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1.
Surg Case Rep ; 10(1): 72, 2024 Mar 29.
Article in English | MEDLINE | ID: mdl-38548968

ABSTRACT

BACKGROUND: Mesenteric cysts are one of the rarest abdominal tumor masses, representing a little-studied pathology. In turn, the variability and non-specificity of clinical manifestations make diagnosis difficult, as it can be reached by imaging findings due to another cause or by non-specific abdominal pain. CASE PRESENTATION: This article describes the case report of an asymptomatic 28-year-old patient who presented a 6-cm abdominal cystic mass with mixed density, which was found incidentally by computed tomography. Exploratory laparoscopy was performed followed by conversion to conventional surgery to extract the tumor mass. The anatomical pathology diagnosis was pseudocyst of the mesentery root. Mesenteric cysts are one of the rarest abdominal tumor masses, representing a little-studied pathology. In turn, the variability and non-specificity of clinical manifestations make diagnosis difficult, as it can be reached by imaging findings due to another cause or by non-specific abdominal pain. CONCLUSIONS: Mesenteric cysts are rare, and their nonspecific symptoms often lead to diagnosis based on imaging findings. Complete laparoscopic enucleation is the standard treatment.

2.
Radiologia (Engl Ed) ; 65(6): 546-553, 2023.
Article in English | MEDLINE | ID: mdl-38049253

ABSTRACT

OBJECTIVE: To review and describe the most characteristic radiological findings of the most frequent esophageal tumor lesions, with emphasis on the esophago-gastric distention technique pneumo-computed tomography performed in our institution. To know the main advantage of this distension technique. CONCLUSION: Malignant tumor lesions (predominantly squamous cell carcinoma in the mid esophagus and adenocarcinoma in the distal esophagus) present as asymmetric wall thickening, mucosal irregularity, or mass extending into adjacent organs with lymph node involvement. Benign tumors (mainly leiomyoma being the most frequent and others such as lipoma) present as endoluminal growth, with defined borders and homogeneous attenuation. Post-contrast enhancement is scarce or moderate. The technique of computed tomography pneumotomography technique achieves an additional distension of the esophageal lumen in all cases. It allows delimiting the superior and inferior borders of the lesions, helping the surgeon to define the therapeutic strategy.


Subject(s)
Adenocarcinoma , Carcinoma, Squamous Cell , Esophageal Neoplasms , Humans , Adenocarcinoma/diagnostic imaging , Carcinoma, Squamous Cell/diagnostic imaging , Carcinoma, Squamous Cell/surgery , Esophageal Neoplasms/diagnostic imaging , Tomography, X-Ray Computed/methods
3.
J Phys Chem A ; 127(19): 4269-4276, 2023 May 18.
Article in English | MEDLINE | ID: mdl-37133983

ABSTRACT

The oxidation of the amino acid methionine (Met) by hypochlorous acid (HOCl) to yield methionine sulfoxide (MetO) has been implicated in both the interfacial chemistry of tropospheric sea spray aerosols and the destruction of pathogens in the immune system. Here, we investigate the reaction of deprotonated methionine water clusters, Met-·(H2O)n, with HOCl and characterize the resulting products using cryogenic ion vibrational spectroscopy and electronic structure calculations. Capture of the MetO- oxidation product in the gas phase requires the presence of water molecules attached to the reactant anion. Analysis of its vibrational band pattern confirms that the sulfide group of Met- has indeed been oxidized. Additionally, the vibrational spectrum of the anion corresponding to the uptake of HOCl by Met-·(H2O)n indicates that it exists as an "exit-channel" complex in which the Cl- product ion is bound to the COOH group following the formation of the S═O motif.

