[Shoulder pain rehabilitation in young athletes]. / Rehabilitacion del hombro doloroso en el atleta joven.

Early specialisation in sports continues to increase and is a risk factor for the incidence of injuries in young athletes. In overhead athletes, the shoulder is the most affected joint, related to a combination of impingement and glenohumeral instability, as well as musculoskeletal immaturity. Identification of risk factors and rehabilitation is usually an effective recovery option for these athletes.

Comment on "Elucidation of charge-transfer SERS selection rules by considering the excited state properties and the role of electrode potential" by M. Mohammadpour, M. H. Khodabandeh, L. Visscher and Z. Jamshidi, Phys. Chem. Chem. Phys., 2017, 19, 7833.

The differences between alternative approaches for quantifying the complex effect of the electronic structure of charged metal-molecule hybrids in SERS (the so-called chemical enhancement mechanism) are highlighted. The discussion is focussed on the predictions obtained by using different methodological tools for modelling the role of the electrode potential in the SERS relative intensities. Finite electric fields are used in the commented paper for this purpose, but we have found some inconsistences in the results and the method for calculating the Raman intensities is not made sufficiently clear, which prevents the assessment of the results.

Raman microspectroscopy for probing the impact of a dietary antioxidant on human breast cancer cells.

Breast cancer is the second most common type of cancer worldwide and the most frequent among women, being the fifth cause of death from neoplastic disease. Since this is an oxidative-stress related neoplasia, it is largely preventable. A dietary isoflavone abundant in soybean - daidzein - is currently being investigated owing to its chemopreventive and/or chemotherapeutic properties towards the human MDA-MB-231 (metastatic, estrogen-unresponsive) and MCF-7 (estrogen-responsive) breast cancer cell lines. Biological assays for evaluation of antitumour and anti-invasive activities were combined with state-of-the-art vibrational microspectroscopy techniques. At 50 and 100 µM concentrations and 48 h incubation time, daidzein was found to induce a marked decrease in cell viability (ca. 50%) for MDA-MB-231 and MCF-7 cells (respectively ca. 50% and 42%) and 40% inhibition of cell migration. MicroRaman analysis of fixed cells upon exposure to this isoflavone unveiled its metabolic impact on both cell lines. Multivariate data analysis (unsupervised PCA) led to a clear discrimination between the control and DAID-exposed cells, with distinctive effects on their biochemical profile, particularly regarding DNA, lipids and protein components, in a cell-dependent way. This is the first reported study on the impact of dietary antioxidants on cancer cells by microRaman techniques.

Adsorption of carbendazim pesticide on plasmonic nanoparticles studied by surface-enhanced Raman scattering.

Surface-Enhanced Raman Spectra (SERS) of methyl N-(1H-benzimidazol-2-yl)carbamate (MBC), usually named carbendazim, have been recorded on silver colloids at different pH values. In order to identify the neutral, protonated or deprotonated species of MBC that originate the SERS, the vibrational wavenumbers of these three isolated forms and linked to a silver atom have been predicted by carrying out DFT calculations. The results indicate that the active SERS species in the studied pH range correspond to the neutral MBC and its deprotonated ion in the amidate form. According to theoretical calculations, neutral MBC is linked to the metal through the imidazolic nitrogen atom, while the deprotonated MBC could be linked through the imidazolic nitrogen together with the amidic nitrogen atom or the carbonyl oxygen atom. Both adsorbed species, neutral and deprotonated, have the benzimidazolic ring orientated almost perpendicular to the silver surface and no molecular reorientation has been detected. pH of the bulk controls the relative abundance of the neutral MBC and its amidate anion which can be monitored through the intensities of the SERS bands recorded at about 1230 and 1270cm(-1). These two key bands correspond to the in-plane NH deformation of amidic and imidazolic groups, respectively.

The electronic structure of metal-molecule hybrids in charged interfaces: surface-enhanced Raman selection rules derived from plasmon-like resonances.

DFT calculations predict that plasmon-like excitations in small metal clusters are able to selectively modify the relative intensities of specific SERS bands of adsorbed molecules. These electronic resonances provide new kinds of SERS selection rules which can explain the huge enhancement of mode 9a of pyridine in the spectra recorded at negative electrode potentials.

On the dual character of charged metal-molecule hybrids and the opposite behaviour of the forward and reverse CT processes.

DFT calculations predict two different electronic structures of metal-molecule hybrids which are selected depending on the surface charge. While the metal-to-molecule CT states are very sensitive to the charge, the energies of the reverse molecule-to-metal CT processes are surprisingly not modified at all by the charge of the metal.

A conformational study of hydroxyflavones by vibrational spectroscopy coupled to DFT calculations.

The conformational preferences of a series of hydroxyflavones were studied by Raman and FTIR spectroscopies, coupled to Density Functional Theory calculations. Special attention was paid to the effect of hydroxyl substitution, due to its importance on the biological activity of these compounds. Their conformational preferences were found to be determined mainly by the orientation of the hydroxylic groups at C(7) and within the catechol moiety, leading to the occurrence of distinct conformers in the solid state. A complete assignment of the experimental spectra was carried out for these molecules, in the light of their most stable conformers and the corresponding predicted vibrational pattern.

HOMA-IR and non-HDL-C as predictors of high cholesteryl ester transfer protein activity in patients at risk for type 2 diabetes.

