes, triphosgene and biphosgene. The excellent discrimination of o-Pab has been demonstrated to be due to the difference in highly reactive and bifunctional phosgene relative to its subst...
107 citations
References
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TL;DR: Although MRI, US, and x-ray CT are often listed as molecular imaging modalities, in truth, radionuclide and optical imaging are the most practical modalities for molecular imaging, because of their sensitivity and the specificity for target detection.
Abstract: In vivo medical imaging has made great progress due to advances in the engineering of imaging devices and developments in the chemistry of imaging probes Several modalities have been utilized for medical imaging, including X-ray radiography and computed tomography (x-ray CT), radionuclide imaging using single photons and positrons, magnetic resonance imaging (MRI), ultrasonography (US), and optical imaging In order to extract more information from imaging, “contrast agents” have been employed For example, organic iodine compounds have been used in X-ray radiography and computed tomography, superparamagnetic or paramagnetic metals have been used in MRI, and microbubbles have been used in ultrasonography Most of these, however, are non-targeted reagents
Molecular imaging is widely considered the future for medical imaging Molecular imaging has been defined as the in vivo characterization and measurement of biologic process at the cellular and molecular level1, or more broadly as a technique to directly or indirectly monitor and record the spatio-temporal distribution of molecular or cellular processes for biochemical, biologic, diagnostic, or therapeutic application2 Molecular imaging is the logical next step in the evolution of medical imaging after anatomic imaging (eg x-rays) and functional imaging (eg MRI) In order to attain truly targeted imaging of specific molecules which exist in relatively low concentrations in living tissues, the imaging techniques must be highly sensitive Although MRI, US, and x-ray CT are often listed as molecular imaging modalities, in truth, radionuclide and optical imaging are the most practical modalities, for molecular imaging, because of their sensitivity and the specificity for target detection
Radionuclide imaging, including gamma scintigraphy and positron emission tomography (PET), are highly sensitive, quantitative, and offer the potential for whole body scanning However, radionuclide imaging methods have the disadvantages of poor spatial and temporal resolution3 Additionally, they require radioactive compounds which have an intrinsically limited half life, and which expose the patient and practitioner to ionizing radiation and are therefore subject to a variety of stringent safety regulations which limit their repeated use4
Optical imaging, on the other hand, has comparable sensitivity to radionuclide imaging, and can be “targeted” if the emitting fluorophore is conjugated to a targeting ligand3 Optical imaging, by virtue of being “switchable”, can result in very high target to background ratios “Switchable” or activatable optical probes are unique in the field of molecular imaging since these agents can be turned on in specific environments but otherwise remain undetectable This improves the achievable target to background ratios, enabling the detection of small tumors against a dark background5,6 This advantage must be balanced against the lack of quantitation with optical imaging due to unpredictable light scattering and absorption, especially when the object of interest is deep within the tissue Visualization through the skin is limited to superficial tissues such as the breast7-9 or lymph nodes10,11 The fluorescence signal from the bright GFP-expressing tumors can be seen in the deep organ only in the nude mice 12,13 However, optical molecular imaging can also be employed during endoscopy14 or surgery 15,16
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TL;DR: All studies since 1940 on the prognosis of squamous cell carcinoma of the skin and lip are reviewed, finding local recurrences occur less frequently when SCC is treated by Mohs micrographic surgery.
Abstract: We reviewed all studies since 1940 on the prognosis of squamous cell carcinoma (SCC) of the skin and lip. The following variables are correlated with local recurrence and metastatic rates: (1) treatment modality, (2) prior treatment, (3) location, (4) size, (5) depth, (6) histologic differentiation, (7) histologic evidence of perineural involvement, (8) precipitating factors other than ultraviolet light, and (9) host immunosuppression. Local recurrences occur less frequently when SCC is treated by Mohs micrographic surgery. This local recurrence rate differential in favor of Mohs micrographic surgery holds true for primary SCC of the skin and lip (3.1% vs 10.9%), for ear SCC (5.3% vs 18.7%), for locally recurrent (previously treated) SCC (10% vs 23.3%), for SCC with perineural involvement (0% Ys 47%), for SCC of size greater than 2 cm (25.2% vs 41.7%), and for SCC that is poorly differentiated (32.6% vs 53.6%).
1,346 citations
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TL;DR: Chenodeoxycholic acid may offer medical treatment for cholesterol cholelithiasis in man and the ratio of bile acids and lecithin to cholesterol in bile increased in all patients.
Abstract: Seven women with gallstones were given 0.75 to 4.5 g per day of chenodeoxycholic acid, a primary bile acid, to promote micellar solubilization of cholesterol in bile. In Case 1 three stones that had remained unchanged in size during six years of observations disappeared after six months of treatment. A single stone in Case 2 and multiple calculi in Cases 3 and 4 progressively grew smaller during 14 to 22 months of chenodeoxycholic acid administration. Gallstone size did not change in the other three. Chenodeoxycholic acid and total bile acid pool sizes (measured in two patients), which were reduced before therapy, were markedly expanded by chenodeoxycholic acid, and the ratio of bile acids and lecithin to cholesterol in bile increased in all patients. Liver function and morphology remained normal; moderate dose-related diarrhea occurred. Chenodeoxycholic acid may offer medical treatment for cholesterol cholelithiasis in man.
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TL;DR: Indicators providing highly sensitive and functional group specific fluorescent response to diisopropyl fluorophosphate (DFP, a nerve gas (G-agent) simulant) are reported.
Abstract: Indicators providing highly sensitive and functional group specific fluorescent response to diisopropyl fluorophosphate (DFP, a nerve gas (G-agent) simulant) are reported. Nonemissive indicator 2 reacts with DFP to give a cyclized compound 2+A- that shows a high emission due to its highly planar and rigid structure. Very weak emission was observed by the addition of HCl. Another indicator based on pyridyl naphthalene exhibits a large shift in its emission spectrum after reaction with DFP, which provides for quantitative ratiometric detection.
440 citations