Proton-Coupled Electron Transfer in the Reaction of 3,4-Dihydroxyphenylpyruvic Acid with Reactive Species in Various Media

<div>Reaction free energies for the reaction <svg height="15.2434pt" id="M148" style="vertical-align:-3.9935pt" version="1.1" viewbox="-0.0498162 -11.2499 155.034 15.2434" width="155.034pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.0135,0,0,-0.0135,0,0)"><path d="M631 18C609 24 585 35 559 65C534 91 514 117 478 169C448 214 406 281 389 313C462 346 516 399 516 485C516 545 490 590 449 616C412 641 363 650 290 650H42V622C120 615 128 612 128 527V125C128 40 120 34 38 28V0H300V28C221 34 212 40 212 125V284H244C295 284 312 272 329 244C359 195 395 133 430 84C475 19 516 -3 592 -7C603 -8 615 -8 627 -8L631 18ZM212 316V563C212 591 215 602 223 607C231 613 248 617 277 617C352 617 423 577 423 469C423 415 407 375 368 345C343 324 310 316 260 316H212Z" id="g190-83"></path><glyph.data ascent="989" descent="-360" horiz-adv-x="621" vert-adv-y="621"></glyph.data></g><g transform="matrix(.0135,0,0,-0.0135,8.305,0)"><path d="M381 665C170 665 44 498 44 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descent="-360" horiz-adv-x="766" vert-adv-y="766"></glyph.data></g><g transform="matrix(.0135,0,0,-0.0135,73.47,0)"><path d="M901 255C861 290 790 361 716 442L694 427L796 280H69V230H796L694 83L716 68C790 149 861 220 901 255Z" id="g117-148"></path><glyph.data ascent="3473" descent="-2876" horiz-adv-x="954" vert-adv-y="954"></glyph.data></g><g transform="matrix(.0135,0,0,-0.0135,92.451,0)"><path d="M631 18C609 24 585 35 559 65C534 91 514 117 478 169C448 214 406 281 389 313C462 346 516 399 516 485C516 545 490 590 449 616C412 641 363 650 290 650H42V622C120 615 128 612 128 527V125C128 40 120 34 38 28V0H300V28C221 34 212 40 212 125V284H244C295 284 312 272 329 244C359 195 395 133 430 84C475 19 516 -3 592 -7C603 -8 615 -8 627 -8L631 18ZM212 316V563C212 591 215 602 223 607C231 613 248 617 277 617C352 617 423 577 423 469C423 415 407 375 368 345C343 324 310 316 260 316H212Z" id="g190-83"></path><glyph.data ascent="989" descent="-360" horiz-adv-x="621" vert-adv-y="621"></glyph.data></g><g transform="matrix(.0135,0,0,-0.0135,100.755,0)"><path d="M381 665C170 665 44 498 44 318C44 125 188 -15 369 -15C552 -15 703 117 703 333C703 534 550 665 381 665ZM359 629C491 629 601 517 601 306C601 114 502 21 390 21C249 21 146 158 146 346S248 629 359 629Z" id="g190-80"></path><glyph.data ascent="989" descent="-360" horiz-adv-x="747" vert-adv-y="747"></glyph.data></g><g transform="matrix(.0095,0,0,-0.0095,110.945,-5.984)"><path d="M333 262C333 337 270 397 193 397S54 337 54 262S116 127 193 127S333 187 333 262Z" id="g54-74"></path><glyph.data ascent="3443" descent="-2856" horiz-adv-x="385" vert-adv-y="385"></glyph.data></g><g transform="matrix(.0135,0,0,-0.0135,118.136,0)"><path d="M535 230V280H323V490H265V280H52V230H265V-3H323V230H535Z" id="g117-36"></path><glyph.data ascent="3473" descent="-2876" horiz-adv-x="587" vert-adv-y="587"></glyph.data></g><g transform="matrix(.0135,0,0,-0.0135,129.117,0)"><path d="M729 650H468V622C546 615 554 610 554 527V365H213V527C213 610 221 616 297 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id="g190-80"></path><glyph.data ascent="989" descent="-360" horiz-adv-x="747" vert-adv-y="747"></glyph.data></g></svg>, in different media. ROH stands for 3,4-DHPPA, while <svg height="11.4901pt" id="M149" style="vertical-align:-0.2402pt" version="1.1" viewbox="-0.0498162 -11.2499 22.7573 11.4901" width="22.7573pt" xmlns="http://www.w3.org/2000/svg" xmlns:xlink="http://www.w3.org/1999/xlink"><g transform="matrix(.0135,0,0,-0.0135,0,0)"><path d="M631 18C609 24 585 35 559 65C534 91 514 117 478 169C448 214 406 281 389 313C462 346 516 399 516 485C516 545 490 590 449 616C412 641 363 650 290 650H42V622C120 615 128 612 128 527V125C128 40 120 34 38 28V0H300V28C221 34 212 40 212 125V284H244C295 284 312 272 329 244C359 195 395 133 430 84C475 19 516 -3 592 -7C603 -8 615 -8 627 -8L631 18ZM212 316V563C212 591 215 602 223 607C231 613 248 617 277 617C352 617 423 577 423 469C423 415 407 375 368 345C343 324 310 316 260 316H212Z" id="g190-83"></path><glyph.data ascent="989" descent="-360" horiz-adv-x="621" vert-adv-y="621"></glyph.data></g><g transform="matrix(.0135,0,0,-0.0135,8.305,0)"><path d="M381 665C170 665 44 498 44 318C44 125 188 -15 369 -15C552 -15 703 117 703 333C703 534 550 665 381 665ZM359 629C491 629 601 517 601 306C601 114 502 21 390 21C249 21 146 158 146 346S248 629 359 629Z" id="g190-80"></path><glyph.data ascent="989" descent="-360" horiz-adv-x="747" vert-adv-y="747"></glyph.data></g><g transform="matrix(.0095,0,0,-0.0095,18.495,-5.984)"><path d="M333 262C333 337 270 397 193 397S54 337 54 262S116 127 193 127S333 187 333 262Z" id="g54-74"></path><glyph.data ascent="3443" descent="-2856" horiz-adv-x="385" vert-adv-y="385"></glyph.data></g></svg> stands for its phenoxyl moiety.</div>

International Journal of Chemical Physics

fig10

Figure 10

Figure 10: Proton-Coupled Electron Transfer in the Reaction of 3,4-Dihydroxyphenylpyruvic Acid with Reactive Species in Various Media 