BACKGROUND AND AIMS: Metabolic syndrome (MS) and type 2 diabetes are highly associated with an abnormal lipoprotein profile, which may be generated and accentuated by high cholesteryl ester transfer protein (CETP) activity. Given the difficulty in measuring CETP activity, the aim was to identify simple biochemical predictors of high CETP activity. DESIGN AND METHODS: Eighty five subjects at risk for type 2 diabetes were classified according to the presence of MS. Lipoprotein profile, HOMA-IR and endogenous CETP activity were evaluated. RESULTS: As expected, MS patients presented higher concentration of glucose, insulin, triglycerides and non-HDL-C and lower HDL-C levels. Moreover, MS patients exhibited increased HOMA-IR and CETP activity. Employing a ROC curve for MS, high CETP activity was defined as >250%ml⁻¹ h⁻¹. The predictive variables of high CETP were non-HDL-C≥160mg/dl (OR=11.1;95%IC=3.3-38.2;p<0.001) and HOMA-IR>2.1 (OR=4.4;95%IC=1.3-14.8;p<0.05). CONCLUSIONS: High non-HDL-C and insulin resistance were predictors for increased CETP activity which measurement is not accessible for clinical laboratories.

[Ectopic pancreas in the stomach of infrequent localization in the muscularis mucosae]. / Páncreas ectópico gástrico de infrecuente localización en la muscularis de la mucosa.

Heterotopic pancreatic tissue in the stomach is an uncommon gastric subepithelial lesion. Is usually an asymptomatic condition which is found incidentally. As with other gastric subepithelial lesions, diagnosis can be challenging. Endoscopic forceps biopsy specimens are of little value. Endoscopic ultrasound findings are helpful in characterize this lesions, but they cannot absolutely determine the type of lesion or whether a lesion is benign or malignant. The sequence endosonography- cap assisted endoscopic mucosal resection allows en bloc resection of small gastric subepithelial lesions with low complication rates. We report a case of an ectopic pancreas of the antrum in the stomach that arises from the second layer of the gastric wall (muscularis mucosa) at endoscopic ultrasound that was removed en bloc with cap-assisted endoscopic mucosal resection technique in one endoscopic session without complications.

Multicomponent direct detection of polycyclic aromatic hydrocarbons by surface-enhanced Raman spectroscopy using silver nanoparticles functionalized with the viologen host lucigenin.

Silver nanoparticles (NPs) functionalized with the molecular assembler bis-acridinium dication lucigenin (LG) have been used as a chemical sensor system to detect a group of polycyclic aromatic hydrocarbon (PAH) pollutants in a multicomponent mixture by means of surface-enhanced raman scattering (SERS). The effectiveness of this system was checked for a group of PAHs with different numbers of fused benzene rings, namely anthracene, pyrene, triphenylene, benzo[c]phenanthrene, chrysene, and coronene. In order to determine the host capacity of this sensor system, the self-assembly of the LG viologen on a metallic surface has been checked by analyzing SERS intensities of PAH bands at different LG concentrations. The NP-LG-analyte affinity is derived from the analysis of PAH band intensities at different concentrations of pollutants, the adsorption isotherm of each PAH on NP-LG cavities has been studied, and the corresponding adsorption constants have been evaluated. The limit of detection at trace-level concentration is confirmed by the presence of their characteristic fingerprint vibrational bands. The SERS spectra of PAH mixtures confirm that LG viologen dication shows a higher analytical selectivity to PAHs constituted by four fused benzene rings, mainly pyrene and benzo[c]phenanthrene, in agreement with their higher affinity which is also related to their better fit into the intermolecular LG cavities. As a conclusion, SERS spectra recorded on modified NP-LG surfaces are a powerful chemical tool to detect organic pollutants.

Chromone-3-carboxylic acid as a potential electron scavenger: a surface-enhanced Raman scattering study.

A SERS study of chromone 3-carboxylic acid adsorbed on silver colloids was undertaken, in order to assess the ability of this compound to accept electrons in charge transfer (CT) processes. Theoretical SERS intensities under photoinduced CT resonant conditions have been carried out for both the neutral and the deprotonated species allowing to conclude, by comparison with the experimental data, that the recorded SER corresponds to the anionic form of the acid linked to the metal. It was shown that the SERS-CT mechanism predominates for this particular compound, thus explaining the strong enhancement of the band at ca. 1600 cm(-1) assigned to the 8a ring stretching mode. The identification of CT processes is of the utmost importance for understanding the mechanism through which these benzopyranes may act as antioxidants.

Endoscopic biliary large-balloon dilation after endoscopic sphincterotomy for the treatment of large common bile duct stones. Case report.

Common bile duct (CBD) stones extraction is usually performed by endoscopic sphincterotomy followed by removal by either a Dormia basket or extraction balloon catheter. However, some stones due to their size are not amenable to these procedures and extracorporeal or mechanical lithotripsy devices need to be used. Mechanical lithotripsy involves usage of a basket that will be inevitably destroyed which increases cost to the patient and endoscopy unit. The use of extracorporeal wave shock lithotripsy is an alternative; however it is not available widely. Reports about the use of hydrostatic large caliber balloon dilator (HLCBD) aiding in the extraction of large caliber CBD stones have concluded that is a safe and feasible therapeutic alternative. We present the case of a 25 mm x 30 mm CBD stone that could not be extracted using conventional methods. CBD dilation using HLCBD was performed after endoscopic sphincterotomy in an attempt to avoid mechanical lithotripsy.