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ABSTRACT: Glyphosate is an organophosphorus compound and the active ingredient in commonly used herbicides, whereas polyoxyethyleneamine (POEA) is a nonionic surfactant often coupled with glyphosate in these herbicides to increase their efficacy. Cases of glyphosate-POEA ingestion have shown a variety of outcomes, ranging from skin and mucosal surface irritation to death. Here, we report mortality after ingestion of at least 237 mL of an herbicide confirmed to contain both glyphosate and POEA. The decedent's electronic medical record indicates presentation to the emergency department shortly after ingestion and rapid decompensation, with death occurring on the fourth day of admission. The autopsy report showed extensive pulmonary edema and congestion with no alimentary tract abnormalities. Microscopically, airway inflammation, edema, and hemorrhage were shown as well as pericentral necrosis and macrovascular hepatic steatosis. This case is unusual for several reasons including the fatal outcome in a young 30-year-old patient, the large volume of the herbicide consumed, the associated large volume aspirated, and the lung pathology associated with exposure to glyphosate-POEA since inhalation, and in this case, aspiration is an uncommon route of glyphosate-POEA exposure. This report therefore offers rare respiratory tract pathological findings and the clinical course after aspiration of a large volume of glyphosate-POEA.
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Glicina/análogos & derivados , Herbicidas/envenenamiento , Polietilenglicoles/envenenamiento , Suicidio Completo , Tensoactivos/envenenamiento , Lesión Renal Aguda/inducido químicamente , Adulto , Edema/patología , Glicina/envenenamiento , Hemorragia/patología , Humanos , Hígado/patología , Fallo Hepático Agudo/inducido químicamente , Pulmón/patología , Masculino , Necrosis , Edema Pulmonar/patología , Insuficiencia Respiratoria/inducido químicamente , GlifosatoRESUMEN
A protocol is presented for the synthesis of chromium(III) complexes of the type cis-[Cr(diimine)2(1-methylimidazole)2](3+). These compounds exhibit large excited-state oxidizing powers and strong luminescence in solution. Emission is quenched by added guanine, yielding rate constants that track the driving force for guanine oxidation. The cis-[Cr(TMP)(DPPZ)(1-MeImid)2](3+) species binds strongly to duplex DNA with a preference for AT base sites in the minor groove and may serve as a precursor for photoactivated DNA covalent adduct formation.
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Imidazoles/síntesis química , Nucleótidos/química , Sitios de Unión , Imidazoles/química , Oxidación-Reducción , Espectroscopía de Protones por Resonancia Magnética , Espectrometría de Masa por Ionización de Electrospray , Espectrofotometría UltravioletaRESUMEN
Silver clusters with â¼10 atoms are molecules, and specific species develop within DNA strands. These molecular metals have sparsely organized electronic states with distinctive visible and near-infrared spectra that vary with cluster size, oxidation, and shape. These small molecules also act as DNA adducts and coordinate with their DNA hosts. We investigated these characteristics using a specific cluster-DNA conjugate with the goal of developing a sensitive and selective biosensor. The silver cluster has a single violet absorption band (λ(max) = 400 nm), and its single-stranded DNA host has two domains that stabilize this cluster and hybridize with target oligonucleotides. These target analytes transform the weakly emissive violet cluster to a new chromophore with blue-green absorption (λ(max) = 490 nm) and strong green emission (λ(max) = 550 nm). Our studies consider the synthesis, cluster size, and DNA structure of the precursor violet cluster-DNA complex. This species preferentially forms with relatively low amounts of Ag(+), high concentrations of the oxidizing agent O2, and DNA strands with â³20 nucleotides. The resulting aqueous and gaseous forms of this chromophore have 10 silvers that coalesce into a single cluster. This molecule is not only a chromophore but also an adduct that coordinates multiple nucleobases. Large-scale DNA conformational changes are manifested in a 20% smaller hydrodynamic radius and disrupted nucleobase stacking. Multidentate coordination also stabilizes the single-stranded DNA and thereby inhibits hybridization with target complements. These observations suggest that the silver cluster-DNA conjugate acts like a molecular beacon but is distinguished because the cluster chromophore not only sensitively signals target analytes but also stringently discriminates against analogous competing analytes.
