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1.
J Virol Methods ; 313: 114667, 2023 03.
Artigo em Inglês | MEDLINE | ID: mdl-36572155

RESUMO

PURPOSE: To investigate the performance of a combined nasal midturbinate- and oropharyngeal (NAOP) self-swab compared to a deep oropharyngeal (OP) swab by health care workers (HCW) in detecting SARS-CoV-2 in a real-life setting. METHODS: Paired swabs from 1119 participants were included. RT-PCR were used to detect SARS-CoV-2 in both swab samples. RESULTS: 330 participants tested positive. The sensitivity of the combined self-swab and OP swab was 96.9 % and 95.4 % respectively, whereas the Ct-values for self-swabs were significantly lower compared to OP swabs. CONCLUSION: The combined NAOP self-swab outperformed the OP swab and thus, the NAOP self-swab may be an alternative sampling method under the given circumstances.


Assuntos
COVID-19 , SARS-CoV-2 , Humanos , SARS-CoV-2/genética , COVID-19/diagnóstico , Nasofaringe , Orofaringe , Manejo de Espécimes/métodos
2.
J Am Chem Soc ; 127(23): 8244-5, 2005 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-15941232

RESUMO

1,6-Enynes bearing (electron-rich) aryl substituents on their alkyne moiety rearrange to cyclobutene derivatives in the presence of catalytic amounts of PtCl2 in toluene. The reaction is significantly accelerated when performed under an atmosphere of CO (1 atm), most likely by increasing the electrophilicity of the metal template by temporary coordination to this pi-acidic ligand. This transformation allows the build up of considerable strain in the products as witnessed by the productive formation of tricyclic skeletons, such as 7 or 9. Moreover, these products provide evidence for the mechanistic scenario of platinum-catalyzed cycloisomerization reactions previously proposed, which are thought to proceed via organo-platinum species that mimic the reactivity of metal-complexed "nonclassical" carbocations.

3.
J Am Chem Soc ; 126(28): 8654-5, 2004 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-15250709

RESUMO

Exposure of enynes containing a hydroxyl group at one of the propargylic positions to catalytic amounts of either PtCl2 or (PPh3)AuCl/AgSbF6 results in a selective rearrangement with formation of bicyclo[3.1.0]hexan-3-one derivatives. The same products are obtained by a "one-pot" process on treatment of an alkynal with allylchlorodimethylsilane (4) and PtCl2 via a reaction cascade involving an initial platinum-catalyzed allylation followed by the cycloisomerization of the homoallylic alcohol formed in situ. This novel skeletal reorganization process was implemented into a concise total synthesis of the terpenes sabinone (18) and sabinol (19). Furthermore it is shown that conversion of the hydroxylated enynes into the corresponding acetates followed by reaction with a cationic gold catalyst formed from (PPh3)AuCl and AgSbF6 opens entry into isomeric products bearing the ketone function at the C-2 position of the bicyclo[3.1.0]hexane skeleton. The outcome of a deuterium labeling experiment and the analysis of the stereochemical course of the cycloisomerization reaction are consistent with the formation of cyclopropylmethyl platinum carbene species as reactive intermediates.


Assuntos
Alcinos/química , Compostos de Ouro/química , Compostos de Platina/química , Alcenos/síntese química , Alcenos/química , Alcinos/síntese química , Catálise , Ciclização , Ciclopropanos/síntese química , Ciclopropanos/química , Isomerismo , Estrutura Molecular , Oxirredução
4.
J Am Chem Soc ; 126(26): 8336-48, 2004 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-15225077

RESUMO

Two highly dipolar merocyanine dyes were tethered by a rigid tris(n-dodecyloxy)xylylene unit that preorganizes the dyes for a supramolecular polymerization process through intermolecular aggregation of the dyes. UV/vis spectroscopy revealed a solvent dependent equilibrium between monomeric dyes and two different types of dye aggregates that are characterized by hypsochromically shifted D- and H-type absorption bands. Taking into account the ditopic nature of the supramolecular building blocks, the occurrence of the D-band indicates the formation of an oligomeric/polymeric supramolecular chain whereas the observation of the H-band suggests a higher order assembly. For the H-aggregated dyes, intrinsic viscosities exceed 0.65 L g(-1) in methylcyclohexane, values typically found for macromolecular solutions. At higher concentration, further association of these aggregates takes place by entanglement of the alkyl groups leading to a substantial increase in viscosity and gelation. Rheology studies show linear viscoelastic behavior which was attributed to the formation of an entangled dynamic network. AFM and cryo-TEM studies of the gel reveal long and stiff rod-type assemblies. X-ray diffraction studies for a solid film show columnar mesomorphism. Based on these results, a structural model is proposed in which six helically preorganized strands of the supramolecular polymer intertwine to form a rod with a diameter of about 5 nm. Within these rods all dyes are tightly aggregated in a tubular fashion giving rise to delocalized excitonic states, and the pi-conjugated tube is jacketed by the tridodecyloxy groups.


Assuntos
Corantes/síntese química , Pirimidinonas/síntese química , Corantes/química , Géis , Ligação de Hidrogênio , Cinética , Substâncias Macromoleculares , Modelos Químicos , Estrutura Molecular , Pirimidinonas/química , Espectrofotometria Ultravioleta , Viscosidade
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