Intramolecular Hydrogen Bond in Pyridine Schiff Bases as Ancillary Ligands of Re(I) Complexes Is a Switcher between Visible and NIR Emissions: A Relativistic Quantum Chemistry Study.

Rhenium(I) tricarbonyl complexes have been described as suitable fluorophores, particularly for biological applications. fac-[Re(CO)3(N,N)L](0 or 1+) complexes, where N,N is a substituted dinitrogenated ligand (bipyridine or derivatives with relatively small substituents) and L the ancillary ligand [a pyridine Schiff base (PSB) harboring an intramolecular hydrogen bond (IHB)], have presented promissory results concerning their use as fluorophores, especially for walled cells (i.e., bacteria and fungi). In this work, we present a relativistic theoretical analysis of two series of fac-[Re(CO)3(N,N)PSB]1+ complexes to predict the role of the IHB in the ancillary ligand concerning their photophysical behavior. N,N corresponds to 2,2'-bipyridine (bpy) (series A) or 4,4'-bis(ethoxycarbonyl)-2,2'-bipyridine (deeb) (series B). We found that all the complexes present absorption in the visible light range. In addition, complexes presenting a PSB with an IHB exhibit luminescent emission suitable for biological purposes: large Stokes shift, emission in the range of 600-700 nm, and τ in the order of 10-2 to 10-3 s. By contrast, complexes with PSB lacking the IHB show a predicted emission with the lowest triplet excited-state energy entering the NIR region. These results suggest a role of the IHB as an important switcher between visible and NIR emissions in this kind of complexes. Since the PSB can be substituted to modulate the properties of the whole Re(I) complex, it will be interesting to explore whether other substitutions can also affect the photophysical properties, mainly the emission range.

Advantages of Sentinel Lymph Node Mapping by Single Photon Emission Computed Tomography/Computed Tomography in Early-Stage Malignant Head-and-Neck Skin Tumors.

Background: The aim of this study was to determine the advantages of preoperative sentinel lymph node mapping (SLNM) by single photon emission computed tomography/computed tomography (SPECT / CT) in patients with early-stage cutaneous head-and-neck malignancies. Materials and Methods: We conduct a 7-year and 6 months retrospective, cross-sectional study. Patients with early-stage malignant head-and-neck skin tumors and cutaneous adnexa who underwent SLNM by SPECT/CT from March 2012 and December 2019, were included in the study. Results: We retrospectively analyzed 28 patients: Melanoma was the most frequent tumor (64.2%), followed by squamous cell carcinoma (25%). The anterior cheek was the most common functional subsite (25%). Twenty-seven patients (96.4%) had a successful SLN detection with SPECT/CT. Neck lymph node dissection was performed in 23 patients (82.1%). According to the pathological specimen, lymph nodes were found in all of them; hence, the efficacy of the SPECT/CT for SLNM was 100%. At 7-year follow-up, systemic recurrence was found in one patient (3.6%), another had locoregional recurrence (3.6%), and the mortality rate was 3.6%. Conclusions: In early-stage malignant head-and-neck skin tumors, there is a high concordance between SLN found by SPECT/CT and the histopathological results. Preoperative SPECT/CT accurately detects the SLN, assesses unexpected lymph nodes and their drainage pathways, and facilitates their location by reliably showing the relationships between sentinel nodes and important anatomic structures. This allows to perform a clear preoperative evaluation, an accurate staging for all patients and to avoid excessive dissections that could result in cosmetic and functional deformities.

Physicochemical and Theoretical Characterization of a New Small Non-Metal Schiff Base with a Differential Antimicrobial Effect against Gram-Positive Bacteria.