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Colorantes/química , ADN/química , Hibridación de Ácido Nucleico/métodos , Plata/química , Secuencia de Bases , ADN de Cadena Simple/química , Conformación de Ácido Nucleico , Oligonucleótidos/química , Espectrofotometría/métodosRESUMEN
With limited COVID-19-guidelines for institutions of higher education (IHEs), colleges and universities began the 2020-2021 academic year with varying approaches. We present a comprehensive COVID-19 prevention and mitigation approach at a residential university during the 2020-2021 academic year, along with campus SARS-CoV-2 transmission during this time. Risk management of COVID-19 was facilitated through (1) a layered approach of primary, secondary, and tertiary prevention measures; (2) a robust committee structure leveraging institutional public health expertise; (3) partnerships with external health entities; and (4) an operations system providing both structure and flexibility to adapt to changes in disease activity, scientific evidence, and public health guidelines. These efforts collectively allowed the university to mitigate SARS-CoV-2 transmission on campus and complete the academic year offering in-person learning on a residential campus. We identified 36 cases of COVID-19 among the 2037 in-person learners during the fall semester, 125 cases in the inter-semester break, and 169 cases among 2095 in-person learners during the spring semester. SARS-CoV-2 infection during the academic year was associated with gender (p = 0.04), race/ethnicity (p = 0.01), and sorority/fraternity membership (p < 0.01). Infection was not associated with undergraduate vs. graduate student status, Division I athlete status, or housing type (all p > 0.05). A multi-faceted public health approach was critical for reducing the impact of COVID-19 while carrying out the university's educational mission.
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COVID-19 , Humanos , Gestión de Riesgos , SARS-CoV-2 , Estudiantes , UniversidadesRESUMEN
The synthesis of photoluminescent Cr(III) complexes of the type [Cr(diimine)(2)(DPPZ)](3+) are described, where DPPZ is the intercalating dipyridophenazine ligand, and diimine corresponds to the ancillary ligands bpy, phen, DMP, and TMP (where bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, DMP = 5,6-dimethyl-1,10-phenanthroline, and TMP = 3,4,7,8-tetramethyl-1,10-phenanthroline). For TMP, DMP, and phen as ancillary ligands, the complexes have also been resolved into their Lambda and Delta optical isomers. A comparison of the photophysical and electrochemical properties reveal similar (2)E(g) --> (4)A(2g) (O(h)) emission wavelengths and lifetimes, and a variation of 110 mV in the (2)E(g) excited state oxidizing power. A detailed investigation has been undertaken of ancillary ligand effects on the DNA binding of these complexes with a range of polynucleotides. For all four complexes, emission is quenched by the addition of calf thymus B-DNA, with the emission lifetime data yielding bimolecular quenching rate constants close to the diffusion controlled limit. Equilibrium dialysis studies have established a general predilection for AT base binding sites, while companion experiments with added distamycin (a selective minor groove binder) provide evidence for a minor groove binding preference. For the case of [Cr(TMP)(2)(DPPZ)](3+), concomitant equilibrium dialysis and circular dichroism measurements have demonstrated very strong enantioselective binding by the Lambda optical isomer. The thermodynamics of DNA binding have also been explored via isothermal titration calorimetry (ITC). The ITC data establish that the primary binding mode for all four Cr(III) complexes is entropically driven, a result that is attributed to the highly favorable free energy contribution associated with the hydrophobic transfer of the Cr(III) complexes from solution into the DNA binding site.