4.
J Chem Phys ; 157(13): 131102, 2022 Oct 07.
Article in English | MEDLINE | ID: mdl-36209005

ABSTRACT

4-aminobenzoic acid (4ABA) is a model scaffold for studying solvent-mediated proton transfer. Although protonation at the carboxylic group (O-protomer) is energetically favored in the gas phase, the N-protomer, where the proton remains on the amino group, can be kinetically trapped by electrospray ionization of 4ABA in an aprotic solvent such as acetonitrile. Here, we report the formation of the hydrated deuterium isotopologues of the N-protomers, RND3 +·(H2O)n=1-3, (R = C6H4COOD), which are generated by condensing water molecules onto the bare N-protomers in a liquid nitrogen cooled, radiofrequency octopole ion trap at 80 K. The product clusters are then transferred to a 20 K cryogenic ion trap where they are tagged with weakly bound D2 molecules. The structures of these clusters are determined by analysis of their vibrational patterns, obtained by resonant IR photodissociation. The resulting patterns confirm that the metastable N-protomer configuration remains intact even when warmed by the sequential condensation of water molecules. The attachment of H2O molecules onto the RND3 + head group also affords the opportunity to explore the possibility of H/D exchange between the acid scaffold and the proximal water network. The spectroscopic results establish that although the RND3 +·(H2O)n=1,2 clusters are formed without H/D exchange, the n = 3 cluster exhibits about 10% H/D exchange as evidenced by the appearance of the telltale HOD bands. The site of exchange on the acid is determined to be the acidic OH group by the emergence of the OH stretching fundamental in the -COOH motif.


Subject(s)
4-Aminobenzoic Acid , Protons , 4-Aminobenzoic Acid/chemistry , Acetonitriles , Deuterium , Nitrogen , Protein Subunits , Solvents/chemistry , Water/chemistry
5.
Radiologia (Engl Ed) ; 64(3): 237-244, 2022.
Article in English | MEDLINE | ID: mdl-35676055

ABSTRACT

OBJECTIVE: This article aims to show the usefulness of the pneumo-computed tomography gastric distention technique in the detection and morphological characterization of subepithelial gastric lesions. We correlate the pneumo-computed tomography and pathology findings in lesions studied at our institution and review the relevant literature. CONCLUSION: Pneumo-computed tomography, combined with multiplanar reconstructions, three-dimensional reconstructions, and virtual endoscopy, is useful for delineating the morphological details of subepithelial gastric lesions, thanks to the additional gastric distention. This technique better delimits and characterizes the upper and lower margins of the lesions. Pneumo-computed tomography can be considered a useful noninvasive imaging techniques for characterizing these lesions.


Subject(s)
Gastroscopy , Stomach Neoplasms , Gastroscopy/methods , Humans , Stomach Neoplasms/diagnostic imaging , Stomach Neoplasms/pathology , Tomography, X-Ray Computed/methods
6.
J Chem Phys ; 156(17): 174303, 2022 May 07.
Article in English | MEDLINE | ID: mdl-35525657

ABSTRACT

We report vibrational spectra of the H2-tagged, cryogenically cooled X- · HOCl (X = Cl, Br, and I) ion-molecule complexes and analyze the resulting band patterns with electronic structure calculations and an anharmonic theoretical treatment of nuclear motions on extended potential energy surfaces. The complexes are formed by "ligand exchange" reactions of X- · (H2O)n clusters with HOCl molecules at low pressure (∼10-2 mbar) in a radio frequency ion guide. The spectra generally feature many bands in addition to the fundamentals expected at the double harmonic level. These "extra bands" appear in patterns that are similar to those displayed by the X- · HOD analogs, where they are assigned to excitations of nominally IR forbidden overtones and combination bands. The interactions driving these features include mechanical and electronic anharmonicities. Particularly intense bands are observed for the v = 0 → 2 transitions of the out-of-plane bending soft modes of the HOCl molecule relative to the ions. These involve displacements that act to break the strong H-bond to the ion, which give rise to large quadratic dependences of the electric dipoles (electronic anharmonicities) that drive the transition moments for the overtone bands. On the other hand, overtone bands arising from the intramolecular OH bending modes of HOCl are traced to mechanical anharmonic coupling with the v = 1 level of the OH stretch (Fermi resonances). These interactions are similar in strength to those reported earlier for the X- · HOD complexes.

7.
Radiología (Madr., Ed. impr.) ; 64(3): 237-244, May-Jun 2022. ilus
Article in Spanish | IBECS | ID: ibc-204581

ABSTRACT

Objetivo: El propósito de este artículo es destacar la utilidad de la técnica de distensión gástrica neumo-tomografía computarizada en la detección y caracterización morfológica de las lesiones subepiteliales gástricas estudiadas en nuestra institución, con su correlación de anatomía patológica y una revisión de la literatura. Conclusión: La neumo-tomografía computarizada combinada con las reconstrucciones multiplanares, las reconstrucciones tridimensionales y la endoscopia virtual es útil para delinear los detalles morfológicos de las lesiones subepiteliales gástricas debido a la distensión gástrica adicional. Se logra una mejor delimitación de sus bordes superior e inferior, así como las características de sus márgenes. Puede considerarse una técnica de imagen útil y no invasiva para la caracterización de estas lesiones.(AU)