Searching for adequate and effective compounds displaying antimicrobial activities, especially against Gram-positive bacteria, is an important research area due to the high hospitalization and mortality rates of these bacterial infections in both the human and veterinary fields. In this work, we explored (E)-4-amino-3-((3,5-di-tert-butyl-2-hydroxybenzylidene)amino) benzoic acid (SB-1, harboring an intramolecular hydrogen bond) and (E)-2-((4-nitrobenzilidene)amino)aniline (SB-2), two Schiff bases derivatives. Results demonstrated that SB-1 showed an antibacterial activity determined by the minimal inhibitory concentration (MIC) against Staphylococcus aureus, Enterococcus faecalis, and Bacillus cereus (Gram-positive bacteria involved in human and animal diseases such as skin infections, pneumonia, diarrheal syndrome, and urinary tract infections, among others), which was similar to that shown by the classical antibiotic chloramphenicol. By contrast, this compound showed no effect against Gram-negative bacteria (Klebsiella pneumoniae, Escherichia coli, and Salmonella enterica). Furthermore, we provide a comprehensive physicochemical and theoretical characterization of SB-1 (as well as several analyses for SB-2), including elemental analysis, ESMS, 1H and 13C NMR (assigned by 1D and 2D techniques), DEPT, UV-Vis, FTIR, and cyclic voltammetry. We also performed a computational study through the DFT theory level, including geometry optimization, TD-DFT, NBO, and global and local reactivity analyses.

A theoretical chemistry-based strategy for the rational design of new luminescent lanthanide complexes: an approach from a multireference SOC-NEVPT2 method.

Theoretical methods of the SOC-NEVPT2 type combined with a molecular fragmentation scheme have been proven to be a powerful tool that allows explaining the luminescence sensitization mechanism in Ln(III) coordination compounds through the antenna effect. In this work, we have used this strategy to predict luminescence in a family of compounds of the Eu(R-phen)(BTA)3 type where R-phen = 5-methyl-1,10-phenanthroline (Me-phen), 5-nitro-1,10-71 phenanthroline (Nitro-phen), 4,5-diazafluoren-9-one (One-phen), or 5,6-epoxy-5,6-dihydro-1,10-72 phenanthroline (Epoxy-phen); and BTA = fluorinated ß-diketone. Possible sensitization pathways were elucidated from the energy difference between the ligand-centered triplet (3T) states and the emissive excited states of the Eu(III) fragments (Latva rules). Calculations show that the most probable mechanism occurs through the triplet state of the BTA which should be enriched by several parallel energy transfer pathways from R-phen substituents. The complexes were synthesized and structurally characterized by X-ray crystallography and various other physicochemical and spectroscopic methods to realize their optical properties and energy transfer pathways from dual antennae. Experimental results were in good agreement with the theoretical predictions, which reinforces the predictive power of the used theoretical methodology.

Perfusión aislada de extremidad: una opción terapéutica para metástasis en tránsito de melanoma nodular y lentiginoso acral.

OBJETIVO: describir la experiencia inicial en Colombia en el manejo del melanoma de extremidad con perfusión aislada y comparar la respuesta de los subtipos histológicos más frecuentes en Colombia con la literatura. MATERIALES Y MÉTODOS: estudio descriptivo, retrospectivo de una serie de pacientes con diagnóstico de melanoma con metástasis en tránsito tratados con perfusión aislada de extremidad, seleccionados entre 2007 y 2016. Las variables cualitativas se analizaron con frecuencias absolutas y relativas. Las cuantitativas con medidas de tendencia central y dispersión. RESULTADOS: 11 pacientes fueron tratados con perfusión aislada de extremidad. Hubo respuesta parcial en siete pacientes (63,6%), enfermedad estable en dos pacientes (18,2%) y progresión en dos pacientes (18,2%). Después del tratamiento, cinco pacientes (45,5%) presentaron complicaciones menores. CONCLUSIONES: la perfusión aislada sigue siendo importante para el tratamiento del melanoma localmente avanzado con el fin de mejorar la calidad de vida de los pacientes. La respuesta puede cambiar según el tipo clínico de melanoma, siendo menor, según este estudio, en pacientes con melanoma lentiginoso acral y nodular, aunque por el bajo poder, esto no se puede concluir. OBJECTIVE: to describe the initial experience in Colombia of locally advanced melanoma treated by isolated limb perfusion and compare the response rate of our melanoma subtypes with the literature. METHODS: descriptive, retrospective study of a series of patients selected between 2007 and 2016. Qualitative variables were analyzed with proportions and frequencies, and quantitative variable with central tendency measures and measures of dispersion. RESULTS: 11 patients were treated by isolated limb perfusion. After the treatment, seven patients (63.6%) had partial response, two patients (18.2%) had stable disease and two patients (18.2%) had disease progression. Five patients (45.5%) had mild complications. CONCLUSIONS: Isolated limb perfusion is still an important treatment strategy for locally advanced melanoma, with the goal of improving the patient quality of life. The response can change according to the type of melanoma, and could be smaller in patients with acral lentiginous and nodular melanoma, although we cannot make this conclusion with this type of study because it has low power and lack of a comparison group.

