An official website of the United States government
The anionic products following (H + H + ) abstraction from o -, m -, and p -methylphenol (cresol) are investigated using flowing afterglow-selected ion flow tube (FA-SIFT) mass spectrometry and anion photoelectron spectroscopy (PES). The PES of the multiple anion isomers formed in this reaction are reported, including those for the most abundant isomers, o -, m - and p -methylenephenoxide distonic radical anions. The electron affinity (EA) of the ground triplet electronic state of neutral m -methylenephenoxyl diradical was measured to be 2.227 ± 0.008 eV. However, the ground singlet electronic states of o - and p -methylenephenoxyl were found to be significantly stabilized by their resonance forms as a substituted cyclohexadienone, resulting in measured EAs of 1.217 ± 0.012 and 1.096 ± 0.007 eV, respectively. Upon electron photodetachment, the resulting neutral molecules were shown to have Franck–Condon active ring distortion vibrational modes with measured frequencies of 570 ± 180 and 450 ± 80 cm −1 for the ortho and para isomers, respectively. Photodetachment to excited electronic states was also investigated for all isomers, where similar vibrational modes were found to be Franck–Condon active, and singlet–triplet splittings are reported. The thermochemistry of these molecules was investigated using FA-SIFT combined with the acid bracketing technique to yield values of 341.4 ± 4.3, 349.1 ± 3.0, and 341.4 ± 4.3 kcal mol −1 for the o -, m -, and p -methylenephenol radicals, respectively. Construction of a thermodynamic cycle allowed for an experimental determination of the bond dissociation energy of the O–H bond of m -methylenephenol radical to be 86 ± 4 kcal mol −1 , while this bond is significantly weaker for the ortho and para isomers at 55 ± 5 and 52 ± 5 kcal mol −1 , respectively. Additional EAs and vibrational frequencies are reported for several methylphenyloxyl diradical isomers, the negative ions of which are also formed by the reaction of cresol with O − .
more »
« less
Setting benchmarks for ethylene and propylene oxidation via electrochemical routes: a process design and technoeconomic analysis approach
Electrochemical ethylene and propylene oxidations are economically feasible under different conditions and process advancements.
more »
« less
- Award ID(s):
- 2029326
- PAR ID:
- 10549644
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Green Chemistry
- Volume:
- 26
- Issue:
- 17
- ISSN:
- 1463-9262
- Page Range / eLocation ID:
- 9455 to 9475
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Hudson, André O (Ed.)ABSTRACT The fungal genusNeonectriacontains many phytopathogenic species currently impacting forests and fruit trees worldwide. Despite their importance, a majority ofNeonectriaspp. lack sufficient genomic resources to resolve suspected cryptic species. Here, we report draft genomes and assemblies forNeonectria magnoliaeNRRL 64651 andNeonectria puniceaNRRL 64653.more » « less
-
Abstract In 1974, Sue Herring described the relationship between two important performance variables in the feeding system, bite force and gape. These variables are inversely related, such that, without specific muscular adaptations, most animals cannot produce high bite forces at large gapes for a given sized muscle. Despite the importance of these variables for feeding biomechanics and functional ecology, the paucity of in vivo bite force data in primates has led to bite forces largely being estimated through ex vivo methods. Here, we quantify and compare in vivo bite forces and gapes with output from simulated musculoskeletal models in two craniofacially distinct strepsirrhines:Eulemur, which has a shorter jaw and slower chewing cycle durations relative to jaw length and body mass compared toVarecia. Bite forces were collected across a range of linear gapes from 16 adult lemurs (suborder Strepsirrhini) at the Duke Lemur Center in Durham, North Carolina representing three species:Eulemur flavifrons(n = 6; 3F, 3M),Varecia variegata(n = 5; 3F, 2M), andVarecia rubra(n = 5; 5F). Maximum linear and angular gapes were significantly higher forVareciacompared toEulemur(p = .01) but there were no significant differences in recorded maximum in vivo bite forces (p = .88). Simulated muscle models using architectural data for these taxa suggest this approach is an accurate method of estimating bite force‐gape tradeoffs in addition to variables such as fiber length, fiber operating range, and gapes associated with maximum force. Our in vivo and modeling data suggestVareciahas reduced bite force capacities in favor of absolutely wider gapes compared toEulemurin relation to their longer jaws. Importantly, our comparisons validate the simulated muscle approach for estimating bite force as a function of gape in extant and fossil primates.more » « less
-
Since the first phylogenetic study of the order Batrachospermales,Batrachospermumwas shown to be paraphyletic. Subsequently, sections of the genus have been methodically investigated usingDNAsequences and morphology in order to propose new genera and delineate species.BatrachospermumsectionTurfosais the last section with multiple species yet to be examined. New sequence data of specimens from Europe and the United States were combined with the sparse sequence data already available. Phylogenetic analyses usingrbcL andCOI‐5P sequences showed this section to be a well‐supported clade, distinct fromBatrachospermumsectionBatrachospermumand its segregate genera. Section Turfosais raised to the generic rank asPaludicolagen. nov. Substantial genetic variation within the genus was discovered and 12 species are recognized based onDNAsequence data as well as morphological characters and geographic distribution. The following morphological characters were applied to distinguish species: branching pattern (pseudodichotomous or irregular), whorl size (reduced or well developed), primary fascicles (curved or straight), spermatangia origin (primary or secondary fascicles), and carposporophyte arrangement (loose or dense). Previously published species were transferred to the new genus:P. turfosa,P. keratophyta,P. orthosticha,P. phangiae,andP. periploca. Seven new species are proposed as follows:P. groenbladiifrom Europe;P. communis,P. johnhallii, andP. leafensisfrom North America; andP. aquanigra,P. diamantinensis, andP. turfosiformisfrom Brazil. In addition, three unsequenced species in the section,P. bakarensis,P. gombakensis, andP. tapirensis, were transferred to the new genus.more » « less
-
Abstract ObjectivesCortical bone geometry is commonly used to investigate biomechanical properties of primate mandibles. However, the ontogeny of these properties is less understood. Here we investigate changes in cortical bone cross‐sectional properties throughout capuchin ontogeny and compare captive versus wild, semi‐provisioned groups. Tufted capuchins (Sapajusspp.) are known to consume relatively hard/tough foods, while untufted capuchins (Cebusspp.) exploit less mechanically challenging foods. Previous research indicates dietary differences are present early in development and adultSapajusmandibles can resist higher bending/shear/torsional loads. Materials and methodsThis study utilized microCT scans of 22Cebusand 45Sapajusfrom early infancy to adulthood from three sample populations: one captiveCebus, one captiveSapajus, and one semi‐provisioned, free‐rangingSapajus. Mandibular cross‐sectional properties were calculated at the symphysis, P3, and M1. If the tooth had not erupted, its position within the crypt was used. A series of one‐way ANOVAs were performed to assess differences between and within the sample populations. ResultsMandible robusticity increases across ontogeny for all three sample populations.Sapajuswere better able to withstand bending and torsional loading even early in ontogeny, but no difference in shear resistance was found. Semi‐provisioned, free‐rangingSapajustend to show increased abilities to resist bending and torsional loading but not shear loading compared to captiveSapajus. DiscussionThis study helps advance our understanding of the primate masticatory system development and opens the door for further studies into adaptive plasticity in shaping the masticatory apparatus of capuchins and differences in captive versus free‐ranging sample populations.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d4gc02672a