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Cromo/química , ADN/química , Compuestos Organometálicos/química , Compuestos Organoplatinos/química , Fenazinas/química , Animales , Bovinos , Ligandos , Luminiscencia , Estructura Molecular , Compuestos Organoplatinos/síntesis químicaRESUMEN
Polymeric biguanides, as well as quaternary ammonium compounds, are ubiquitous antimicrobial agents in healthcare. Due to the highly cationic and polymeric nature of these compounds and the complex matrices in which they are found, the analytical characterization of products containing them remains challenging. In this work an efficient, sensitive, and high-resolution separation protocol was developed to perform quantitative measurements (sub-mg L-1) of alexidine dihydrochloride (ADH) and polyhexamethylene biguanide (PHMB) in commercial multipurpose contact lens solutions (MPS). Initially, contactless conductivity (C4D) detection was explored, but lacked adequate selectivity and sensitivity to quantify PHMB or ADH in commercial MPS. To overcome these limitations, an alternative approach using solid phase extraction (SPE) followed by separation with reversed phase ultra-performance liquid chromatography (RP-UPLC) was developed for both ADH and PHMB separation and detection. The most sensitive and reliable method investigated utilized standard additions to compensate for matrix effects. For ADH, concentration values measured with the presented method were consistent with data provided by the MPS manufacturer (1.6â¯mgâ¯L-1) within 0.10â¯mgâ¯L-1. PHMB quantification in MPS products was successful at concentrations <1â¯mgâ¯L-1 with quantitative reproducibility better than 2% RSD. Comparison of blind sample testing using the RP-UPLC method showed strong correlation (R2â¯=â¯0.939) of PHMB concentrations with results obtained by the United States Food and Drug Administration using a published HPLC-Evaporative light scattering detection (ELSD) assay. A significant advantage of this method is the ability to partially resolve PHMB polydispersity, which to date has been minimally studied and explained. By coupling with electrospray mass spectrometry (MS), a general trend was observed for increased retention as a function of PHMB chain length. The improved robustness and reproducibility of UV detection versus ELSD coupled with the superior resolving power of UPLC is an asset to the detection and characterization of PHMB and ADH. In addition to quality control of MPS, this method has potential application to the analyses skin wipes, wound dressings and other medical products where understanding how manufacturing processes lead to differences in polydispersity is important to maximize the antimicrobial properties while minimizing toxicologic effects.
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Biguanidas/análisis , Soluciones para Lentes de Contacto/análisis , Electroforesis Capilar/métodos , Espectrometría de Masas/métodos , Cromatografía Liquida/métodos , Cromatografía de Fase Inversa , Desinfectantes/análisis , Reproducibilidad de los Resultados , Extracción en Fase SólidaRESUMEN
Solid-phase microextraction (SPME) is well documented with respect to its convenience and applicability to sampling volatiles. Nonetheless, fire debris analysts have yet to widely adopt SPME as a viable extraction technique, although several fire debris studies have demonstrated the utility of SPME coupled with gas chromatography-mass spectrometry (GC-MS) to identify ignitable liquids. This work considers the expansion of SPME sampling from the customary thermal desorption mode to solvent-based analyte desorption for the analysis of ignitable residues. SPME extraction fibers are desorbed in 30 microL of nonaqueous solvent to yield a solution amenable to conventional GC-MS analysis with standard autosampler apparatus. This approach retains the advantages of convenience and sampling time associated with thermal desorption while simultaneously improving the flexibility and throughput of the method. Based on sampling results for three ignitable liquids (gasoline, kerosene, anddiesel fuel) in direct comparisons with the widely used activated charcoal strip (ACS) method this methodology appears to be a viable alternative to the routinely used ACS method.
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Recently, we have demonstrated the capacity to separate chiral transition metal (TM) complexes of the type [M(diimine)(3)](n+) using CE buffers containing chiral tartrate salts. In separate work, several chromium(III)-tris-diimine complexes in particular have been shown to bind enantioselectively with calf-thymus (CT) DNA, and a qualitative assessment of the relative strength and enantiospecificity of this interaction is of significant interest in the characterization of these complexes as potential DNA photocleavage agents. Here, we describe two convenient approaches to investigate such binding behavior using chiral CE. For complexes with lower DNA affinities exhibiting primarily surface binding, DNA itself is used as the chiral resolving agent in the electrophoretic buffer. In this approach, resolution of the TM complexes into their Lambda and Delta isomers is achieved with the isomer eluting later exhibiting superior binding affinity toward DNA. For more strongly bound TM complexes containing ligands known to intercalate with DNA, the [Cr(diimine)(3)](3+) complexes are preincubated with oligonucleotide and subsequently enantiomerically resolved in a dibenzoyl-L-tartrate buffer system that facilitates analysis of the unbound TM species only. Differences in isomer binding affinity are distinguished by the relative peak areas of the Lambda- and Delta-isomers, and relative binding strengths of different complexes can be inferred from comparison of the total amount of unbound complex at equivalent DNA/TM ratios.