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1.
Sci Rep ; 8(1): 7559, 2018 05 15.
Article in English | MEDLINE | ID: mdl-29765089

ABSTRACT

E-cigarette aerosol emission studies typically focus on benchmarking toxicant levels versus those of cigarettes. However, such studies do not fully account for the distinct chemical makeup of e-liquids and their unique properties. These approaches often conclude that there are fewer and lower levels of toxins produced by e-cigarettes than by cigarettes. In 2015, we reported the discovery of new hemiacetals derived from the reaction of formaldehyde and the e-liquid solvents. The main finding was that they constituted a significant proportion of potentially undetected formaldehyde. Moreover, unlike gaseous formaldehyde, the hemiacetals reside in the aerosol particulate phase, and thus are capable of delivering formaldehyde more deeply into the lungs. However, the findings were criticized by those claiming that some of the results were obtained under conditions that are averse to vapers. A "reinvestigation" of our study was recently published addressing this latter issue. However, this reinvestigation ignored major details, including no mention of the formaldehyde hemiacetals. Herein, we isolated both gaseous formaldehyde and formaldehyde hemiacetals at an intermediate power level claimed, in the "reinvestigation", to be relevant to "non-averse," "normal" usage. The results were that both gaseous formaldehyde and formaldehyde from hemiacetals were produced at levels above OSHA workplace limits.


Subject(s)
Acetals/isolation & purification , Aerosols/isolation & purification , Formaldehyde/isolation & purification , Acetals/toxicity , Aerosols/toxicity , Chromatography, High Pressure Liquid , Electronic Nicotine Delivery Systems , Formaldehyde/toxicity , Magnetic Resonance Spectroscopy
2.
Anal Chem ; 90(11): 7018-7024, 2018 06 05.
Article in English | MEDLINE | ID: mdl-29756765

ABSTRACT

Herein we utilize the similar though divergent nucleophilic properties of cysteine, homocysteine, and glutathione to achieve the selective detection of cysteine under mildly acidic conditions. This enables the specific in situ detection of lysosomal cysteine. Employing time-dependent fluorescent imaging of probe-labeled A549 cells, we demonstrate that dexamethasone-induced apoptosis is not dependent on lysosomal cysteine. This methodology can thus produce useful information about pathogenesis associated with cysteine and lysosomes.


Subject(s)
Apoptosis/drug effects , Cysteine/analysis , Dexamethasone/pharmacology , Lysosomes/chemistry , Optical Imaging , A549 Cells , Animals , Humans , Microscopy, Confocal , Molecular Structure , Tumor Cells, Cultured , Zebrafish
3.
Sci Rep ; 7(1): 11044, 2017 09 08.
Article in English | MEDLINE | ID: mdl-28887552

ABSTRACT

The electronic cigarette solvents propylene glycol and glycerol are known to produce toxic byproducts such as formaldehyde, acetaldehyde and acrolein. However, the aerosol toxin yield depends upon a variety of chemical and physical variables. The formaldehyde hemiacetals derived from these solvents were reported as major electronic cigarette aerosol components by us in 2015. In the study described herein, the formaldehyde hemiacetals were found at higher levels than those of free formaldehyde via an orthogonal sample collection protocol. In addition, the common aldehyde collection methods for electronic cigarettes, such as impingers and sorbent tubes containing DNPH, significantly underestimate the levels of formaldehyde. The reason for this is that formaldehyde hemiacetals follow other reaction pathways, such as the formation of a less reactive full cyclic acetal catalyzed by the acidity of the DNPH solution and the silica. We found that formaldehyde hemiacetals are a considerable fraction of the total formaldehyde produced in electronic cigarette that cannot be determined accurately by DNPH derivatization methods. Although the health effects of the hemiacetals are not yet known, they warrant further investigation.


Subject(s)
Aerosols/chemistry , Electronic Nicotine Delivery Systems , Formaldehyde/analogs & derivatives , Formaldehyde/analysis , Chromatography, High Pressure Liquid , Magnetic Resonance Spectroscopy
4.
Angew Chem Int Ed Engl ; 56(43): 13188-13198, 2017 10 16.
Article in English | MEDLINE | ID: mdl-28703457

ABSTRACT

Biothiols such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH) play crucial roles in maintaining redox homeostasis in biological systems. This Minireview summarizes the most significant current challenges in the field of thiol-reactive probes for biomedical research and diagnostics, emphasizing the needs and opportunities that have been under-investigated by chemists in the selective probe and sensor field. Progress on multiple binding site probes to distinguish Cys, Hcy, and GSH is highlighted as a creative new direction in the field that can enable simultaneous, accurate ratiometric monitoring. New probe design strategies and researcher priorities can better help address current challenges, including the monitoring of disease states such as autism and chronic diseases involving oxidative stress that are characterized by divergent levels of GSH, Cys, and Hcy.

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