Safety and efficacy of sorafenib in patients with advanced thyroid carcinoma: a phase II study (NCT02084732)

ABSTRACT Objective: Sorafenib significantly prolonged progression-free survival in patients with iodine-refractory advanced thyroid cancer. The present study was initiated before sorafenib was approved in Colombia and therefore represents an effort by an oncology institution to evaluate its efficacy and safety in this population. Subjects and methods: This phase II clinical trial had a single treatment arm. We included adult patients with progressive metastatic iodine-refractory thyroid cancer who received treatment with sorafenib 800 mg/day (400 mg every 12 hours) up to a maximum of 24 months or until the occurrence of limiting related toxicity, the progression of the disease, or voluntary withdrawal. Results: Nineteen patients received the treatment and were included in the safety analysis. However, for the efficacy analysis, 6 patients were excluded because they received only one month of therapy. Thirteen (68%) patients were women, and the mean age at diagnosis was 61.8 years. No complete responses were observed; 5 patients had a partial response (35.7%), 6 patients had stable disease, and 3 showed progression. Mean progression-free survival was calculated at 18 months (95% CI 10.7-20.3). Overall survival was estimated at 21.3 months (95% CI 17.8-24.8). Conclusion: For the first time in Colombia, the efficacy of sorafenib was evaluated in patients with advanced and progressive thyroid carcinoma refractory to radioactive iodine, with an efficacy and a safety profile similar to those previously reported.

"One for All": Functional Transfer of OMV-Mediated Polymyxin B Resistance From Salmonella enterica sv. Typhi ΔtolR and ΔdegS to Susceptible Bacteria.

The appearance of multi-resistant strains has contributed to reintroducing polymyxin as the last-line therapy. Although polymyxin resistance is based on bacterial envelope changes, other resistance mechanisms are being reported. Outer membrane vesicles (OMVs) are nanosized proteoliposomes secreted from the outer membrane of Gram-negative bacteria. In some bacteria, OMVs have shown to provide resistance to diverse antimicrobial agents either by sequestering and/or expelling the harmful agent from the bacterial envelope. Nevertheless, the participation of OMVs in polymyxin resistance has not yet been explored in S. Typhi, and neither OMVs derived from hypervesiculating mutants. In this work, we explored whether OMVs produced by the hypervesiculating strains Salmonella Typhi ΔrfaE (LPS synthesis), ΔtolR (bacterial envelope) and ΔdegS (misfolded proteins and σ E activation) exhibit protective properties against polymyxin B. We found that the OMVs extracted from S. Typhi ΔtolR and ΔdegS protect S. Typhi WT from polymyxin B in a concentration-depending manner. By contrast, the protective effect exerted by OMVs from S. Typhi WT and S. Typhi ΔrfaE is much lower. This effect is achieved by the sequestration of polymyxin B, as assessed by the more positive Zeta potential of OMVs with polymyxin B and the diminished antibiotic's availability when coincubated with OMVs. We also found that S. Typhi ΔtolR exhibited an increased MIC of polymyxin B. Finally, we determined that S. Typhi ΔtolR and S. Typhi ΔdegS, at a lesser level, can functionally and transiently transfer the OMV-mediated polymyxin B resistance to susceptible bacteria in cocultures. This work shows that mutants in genes related to OMVs biogenesis can release vesicles with improved abilities to protect bacteria against membrane-active agents. Since mutations affecting OMV biogenesis can involve the bacterial envelope, mutants with increased resistance to membrane-acting agents that, in turn, produce protective OMVs with a high vesiculation rate (e.g., S. Typhi ΔtolR) can arise. Such mutants can functionally transfer the resistance to surrounding bacteria via OMVs, diminishing the effective concentration of the antimicrobial agent and potentially favoring the selection of spontaneous resistant strains in the environment. This phenomenon might be considered the source for the emergence of polymyxin resistance in an entire bacterial community.

New Cationic fac-[Re(CO)3(deeb)B2]+ Complex, Where B2 Is a Benzimidazole Derivative, as a Potential New Luminescent Dye for Proteins Separated by SDS-PAGE.

