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1.
ACS Nano ; 2024 Oct 11.
Artículo en Inglés | MEDLINE | ID: mdl-39392333

RESUMEN

We achieve, at room temperature, conductance enhancements over 2 orders of magnitude in single molecule circuits formed with polycyclic benzoquinoidal (BQn) diradicals upon increasing molecular length by ∼5 Å. We find that this extreme and atypical anti-ohmic conductance enhancement at longer molecular lengths is due to the diradical character of the molecules, which can be described as a topologically nontrivial electronic state, and results in constructive interference between the frontier molecular orbitals. The distinct feature of the compounds studied here as molecular wires is that they are characterized by moderate diradical character in the neutral state, allowing for robust and facile measurements of their transport properties. We adapt the 1D-SSH model, originally developed to examine electronic topological order in linear carbon chains, to the polycyclic systems studied here and find that it captures the anti-ohmic trends in this molecular series. Specifically, our model reveals that the mechanism of conductance enhancement with length in polycyclic systems is constructive quantum interference between the frontier orbitals with nontrivial topology, which is present in acene-like, but not in linear, molecular systems. Importantly, we use our model to predict and experimentally validate that anti-ohmic trends can be engineered through synthetic adjustments of the diradical character of the acene-like molecules. Overall, we achieve extreme anti-ohmic enhancement and mechanistic insight into electronic transport in a class of materials that we identify here as promising candidates for creating highly conductive and tunable nanoscale wires.

2.
J Org Chem ; 89(19): 14515-14519, 2024 Oct 04.
Artículo en Inglés | MEDLINE | ID: mdl-39302450

RESUMEN

To further the ability to manipulate the properties of open-shell molecules, logical and incremental modifications to molecular structure are key steps that provide fine-tuning of established diradicaloid scaffolds. We report the synthesis of an electronically "pure" diradicaloid based on a 2,6-anthroquinoidal core where the once necessary ethynyl "wings" are removed. Through the simplification of the overall electronic structure, the singlet-triplet energy gap increases by 0.3-0.4 kcal mol-1 in the reported diradicaloids while avoiding significant disruption to their optoelectronic properties.

3.
J Plant Physiol ; 243: 153056, 2019 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-31704533

RESUMEN

Plant wax n-alkanes are a major constituent of the leaf and grain surface. In this study, we explored what can be learned from the abundance and carbon isotopic composition (δ13C) of n-alkanes in historical winter wheat cultivars. We investigated leaf and grain wax n-alkane concentration (ΣalkLand ΣalkG) and carbon isotopes (δ13CalkL and δ13CalkG) on C29 as well as bulk leaf and grain carbon isotopes (δ13CbulkL and δ13CbulkG) to assess if these wax components changed across five wheat cultivars released from the 1950s to the early 2010s. Results showed that ΣalkL and grain yield increased, while δ13CalkL and δ13CbulkL decreased across the historical wheat cultivars. We found a significant correlation between ΣalkL and shoot biomass at the early growth stage, and a strong correlation between ΣalkL at the grain-filling stage and grain yield. Grain measures, including ΣalkG, δ13CalkG, and δ13CbulkG did not correlate with crop production. Although δ13CalkL and grain yield were not correlated at the flowering stage, they were correlated at the grain-filling stage under dry conditions. Our results indicate that increased ΣalkL has been indirectly selected in breeding efforts to improve crop production in winter wheat, suggesting that greater leaf waxiness confers advantages for crop growth.


Asunto(s)
Alcanos/metabolismo , Fitomejoramiento , Hojas de la Planta/fisiología , Triticum/fisiología , Isótopos de Carbono/análisis , Productos Agrícolas , Hojas de la Planta/genética , Triticum/genética , Triticum/crecimiento & desarrollo , Ceras/metabolismo
4.
Bol. Asoc. Méd. P. R ; Bol. Asoc. Méd. P. R;81(9): 355-8, sept. 1989. ilus
Artículo en Inglés | LILACS | ID: lil-103670

RESUMEN

Anatomical variantions of the biliary tract occur frequently enough so as to worry the general surgeon dealing with this problem. Generally speaking, these anatomical variations are not identified prior to surgery. Anamalous drainage of the common hepatic duct into the gall bladder was identified while performing a cholecystectomy. The common bile duct proximal to the cystic duct was a tretic. The problem described above was successfully managed by hepatico-jejunostomy


Asunto(s)
Colelitiasis/cirugía , Conducto Colédoco/anomalías , Conducto Hepático Común/anomalías , Anemia de Células Falciformes/complicaciones , Colecistectomía/métodos , Colelitiasis/complicaciones , Conducto Hepático Común/cirugía , Yeyuno/cirugía
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