ABSTRACT
Three helicenes based on a borylated arylisoquinoline skeleton have been prepared in their enantiopure forms and characterized with respect to their photophysical properties, including the use of chiroptical spectroscopies. The dyes show varying charge-transfer characteristics and efficient emission (quantum yields between 0.13 and 0.30, in toluene), which is governed by the electron-donor substitution (p-MeO-phenyl, p-Me2 N-phenyl) at the helicene. Marked differences in the emission wavelength and Stokes shift are observed, with the dimethylamino-substituted derivative emitting most red-shifted (maximum at ca. 590â nm) and displaying the highest Stokes shift (ca. 6000â cm-1 ) in toluene. The helicenes show electronic circular dichroism (ECD) and significant circularly polarized luminescence (CPL) with dissymmetry factors of up to 3.5×10-3 . The sign of the ECD band corresponding to the first transition and of the CPL spectrum depend sensibly on the electron-donor substitution.
ABSTRACT
Six strongly fluorescent four-coordinate organoboron N,C chelates containing an aryl isoquinoline skeleton were prepared. Remarkably, the fluorescence quantum yields reach values of up to 0.74 in oxygen-free toluene. The strong B-N interaction was corroborated by the single-crystal X-ray analysis of two dyes. The intramolecular charge-transfer character of the fluorophores was evidenced by solvatochromism studies and time-dependent DFT calculations at the PCM(toluene)/CAM-B3LYP/6-311++G(2d,p)//PCM(toluene)/B3LYP/6-311G(2d,p) level of theory. The compounds combine high chemical stability with high photostability, especially when equipped with electron-donating substituents. The strong fluorescence and the large Stokes shifts predestine these compounds for use in confocal fluorescence microscopy. This was demonstrated for the imaging of the N13 mouse microglial cell line. Moreover, significant two-photon absorption cross sections (up to 61â GM) allow the use of excitation wavelengths in the near-infrared region (>800â nm).
ABSTRACT
El objetivo de este artículo es presentar un caso infrecuente de adenoma folicular de tiroides productor de mucina. Es un tumor benigno tiroideo encapsulado que afecta en su mayor parte a mujeres de edad media. Suele presentarse como un nódulo solitario con un tamaño medio entre 1-3 cm. En el patrón histológico muestra una arquitectura macro-microfolicular con presencia de mucina intersticial y en estructuras lacunares. Puede tener cambios a células en anillo de sello o a células claras. Con hematoxilina-eosina, la mucina es basófila, es roja con tinción de mucicarmin y azul con alcian blue, siendo de positividad variable para la tinción con PAS y PAS-diastasa. De igual modo muestra positividad para la mucina tipo MUC1. Las células epiteliales muestran positividad para tiroglobulina, importante en el diagnóstico diferencial, siendo el material mucoide negativo para este marcador. En la revisión de la literatura encontramos 13 casos con mucina en adenomas foliculares y 29 casos en carcinomas primarios tiroideos de distinta índole. Haciendo un recuento anual en nuestros casos con presencia de mucina ocasional, sean adenomas o carcinomas primarios tiroideos, el hallazgo de estos cambios mucinosos focales supone una frecuencia entre 0,25-0,8%, aproximadamente un caso o menos de cada 150 de estas neoplasias. En conclusión, la producción de mucina es un hallazgo no habitual en los adenomas tiroideos. En el diagnóstico diferencial debe considerarse la posibilidad de metástasis u otros tumores tiroideos no derivados del epitelio folicular (AU)
Mucin producing thyroid adenoma is a rare entity affecting mainly middle-aged women. It is a benign, encapsulated tumour presenting as a solitary nodule 1 to 3 cm in size with a macro-microfollicular architecture with areas of interstitial mucin. Occasionally, signet-ring or clear cells are present. The mucin is seen to be basophilic with H&E, stains red with mucicarmin and blue with alcian blue. It is variable for PAS and PAS-Diastase, but shows positivity for MUC1. The epithelial cells stain positive for thyroglobuline, but the mucin is negative. We have found 13 cases of follicular adenomas and 29 cases of thyroid carcinomas with mucinous production in the literature. In our experience, this feature is found in 0.25% to 0.8% of thyroid neoplasms or 1 in 150 annually. In conclusion, mucin production is rare in thyroid adenomas and metastases or other thyroid tumours, including those not derived from the follicular epithelium, in the differential diagnosis (AU)
Subject(s)
Humans , Male , Middle Aged , Adenoma/diagnosis , Adenoma/pathology , Adenocarcinoma, Follicular/complications , Adenocarcinoma, Follicular/diagnosis , Adenocarcinoma, Follicular/pathology , Diagnosis, Differential , Thyroid Gland/pathology , Thyroid Neoplasms/diagnosis , Thyroid Neoplasms/pathologyABSTRACT
The preparation of pH-switchable fluorescent borylated arylisoquinoline dyes via a flexible iridium-catalyzed route is reported. The obtained dyes feature aromatic amino substitution and lateral aliphatic amino groups as electron donors. The photophysical properties of the internal charge transfer dyes were studied, which was complemented by density functional theory calculations. Appreciable fluorescence quantum yields (Φf up to ca. 0.4) and characteristic spectral fingerprints in the green to red emission range were observed. The fluorescence modulation upon multiple and orthogonal protonation with triflic acid was studied and led to the interpretation of multilevel switching including off-on-off, ternary, and quaternary responses.