Objective: This article aims to show the usefulness of the pneumo-computed tomography gastric distention technique in the detection and morphological characterization of subepithelial gastric lesions. We correlate the pneumo-computed tomography and pathology findings in lesions studied at our institution and review the relevant literature. Conclusion: Pneumo-computed tomography, combined with multiplanar reconstructions, three-dimensional reconstructions, and virtual endoscopy, is useful for delineating the morphological details of subepithelial gastric lesions, thanks to the additional gastric distention. This technique better delimits and characterizes the upper and lower margins of the lesions. Pneumo-computed tomography can be considered a useful noninvasive imaging techniques for characterizing these lesions.(AU)


Subject(s)
Humans , Tomography, X-Ray Computed , Stomach , Stomach Neoplasms/diagnostic imaging , Thorax/diagnostic imaging , Radiography
8.
J Phys Chem Lett ; 13(12): 2750-2756, 2022 Mar 31.
Article in English | MEDLINE | ID: mdl-35315676

ABSTRACT

In the presence of a halide ion, hypohalous acids can adopt two binding motifs upon formation of the ion-molecule complexes [XHOY]- (X, Y = Cl, Br, I): a hydrogen (HB) bond to the acid OH group and a halogen (XB) bond between the anion and the acid halogen. Here we isolate the X-bonded Cl-·IOH ion-molecule complex by collisions of I-·(H2O)n clusters with HOCl vapor and measure its vibrational spectrum by IR photodissociation of the H2-tagged complex. Anharmonic analysis of its vibrational band pattern reveals that formation of the XB complex results in dramatic lowering of the HOI bending fundamental frequency and elongation of the O-I bond (by 168 cm-1 and 0.13 Å, respectively, relative to isolated HOI). The frequency of the O-I stretch (estimated 436 cm-1) is also encoded in the spectrum by the weak v = 0 → 2 overtone transition at 872 cm-1.


Subject(s)
Halogens , Vibration , Halogens/chemistry , Hydrogen/chemistry , Hydrogen Bonding , Spectrum Analysis
9.
Animals (Basel) ; 12(4)2022 Feb 10.
Article in English | MEDLINE | ID: mdl-35203125

ABSTRACT

The addition of the antioxidant α-lipoic acid (ALA) to a balanced diet might be crucial for the prevention of comorbidities such as cardiovascular diseases, diabetes, and obesity. Due to its low half-life and instability under stomach-like conditions, α-lipoic acid was encapsulated into chitosan nanoparticles (Ch-NPs). The resulting chitosan nanoparticles containing 20% w/w ALA (Ch-ALA-NPs) with an average diameter of 44 nm demonstrated antioxidant activity and stability under stomach-like conditions for up to 3 h. Furthermore, fluorescent Ch-ALA-NPs were effectively internalized into 3T3-L1 fibroblasts and were able to cross the intestinal barrier, as evidenced by everted intestine in vitro experiments. Thus, chitosan-based nanoparticles seem to be an attractive administration method for antioxidants, or other sensible additives, in food.

10.
J Infect ; 81(2): 289-296, 2020 08.
Article in English | MEDLINE | ID: mdl-32473234

ABSTRACT

OBJECTIVES: Guidelines recommend routine testing for latent TB infection (LTBI) in people living with HIV. However there are few cost-effectiveness studies to justify this in contemporary high resource, low TB/HIV incidence settings. We sought to assess the uptake, yield and cost-effectiveness of testing for latent and active TB. METHODS: Adults attending an ambulatory HIV clinic in London, UK were prospectively recruited by stratified selection and tested for TB infection using symptom questionnaires, chest radiograph (CXR), tuberculin skin test (TST), T-Spot.TB and induced sputum. From this, 30 testing strategies were compared in a cost-effectiveness model including probabilistic sensitivity analysis using Monte Carlo simulation. RESULTS: 219 subjects were assessed; 95% were using antiretroviral therapy (ART). Smear negative, culture positive TB was present in 0.9% asymptomatic subjects, LTBI in 9%. Only strategies testing those from subSaharan Africa with a TST or interferon gamma release assay (IGRA) with or without CXR, or testing those from countries with a TB incidence of >40/100,000 with TST alone were cost-effective using a £30,000/QALY threshold. CONCLUSIONS: Cost-effectiveness analysis in an adult HIV cohort with high ART usage suggests there is limited benefit beyond routine testing for latent TB in people from high and possibly medium TB incidence settings.