Sodium-dodecyl-sulfate polyacrylamide gel electrophoresis (SDS-PAGE) can be used to separate proteins based mainly on their size such as in denaturing gels. Different staining methods have been reported to observe proteins in the gel matrix, where the most used dyes are generally anionic. Anionic dyes allow for interactions with protonated amino acids, retaining the dye in the proteins. Fluorescent staining is an alternative technique considered to be sensitive, safe, and versatile. Some anionic complexes based on d6 transition metals have been used for this purpose, where cationic dyes have been less explored in this context. In this work, we synthesized and characterized a new monocationic rhenium complex fac-[Re(CO)3(deeb)B2]+ (where deeb is 4,4'-bis(ethoxycarbonyl)-2,2'-bpy and B2 is 2,4-di-tert-butyl-6-(3H-imidazo[4,5-c]pyridine-2-yl)phenol). We carried out a structural characterization of this complex by MS+, FTIR, 1H NMR, D2O exchange, and HHCOSY. Moreover, we carried out UV-Vis, luminescence, and cyclic voltammetry experiments to understand the effect of ligands on the complex's electronic structure. We also performed relativistic theoretical calculations using the B3LYP/TZ2P level of theory and R-TDDFT within a dielectric continuum model (COSMO) to better understand electronic transitions and optical properties. We finally assessed the potential of fac-[Re(CO)3(deeb)B2]+ (as well as the precursor fac-Re(CO)3(deeb)Br and the free ligand B2) to stain proteins separated by SDS-PAGE. We found that only fac-[Re(CO)3(deeb)B2]+ proved viable to be directly used as a luminescent dye for proteins, presumably due to its interaction with negatively charged residues in proteins and by weak interactions provided by B2. In addition, fac-[Re(CO)3(deeb)B2]+ seems to interact preferentially with proteins and not with the gel matrix despite the presence of sodium dodecyl sulfate (SDS). In future applications, these alternative cationic complexes might be used alone or in combination with more traditional anionic compounds to generate counterion dye stains to improve the process.

Safety and efficacy of sorafenib in patients with advanced thyroid carcinoma: a phase II study (NCT02084732).

OBJECTIVE: Sorafenib significantly prolonged progression-free survival in patients with iodine-refractory advanced thyroid cancer. The present study was initiated before sorafenib was approved in Colombia and therefore represents an effort by an oncology institution to evaluate its efficacy and safety in this population. METHODS: This phase II clinical trial had a single treatment arm. We included adult patients with progressive metastatic iodine-refractory thyroid cancer who received treatment with sorafenib 800 mg/day (400 mg every 12 hours) up to a maximum of 24 months or until the occurrence of limiting related toxicity, the progression of the disease, or voluntary withdrawal. RESULTS: Nineteen patients received the treatment and were included in the safety analysis. However, for the efficacy analysis, 6 patients were excluded because they received only one month of therapy. Thirteen (68%) patients were women, and the mean age at diagnosis was 61.8 years. No complete responses were observed; 5 patients had a partial response (35.7%), 6 patients had stable disease, and 3 showed progression. Mean progression-free survival was calculated at 18 months (95% CI 10.7-20.3). Overall survival was estimated at 21.3 months (95% CI 17.8-24.8). CONCLUSION: For the first time in Colombia, the efficacy of sorafenib was evaluated in patients with advanced and progressive thyroid carcinoma refractory to radioactive iodine, with an efficacy and a safety profile similar to those previously reported.

The role of substituted pyridine Schiff bases as ancillary ligands in the optical properties of a new series of fac-rhenium(i) tricarbonyl complexes: a theoretical view.