Subject(s)
Boron Compounds/chemistry , Boron Compounds/chemical synthesis , Fluorescence , Isoquinolines/chemistry , Catalysis , Hydrogen-Ion Concentration , Iridium/chemistry , Molecular Structure , Quantum TheoryABSTRACT
A mild procedure for the Ir(III)-catalyzed nitrogen-directed ortho borylation of aromatic N,N-dialkylhydrazones using pinacolborane as the boron source has been developed. The methodology relies on a modified, hemilabile N,N ligand built on a 4-N,N-dimethylaminopyridine unit that provides high reactivity while maintaining exclusive ortho-selectivity. This procedure can be combined with Suzuki-Miyaura cross-couplings in a 'one-pot' fashion to afford functionalized biaryl derivatives that, upon subsequent 'one-pot', high yielding transformations, provide a convenient entry for the preparation of advanced benzonitrile intermediates for the synthesis of Sartan-type drugs.
Subject(s)
Boron Compounds/chemistry , Boron/chemistry , Hydrazones/chemistry , Iridium/chemistry , Methylamines/chemistry , Nitriles/chemistry , Nitrogen/chemistry , Pyridines/chemistry , Catalysis , Molecular StructureABSTRACT
The use of hemilabile pyridine-hydrazone N,N-ligands allows the highly selective Ir-catalyzed ortho,ortho'-directed diborylation of aromatic N,N-dimethylhydrazones in near-quantitative yields. One-pot sequential Suzuki-Miyaura cross-coupling with different aryl bromides provides a short entry to unsymmetrically substituted 2,6-diarylbenzaldehyde derivatives.
ABSTRACT
The aim of this study was to evaluate the Campbell test and discover if there is a link between a puppy's scores and factors such as age, breed, sex, sex-breed interaction, size, Fédération Cynologique Internationale (FCI) groups, and coat color. The Campbell test was performed on 342 puppies (191 males and 151 females) of different breeds. The results show that the criteria used by Campbell to classify puppies are incomplete, and that it is more appropriate to use numerical values for each type of answer. In general, the mean value obtained, regardless of sex and breed, corresponded to the Campbell's submissive stable category. The mean value was higher in male dogs than in females.
Subject(s)
Behavior, Animal/physiology , Dogs/physiology , Hair Color , Pedigree , Age Distribution , Animals , Body Size/physiology , Female , Male , Sex Distribution , Species SpecificityABSTRACT
En el presente trabajo se han determinado las concentraciones plasmáticas de proteínas totales e inmunoglobulinas mediante inmunodifusión radial, en 40 caballos de Pura Raza Española, de la provincia de Córdoba, España. Los niveles medios obtenidos son similares a los determinados anteriormente para la especie equina, en cambio se pueden encontrar variaciones en cuanto a los niveles medios de inmunoglobulinas plasmáticas con respecto a otras raza, con un valor medio para la IgG de 1293.55ñ77.39 mg/dl, para la IgGT 105.17ñ145.03 mg/dl, para la IgM 56.39ñ5.38 mg/dl y para la IgA 44.92ñ3.525 mg/dl. El sexo y la edad modifican los niveles medios de algunas de estas inmunoglobulinas