Subject(s)
HIV Infections , Latent Tuberculosis , Adult , Cost-Benefit Analysis , HIV Infections/complications , Humans , Interferon-gamma Release Tests , Latent Tuberculosis/diagnosis , Latent Tuberculosis/epidemiology , London/epidemiology , Tuberculin Test
11.
Environ Sci Technol ; 53(1): 176-184, 2019 01 02.
Article in English | MEDLINE | ID: mdl-30500166

ABSTRACT

Extensive studies of secondary organic aerosol (SOA) formation have identified isoprene epoxydiol (IEPOX) intermediates as key species in the formation of isoprene-derived SOA. Recent work has suggested that isoprene-derived dimers and oligomers may constitute a significant fraction of SOA, but a mechanism for the formation of such abundant SOA components has yet to be established. The potential for dimer formation from the nucleophilic addition of 2-methyltetrol to trans-ß-IEPOX was assessed through a series of model epoxide-nucleophile experiments using nuclear magnetic resonance (NMR) spectroscopy. These experiments helped establish a rigorous understanding of structural, stereochemical, and NMR chemical shift trends, which were used along with nucleophilic strength calculations to interpret the results of the trans-ß-IEPOX + 2-methyltetrol reaction and evaluate its relevance in the atmosphere. A preference for less sterically hindered nucleophiles was observed in all model systems. In all addition products, a significant increase in NMR chemical shift was observed directly adjacent to the epoxide-nucleophile linkage, with smaller decreases in chemical shift at all other sites. A partial NMR assignment of a single trans-ß-IEPOX + 2-methyltetrol nucleophilic addition product was obtained, but nucleophilic strength calculations suggest that 2-methyltetrol is a poor nucleophile. Therefore,  this reaction is unlikely to significantly contribute to dimer and oligomer formation on SOA. Nevertheless, the structural and stereochemical considerations, NMR assignments, and NMR chemical shift trends reported here will prove useful in future attempts to synthesize dimer and oligomer analytical standards.


Subject(s)
Hemiterpenes , Pentanes , Aerosols , Butadienes
12.
Environ Sci Technol ; 52(15): 8346-8354, 2018 08 07.
Article in English | MEDLINE | ID: mdl-29952554

ABSTRACT

Laboratory and field measurements have demonstrated that isoprene epoxydiol (IEPOX) is the base component of a wide range of chemical species found in isoprene-derived secondary organic aerosol (SOA). To address newly raised questions concerning the chemical identities of IEPOX-derived SOA, the results of laboratory experiments carried out in bulk aqueous and organic media and analyzed via nuclear magnetic resonance spectroscopy and computed free energies of possible products are reported. The IEPOX nucleophilic addition product 2-methyltetrol was found to react too slowly in aqueous solution to explain the previous observation of tetrahydrofuran-based species. The IEPOX isomerization reactions in organic media were shown to mainly produce 3-methyltetrahydrofuran-2,4-diols, which were also established by the computational results as one of the most thermodynamically favorable possible IEPOX reaction products. However, these isomerization reactions were found to be relatively slow as compared to nucleophilic addition reactions, indicating that their occurrence on ambient SOA might be limited to low water content situations. No evidence was found for the production of the C5 alkene triols or 3-methyltetrahydrofuran-3,4-diols previously reported for IEPOX reaction on SOA as analyzed via the gas chromatography/electron ionization-quadrupole mass spectrometry with prior trimethylsilyl derivatization method.


Subject(s)
Atmosphere , Hemiterpenes , Aerosols , Butadienes , Gas Chromatography-Mass Spectrometry , Isomerism
13.
J Phys Chem A ; 119(40): 10181-9, 2015 Oct 08.
Article in English | MEDLINE | ID: mdl-26381226

ABSTRACT

Nuclear magnetic resonance techniques were used to study the kinetics and products of the reaction of a variety of epoxides with various amines under varying pH conditions. In agreement with a previous finding, the amine-epoxide reactions were found to be water-catalyzed and not directly dependent on the pH of the reaction environment. At pH values higher than the pK(a) of the particular amine, the amine-epoxide reactions were extremely efficient, outcompeting hydrolysis reactions even for conditions where water was the solvent and the amine was a relatively low-concentration solute. This finding was rationalized by measurements that showed that the relative nucleophilic strength of amines relative to water was on the order of 1000, while the nucleophilic strength of protonated amines (which are predominant when pH < pK(a)) was negligible. The epoxide carbon substitution environment was found to have a large effect on the measured rate constants (more substituted epoxides had slower rate constants), while the amine carbon substitution environment had a much more limited effect. While the amine-epoxide rate constants are large enough such that amine-epoxide reactions may be kinetically feasible for isoprene-derived epoxides and high amine secondary organic aerosol (SOA) concentrations, most atmospheric amines are expected to be present in protonated form on the largely acidic SOA found in the atmosphere and thus are expected to be largely unreactive toward epoxides.