Over the last few years, luminescent Re(i) tricarbonyl complexes have been increasingly proposed as fluorophores suitable for fluorescence microscopy to visualize biological structures and cells. In this sense, incorporating an asymmetrical pyridine Schiff base (PSB) as the ancillary ligand strongly modifies the staining and luminescent properties of Re(i) tricarbonyl complexes. In this work, we analyzed two series of Re(i) tricarbonyl complexes with their respective PSB ligands: (1) fac-[Re(CO)3(2,2'-bpy)(PSB)]1+ and (2) fac-[Re(CO)3(4,4'-bis(ethoxycarbonyl)-2,2'-bpy)(PSB)]1+, where the PSB exhibits substitutions at positions 4 or 6 in the phenolic ring with methyl or halogen substituents. Thus, we performed computational relativistic DFT and TDDFT studies to determine their optical properties. The ten complexes analyzed showed absorption in the visible light range. Furthermore, our analyses, including zero-field splitting (ZFS), allowed us to determine that the low-lying excited state locates below the 3LLCT states. Interestingly, seven of the ten analyzed complexes, whose corresponding PSB harbors an intramolecular hydrogen bond (IHB), exhibited luminescent emission that could be suitable for biological purposes: large Stokes shift, emission in the range 600-700 nm and τ in the order of 10-2 to 10-3 s. Conversely, the three complexes lacking the IHB due to two halogen substituents in the corresponding PSB showed a predicted emission with the lowest triplet excited state energy entering the NIR region. The main differences in the complexes' photophysical behavior have been explained by the energy gap law and time-resolved luminescence. These results emphasize the importance of choosing suitable substituents at the 4 and 6 positions in the phenolic ring of the PSB, which determine the presence of the IHB since they modulate the luminescence properties of the Re(i) core. Therefore, this study could predict Re(i) tricarbonyl complexes' properties, considering the desired emission features for biological and other applications.

Correction: The role of substituted pyridine Schiff bases as ancillary ligands in the optical properties of a new series of fac-rhenium(i) tricarbonyl complexes: a theoretical view.

[This corrects the article DOI: 10.1039/D1RA05737E.].

Structural Characterization, DFT Calculation, NCI, Scan-Rate Analysis and Antifungal Activity against Botrytis cinerea of (E)-2-{[(2-Aminopyridin-2-yl)imino]-methyl}-4,6-di-tert-butylphenol (Pyridine Schiff Base).

Botrytis cinerea is a ubiquitous necrotrophic filamentous fungal phytopathogen that lacks host specificity and can affect more than 1000 different plant species. In this work, we explored L1 [(E)-2-{[(2-aminopyridin-2-yl)imino]-methyl}-4,6-di-tert-butylphenol], a pyridine Schiff base harboring an intramolecular bond (IHB), regarding their antifungal activity against Botrytis cinerea. Moreover, we present a full characterization of the L1 by NMR and powder diffraction, as well as UV-vis, in the presence of previously untested different organic solvents. Complementary time-dependent density functional theory (TD-DFT) calculations were performed, and the noncovalent interaction (NCI) index was determined. Moreover, we obtained a scan-rate study on cyclic voltammetry of L1. Finally, we tested the antifungal activity of L1 against two strains of Botrytis cinerea (B05.10, a standard laboratory strain; and A1, a wild type strains isolated from Chilean blueberries). We found that L1 acts as an efficient antifungal agent against Botrytis cinerea at 26 °C, even better than the commercial antifungal agent fenhexamid. Although the antifungal activity was also observed at 4 °C, the effect was less pronounced. These results show the high versatility of this kind of pyridine Schiff bases in biological applications.

Rhenium (I) Complexes as Probes for Prokaryotic and Fungal Cells by Fluorescence Microscopy: Do Ligands Matter?

Re(I) complexes have exposed highly suitable properties for cellular imaging (especially for fluorescent microscopy) such as low cytotoxicity, good cellular uptake, and differential staining. These features can be modulated or tuned by modifying the ligands surrounding the metal core. However, most of Re(I)-based complexes have been tested for non-walled cells, such as epithelial cells. In this context, it has been proposed that Re(I) complexes are inefficient to stain walled cells (i.e., cells protected by a rigid cell wall, such as bacteria and fungi), presumably due to this physical barrier hampering cellular uptake. More recently, a series of studies have been published showing that a suitable combination of ligands is useful for obtaining Re(I)-based complexes able to stain walled cells. This review summarizes the main characteristics of different fluorophores used in bioimage, remarking the advantages of d6-based complexes, and focusing on Re(I) complexes. In addition, we explored different structural features of these complexes that allow for obtaining fluorophores especially designed for walled cells (bacteria and fungi), with especial emphasis on the ligand choice. Since many pathogens correspond to bacteria and fungi (yeasts and molds), and considering that these organisms have been increasingly used in several biotechnological applications, development of new tools for their study, such as the design of new fluorophores, is fundamental and attractive.

New Properties of a Bioinspired Pyridine Benzimidazole Compound as a Novel Differential Staining Agent for Endoplasmic Reticulum and Golgi Apparatus in Fluorescence Live Cell Imaging.

