A Greener Chemiluminescence Demonstration

Abstract

b S Supporting Information C hemiluminescence is light emission from a chemical reaction. Peroxyoxalate chemiluminescence involves the reaction of oxalate diesters with hydrogen peroxide to generate unstable 1,2-dioxetanedione, which decomposes into electronically excited carbon dioxide (Scheme 1). The excited CO 2 transfers energy to a fluorescer or fluorophore, which releases light upon decay to the ground state. 1,2 Cyalume "light sticks" utilize this same chemistry for emergency lighting, fishing lures, and entertainment. The commercially available oxalate diesters, bis(2,4,6-trichlorophenyl)oxalate (TCPO) and bis(2,4-nitrophenyl)oxalate (DNPO), are typically used in both lecture demonstrations and laboratory experiments in chemiluminescence. 3À6 However, the serious environmental toxicities of the products 2,4,6-trichlorophenol 7 and 2,4-dinitrophenol, 8 as well as exposure to potentially hazardous organic solvent vapors in an open air setting, have encouraged us to redesign this demonstration along greener lines. In our demonstration, hazardous solvents such as dichloromethane are replaced with triacetin, a low volatility, nontoxic, and biodegradable compound, 9 and the oxalate diester is divanillyl oxalate 1, 10 which is readily prepared in one step from the artificial flavoring agent vanillin 2 (Scheme 2). In addition to CO 2 , the product of our chemiluminescent reaction is terrestrially nontoxic vanillin 2. 11 ' AUTHOR INFORMATION

A Photochemical Ligation System Enabling Solid‐Phase Chemiluminescence Read‐Out

“…Due to the high reactivity of oxalyl chloride employed in the last step, the aromatic compound needs orthogonal functional groups to be able to incorporate maleimides as reactive double bond for the NITEC reaction. The most frequently used POs -bis(trichlorophenyl) oxalate (TCPO), [33] bis (2,4-nitrophenyl)oxalate (DNPO), [33] bis(pentafluorophenyl) oxalate (PFPO) [19] or divanillyl oxalate (DVO) [34] do not present orthogonal pre or post-modifiable functionalities in their structure, requiring alternative synthetic pathways. Accordingly, a maleimide-PO compound (MPO) based on commercially available 4-amino phenol was synthesized in a simple three-step procedure.…”

In‐situ Chemiluminescence‐Driven Reversible Addition–Fragmentation Chain‐Transfer Photopolymerization

“…Many commercial systems employ a oxalate/peroxide system in combination with a fluorophore to generate light . Chemiluminescence has been observed in many different colors (blue, violet, red, yellow, green) using different dyes in the oxalate/peroxide system . The simplicity of this system also makes it useful in commercially available toys such as glow sticks.…”

Extraction of dyes contained in glow sticks using liquid CO2

“…Chemiluminescence is another topic that has been extensively covered in the chemistry curriculum (9)(10)(11)(12)(13)(14). In fact, chemiluminescent reactions have even been referred to as the most "exocharmic" reactions known, based on the high interest they generate in students and other observers (9).…”

“…In fact, chemiluminescent reactions have even been referred to as the most "exocharmic" reactions known, based on the high interest they generate in students and other observers (9). Chemiluminescent reactions have been used to introduce students to topics as varied as fluorescence, kinetics, thermodynamics, chromatography, catalysis, organic synthesis, and principles of green chemistry (9)(10)(11)(12)(13)(14). Many of these experiments have focused on the chemistry of glow sticks, which provide very easily obtained sources of chemiluminescent reactions.…”