15.
Rev. argent. cir ; 101: 48-52, dic. 2011. tab
Article in Spanish | LILACS | ID: lil-700364

ABSTRACT

Antecedentes: En la re-estadificación post-neoadyuvancia del cáncer de recto existen discrepancias clínico-patológicas y actualmente no existen métodos complementarios útiles para diferenciar la presencia o ausencia de tumor viable. Objetivo: Determinar el valor de la resonancia nuclear magnética con técnica de difusión en la identificación de la respuesta patológica completa luego de la neoadyuvancia y determinar su relación con el grado de respuesta clínica. Lugar de aplicación: Hospital Privado de la Comunidad. Diseño: Retrospectivo Población: 24 pacientes (10 mujeres), mediana de edad: 61 años, operados por cáncer de recto entre junio 2009 y enero 2011. Medidas de evaluación: De acuerdo a la respuesta clínica, fueron agrupados en Respondedores y No Respondedores. Todo valor de coeficiente de difusión aparente mayor a 1.2 x 10-3 mm²/seg fue considerado como respuesta patológica completa. Resultados: La mediana del coeficiente de difusión aparente fue de 1.1 (rango 0.7-2). En 4 casos (17%) se obtuvieron valores de coeficiente de difusión aparente mayores a 1.2 y fueron considerados como respuesta patológica completa. La mediana de coeficiente de difusión aparente en los casos con respuesta patológica completa fue significativamente mayor que la de los casos sin respuesta patológica completa (1.45 vs 1.01 respectivamente, p = 0.0002). De los 24 pacientes, 5 (21%) correspondieron al grupo de respuesta clínica. De ellos, 4 tuvieron una respuesta patológica completa. La resonancia nuclear magnética con técnica de difusión logró identificar estos 4 casos. En el paciente de este grupo que presentaba persistencia tumoral, el valor de coeficiente de difusión aparente fue de 1.1. De esta manera la resonancia nuclear magnética con técnica de difusión logró identificar al único caso en que se justificaría una cirugía radical. De los 19 pacientes que fueron considerados no respondedores, ninguno tuvo respuesta patológica completa. En todos estos casos los índices de coeficiente de difusión aparente fueron menores a 1.2 x 10-3 mm²/seg y en consecuencia no hubo ningún caso de falso negativo. Conclusiones: La resonancia nuclear magnética con técnica de difusión es una herramienta útil para la reestadificación post-neoayuvancia en cáncer de recto.


Background: There exist clinical-pathological discrepancies at the staging after neoadyuvant therapy of rectal cancer, and there are currently no additional useful methods to distinguish the presence or absence of viable tumor. Objective: To determine the value of magnetic resonance diffusion imaging technique in the identification of the pathological complete response after the neoadyuvant therapy and to determine its relationship with the degree of clinical response. Setting: Private Community Hospital. Design: Retrospective Population: 24 patients (10 women), median age: 61, operated on for rectal cancer from June 2009 to January 2011. Outcome measures: According to the clinical response, patients grouped in responders and non-responders. All apparent diffusion coefficient value greater than 1.2 x 10-3 mm²/seg was regarded as pathological response. Results: Median of apparent diffusion coefficient was 1.1 (0.7 and 2 range). In 4 cases (17 per cent) the apparent diffusion coefficient was greater than 1.2 x 10-3 mm², and were regarded as pathological complete. The medianm of apparent diffusion coefficien in cases with complete pathological response was significantly higher than the cases without pathological complete response (1.45 vs 1.01 respectively, p = 0.0002). Five out of 24 patients (21%) corresponded to the group in clinical response. Of these, 4 were n pathological compete response. The magnetic resonance imaging technique was able to identify these 4 cases. In the patient of this group which featured tumor persistence, the apparent diffusion coefficient value was 1.1. Thus the magnetic resonance diffusion imaging technique was able to identify the only case in which a radical surgery would be justified. Among the19 Patients were considered non-responders, none had pathological complete response. In all these cases apparent diffusion coefficient rates were lower to 1.2 x 10-3 mm²/ sec and therefore there was no case of false negative. Conclusions: The magnetic resonance diffusion technique is a useful tool for the staging after neoayuvant therapy in rectal cancer.

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