In this study, we explored new properties of the bioinspired pyridine benzimidazole compound B2 (2,4-di-tert-butyl-6-(3H-imidazo[4,5-c]pyridine-2-yl)phenol) regarding its potential use as a differential biomarker. For that, we performed 1D 1HNMR (TOCSY), UV-Vis absorption spectra in different organic solvents, voltammetry profile (including a scan-rate study), and TD-DFT calculations that including NBO analyses, to provide valuable information about B2 structure and luminescence. In our study, we found that the B2 structure is highly stable, where the presence of an intramolecular hydrogen bond (IHB) seems to have a crucial role in the stability of luminescence, and its emission can be assigned as fluorescence. In fact, we found that the relatively large Stokes Shift observed for B2 (around 175 nm) may be attributed to the stability of the B2 geometry and the strength of its IHB. On the other hand, we determined that B2 is biocompatible by cytotoxicity experiments in HeLa cells, an epithelial cell line. Furthermore, in cellular assays we found that B2 could be internalized by passive diffusion in absence of artificial permeabilization at short incubation times (15 min to 30 min). Fluorescence microscopy studies confirmed that B2 accumulates in the endoplasmic reticulum (ER) and Golgi apparatus, two organelles involved in the secretory pathway. Finally, we determined that B2 exhibited no noticeable blinking or bleaching after 1 h of continuous exposure. Thus, B2 provides a biocompatible, rapid, simple, and efficient way to fluorescently label particular organelles, producing similar results to that obtained with other well-established but more complex methods.

Two New Fluorinated Phenol Derivatives Pyridine Schiff Bases: Synthesis, Spectral, Theoretical Characterization, Inclusion in Epichlorohydrin-ß-Cyclodextrin Polymer, and Antifungal Effect.

It has been reported that the structure of the Schiff bases is fundamental for their function in biomedical applications. Pyridine Schiff bases are characterized by the presence of a pyridine and a phenolic ring, connected by an azomethine group. In this case, the nitrogen present in the pyridine is responsible for antifungal effects, where the phenolic ring may be also participating in this bioactivity. In this study, we synthesized two new pyridine Schiff Bases: (E)-2-[(3-Amino-pyridin-4-ylimino)-methyl]-4,6-difluoro-phenol (F1) and (E)- 2-[(3-Amino-pyridin-4-ylimino)-methyl]-6-fluoro-phenol (F2), which only differ in the fluorine substitutions in the phenolic ring. We fully characterized both F1 and F2 by FTIR, UV-vis, 1H; 13C; 19F-NMR, DEPT, HHCOSY, TOCSY, and cyclic voltammetry, as well as by computational studies (DFT), and NBO analysis. In addition, we assessed the antifungal activity of both F1 (two fluorine substitution at positions 4 and 6 in the phenolic ring) and F2 (one fluorine substitution at position 6 in the phenolic ring) against yeasts. We found that only F1 exerted a clear antifungal activity, showing that, for these kind of Schiff bases, the phenolic ring substitutions can modulate biological properties. In addition, we included F1 and F2 into in epichlorohydrin-ß-cyclodextrin polymer (ßCD), where the Schiff bases remained inside the ßCD as determined by the ki , TGA, DSC, and SBET. We found that the inclusion in ßCD improved the solubility in aqueous media and the antifungal activity of both F1 and F2, revealing antimicrobial effects normally hidden by the presence of common solvents (e.g., DMSO) with some cellular inhibitory activity. The study of structural prerequisites for antimicrobial activity, and the inclusion in polymers to improve solubility, is important for the design of new drugs.

Características del melanoma cutáneo primario en el Instituto Nacional de Cancerología 2006-2010 / Characteristics of primary cutaneous melanoma in the Colombian National Cancerology Institute 2006-2010

