Special Issue "Radical Chemistry"
Deadline for manuscript submissions: 10 February 2018
Prof. Dr. John C. Walton
Radicals play an astonishing variety of roles in an amazingly diverse range of sciences and technologies. Our understanding of the almost unlimited flexibility of their structures and the huge breadth of their activities has expanded wonderfully in the last few years. Notable new advances include: The burgeoning exploitation of photoredox catalysis in mild synthetic procedures, boron-containing radicals in syntheses, oxime derivatives as radical precursors, radical cascade reactions, novel controlled/living radical mediated polymerization methods, double spin labelling for EPR distance measurements in biopolymers and organic super electron donors. Radical-mediated syntheses are steadily taking their place alongside more traditional nucleophile/electrophile preparative procedures. In fact, radical-mediated preparations frequently enable tedious protection/deprotection steps to be dispensed with and this, coupled with the neutral conditions and absence of harsh acidic/basic reagents, makes their use particularly attractive. Radical reactivity depends strongly on the underlying thermodynamics. Key thermodynamic parameters have been obtained for many model radicals and archetype radical clocks are available for assessing reactivity. These tools, supplemented and augmented by DFT computational methods, ensure that synthetic planning is comparatively easy and that mechanisms can be rationally established. Furthermore, radical intermediates can often be elegantly characterized and monitored by EPR spectroscopic methods. Persistent radicals are finding more and more uses in both biological and materials sciences. The aim of this Special Issue is to review and showcase recent research across the whole field. Papers and review articles are welcomed in the heartland areas of radical-based synthesis and physical organic chemistry, as well as in all the newly-developing fields.Prof. Dr. John C. Walton
Manuscript Submission Information
Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.
Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access monthly journal published by MDPI.
Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.
- Reactive intermediates
- Radical-mediated synthetic methods
- Radical reagents
- Radical cyclizations
- Radical rearrangements
- Radical kinetics and mechanisms
- Redox properties of radicals
- Thermochemistry of radicals
- Photoredox catalysis
- Spin trapping and spin labelling
- Radical mediated polymerizations
- Applications of EPR spectroscopy
The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.
Title: Mechanistic Insight into the Reactivity of Hydroxyl Radical with Dissolved Organic Matter in the Aqueous phase Advanced Oxidation System: Ab Initio and Density Functional Theory Quantum Mechanical Calculations
Authors: Mallika Khare 1, Daisuke Minakata 1,*
Affiliations: Department of Civil and Environmental Engineering, Michigan Technological University, 1400 Townsend Drive, Houghton, MI, 49931, USA
Abstract: Advanced Oxidation Processes (AOPs) that produce highly reactive hydroxyl radicals (HO∙) are promising water treatment technologies that can destroy a wide variety of organic chemical contaminants in water. However, the presence of background dissolved organic matter (DOM) is detrimental to the overall performance of AOPs because it scavenges HO∙. While overall reactivity of hydroxyl radicals (HO∙) with surrogate DOM has been extensively studied, little is known about their molecular-level reactivity. In this study, we use ab initio and density functional theory quantum mechanical calculations to study the molecular-level reactivity of HO∙ with a relatively larger model monomer of a Suwanee River Fulvic Acid Temple Northeastern Birmingham (TNB) model. We calculated the aqueous-phase free energies of activation to examine the HO∙ reactivity at the representative reactive sites of the TNB model. We also calculated those energies for the segmented TNB model and compared to those for the entire TNB model. These comparisons revealed that the surrounding functional group(s) significantly affects the HO∙ reactivity with the specific site of the TNB model by reducing the aqueous phase free energies of activation. This is the first study to investigate the molecular-level reactivity of HO∙ with a model monomer of surrogate DOM. The results provide mechanistic insights into the local reactivity of HO∙ and the initial fate of DOM transformation.