Objetivos: Describir las principales características del melanoma cutáneo en el Instituto Nacional de Cancerología, centro de referencia del cáncer, en Bogotá, Colombia. Materiales y métodos: Estudio descriptivo, retrospectivo, de las características demográficas, clínicas e histológicas de los pacientes con diagnóstico de melanoma cutáneo primario, en el Instituto Nacional de Cancerología entre 2006 y 2010. Resultados: Se incluyeron un total de 599 pacientes, de los cuales el 57,4% eran mujeres (n = 344) y el 42,6% hombres (n = 255). La edad media de diagnóstico fue de 60,8 años. La mayoría de los casos fueron procedentes de Bogotá, con el 56,3% (n = 329). Fue más frecuente el área urbana como sitio de residencia habitual (n = 500). La media de frecuencia anual fue de 115 casos nuevos por año. La localización más frecuente fue acral, con el 42,2% (n = 253), seguido de cabeza y cuello (n = 186). Concordando con la localización, el subtipo más frecuente fue el melanoma lentiginoso acral, con el 43,7% (n = 262), seguido por el lentigo maligno, con el 24% (n = 144). En cuanto a la profundidad, se observó una frecuencia igual de melanomas in situ y melanomas con Breslow > 4 mm, ambos con el 19% de los casos. Se encontró que la mayoría de los lentigos malignos, el 75% (n = 108), fueron in situ o con un Breslow ≤ 1 mm; por el contrario, los lentiginosos acrales y los nodulares tuvieron un Breslow > 4 mm con mayor frecuencia (con el 26,3%, n = 69, y el 45,4%, n = 10, respectivamente). El estadio más frecuente fue el III, con el 26,2% de los casos (n = 157). Conclusiones: Se evidenció un mayor porcentaje de melanomas en mujeres y mayor frecuencia de melanomas acrales. Un número importante de pacientes se ubicaron en estado avanzado, por lo que se requieren mayores acciones para la detección temprana del melanoma.

Objectives: To describe the main characteristics of cutaneous melanoma in the National Cancerology Institute, a cancer reference center in Bogota, Colombia. Materials and methods: A descriptive, retrospective study was conducted on the demographic, clinical and histological characteristics of patients diagnosed with primary cutaneous melanoma in the National Cancerology Institute between 2006 and 2010. Results: A total of 599 patients were included, of whom 57.4% were females (n= 344) and 42.6% males (n=255). The mean age at diagnosis was 60.8 years. The majority of cases, 56.3% (n=329), were from Bogota. It was also the most common urban area where the patients had their usual residence (n=500). The mean annual frequency was 115 new cases per year. The most frequent location was acral, with 42.2% (n=253), followed by head and neck (n=186). In accordance with the location, the most common sub-type was acral lentiginous melanoma, with con 43.7% (n=262), followed by lentigo maligna, with 24% (n=144). As regards the depth, a similar frequency was observed for melanomas in situ and melanomas with Breslow >4 mm, both with 19% of the cases. It was found that the large majority of the lentigo maligna, 75% (n=108) were in situ or with a Breslow ≤1 mm. On the other hand, acral lentiginous and nodular melanomas had a higher frequency of Breslow >4 mm (with 26.3% n=69 and 45.4% n=10, respectively). Stage III was the most common stage, with 26.2% (n=157) of the cases. Conclusions: A higher percentage of melanomas were observed in women, as well as a higher frequency of acral melanomas. A signifi cant number of patients were in an advanced stage, thus greater action is required for the early detection of melanoma.

(E)-2-{[(2-Amino-pyridin-3-yl)imino]-meth-yl}-4,6-di-tert-butyl-phenol.

In the title compound, C(20)H(27)N(3)O, the hy-droxy group forms an intra-molecular O-H⋯N hydrogen bond with the imino N atom. The dihedral angle between the aromatic rings is 33.09 (9)°. In the crystal, mol-ecules form centrosymmetric dimers via pairs of N-H⋯N hydrogen bonds involving amino-pyridine fragments.

Phenyl 3,5-di-tert-butyl-2-hy-droxy-benzoate.

The title mol-ecule, C(21)H(26)O(3), has a six-membered planar carbon ring as the central core, substituted at position 1 with phen-oxy-carbonyl, at position 2 with hy-droxy and at positions 3 and 5 with tert-butyl groups. The structure shows two independent but very similar mol-ecules within the asymmetric unit. For both independent mol-ecules, the ester carboxyl-ate group is coplanar with the central core, as reflected by the small C-C-O-C torsion angles [179.95 (17) and 173.70 (17)°]. In contrast, the phenyl substituent is almost perpendicular to the carboxyl-ate -CO(2) fragment, as reflected by C-O-C-C torsion angles, ranging from 74 to 80°. The coplanarity between the central aromatic ring and the ester carboxyl-ate -CO(2)- group allows the formation of an intra-molecular hydrogen bond, with O⋯O distances of 2.563 (2) and 2.604 (2) Å.