Covalently Immobilizable Tris(Pyridino)-Crown Ether for Separation of Amines Based on Their Degree of Substitution.

A great number of biologically active compounds contain at least one amine function. Appropriate selectivity can only be accomplished in a few cases upon the substitution of these groups, thus functionalization of amines generally results in a mixture of them. The separation of these derivatives with very similar characteristics can only be performed on a preparative scale or by applying pre-optimized HPLC methods. A tris(pyridino)-crown ether was designed and synthetized for overcoming these limitations at a molecular level. It is demonstrated, that this selector molecule is able to distinguish protonated primary, secondary and tertiary amines by the formation of reversible complexes with different stabilities. This degree of substitution-specific molecular recognition of amines opens the door to develop separation processes primarily focusing on the purification of biologically active compounds in a nanomolar scale.

Resolution of 1-n-butyl-3-methyl-3-phospholene 1-oxide with TADDOL derivatives and calcium salts of O,O'-Dibenzoyl-(2R,3R)- or O,O'-di-p-toluoyl-(2R,3R)-tartaric acid.

The resolution methods applying (-)-(4R,5R)-4,5-bis(diphenylhydroxymethyl)-2,2-dimethyldioxolane ("TADDOL"), (-)-(2R,3R)-α,α,α',α'-tetraphenyl-1,4-dioxaspiro[4.5]decan-2,3-dimethanol ("spiro-TADDOL"), as well as the acidic and neutral Ca(2+) salts of (-)-O,O'-dibenzoyl- and (-)-O,O'-di-p-toluoyl-(2R,3R)-tartaric acid were extended for the preparation of 1-n-butyl-3-methyl-3-phospholene 1-oxide in optically active form. In one case, the intermediate diastereomeric complex could be identified by single-crystal X-ray analysis. The absolute P-configuration of the enantiomers of the phospholene oxide was also determined by comparing the experimentally obtained and calculated CD spectra.

[Preoperative chemotherapy in the surgical treatment of colorectal liver metastases]. / Preoperatív kemoterápia a colorectalis májáttétes betegek sebészi kezelésében.

INTRODUCTION: The only curative treatment of colorectal liver metastases (CRLM) is surgical resection. Preoperative/neoadjuvant chemotherapy can be used for resectable, for borderline resectable or even for irresectable CRLM patients. PATIENTS: Data of CRLM patients treated with surgical resection at the Uzsoki Hospital were analysed. Patients were classified into two groups, (A) who received preoperative chemotherapy before hepatic resection, and (B) who received no chemotherapy before resection. RESULTS: Between 01.01.2007. and 31.12.2010. 128 CRLM patients were treated with hepatic resection. 68 patients (53%) received chemotherapy before hepatic resection, 60 patients (47%) were resected without neoadjuvant chemotherapy. There was no significant difference in the complications between the groups (p = 0.39). Median overall survival was 41 months. The progression free survival (PFS) at 3 and 5 years were 25%, the 3 and 5 year overall survival (OS) were 55% and 31%. Both PFS and OS were significantly worse in the chemotherapy group (p = 0.014, p = 0.015). The subgroup of patients receiving bevacizumab containing preoperative chemotherapy has significanly better PFS than patients receiving only cytotoxic chemotherapy (p = 0.004). CONCLUSION: Surgical resection of CRLM patients results good survival data even in non-selected patients, although the very long survival results reported in the literature couldn't have been reproduced in this patient population. When preoperative chemotherapy was combined with bevacizumab, survival was similar to the upfront resected patients.

Sensory evaluation and electronic tongue for sensing flavored mineral water taste attributes.

In this article a trained sensory panel evaluated 6 flavored mineral water samples. The samples consisted of 3 different brands, each with 2 flavors (pear-lemon grass and josta berry). The applied sensory method was profile analysis. Our aim was to analyze the sensory profiles and to investigate the similarities between the sensitivity of the trained human panel and an electronic tongue device. Another objective was to demonstrate the possibilities for the prediction of sensory attributes from electronic tongue measurements using a multivariate statistical method (Partial Least Squares regression [PLS]). The results showed that the products manufactured under different brand name but with the same aromas had very similar sensory profiles. The panel performance evaluation showed that it is appropriate (discrimination ability, repeatability, and panel consensus) to compare the panel's results with the results of the electronic tongue. The samples can be discriminated by the electronic tongue and an accurate classification model can be built. Principal Component Analysis BiPlot diagrams showed that Brand A and B were similar because the manufacturers use the same aroma brands for their products. It can be concluded that Brand C was quite different compared to the other samples independently of the aroma content. Based on the electronic tongue results good prediction models can be obtained with high correlation coefficient (r(2) > 0.81) and low prediction error (RMSEP < 13.71 on the scale of the sensory evaluation from 0 to 100).

Discrimination of mineral waters by electronic tongue, sensory evaluation and chemical analysis.

Mineral, spring and tap water samples of different geographical origins (7 classes) were distinguished by various methods, such as sensory evaluation, electronic tongue measurement, inductively coupled plasma atomic emission spectroscopy and ion chromatography. Samples from the same geographical origin were correctly classified by chemical analysis and electronic tongue (100%), but it was found that only 80% classification rate can be achieved by sensory evaluation. Different water brands (different brand names) from the same geographical origin did not show definite differences, as expected. Forward stepwise algorithm selected three chemical parameters namely, chloride (Cl(-)), sulphate (SO(4)(2-)) and magnesium (Mg) content and two electronic tongue sensor signals (ZZ and HA) to discriminate according to the geographical origins.

[Posterior locked shoulder fracture-dislocation: anatomical resconstruction of reverser Hill-Sachs lession]. / Fractura-luxación posterior inestable del hombro: reconstrucción anatómica de la lesión de Hill-Sachs invertida.

The posterior instability of the shoulder only represents 4% of the shoulder instabilities. For the diagnosis, the antero-posterior, transtoracic and axilar radiographic projections are recommended. The inverted Hill-Sachs lesion is a fracture caused by compression of the antero-medial part of the humeral head during the posterior dislocation. Its treatment results, at least, controverted. Choosing the treatment of these lesions one of the main factors is the size of the defect in the humeral head. When it is smaller than 20%, the simple reduction usually is enough. Between 20-40%, we can opt for a transposition of the subescapular insertion to the bony defect (technique of MacLaughlin) or the anatomical reconstruction of the head by means of the fixation of an allograft. The transposition of the subescapular´s tendon carries a reduction of the internal rotation by medializing its insertion, for this reason, we opted for the anatomical reconstruction with allograft of femoral head that reestablishes the muscular balance. The shoulder artroplasty is elective when bony defects are bigger (>40-50 % of the articulation surface). We present the case of a 32 year-old patient, with the antecedent of convulsive crisis. Clinically he suffered intense pain with functional impotence and elastic limitation for the external rotation in left shoulder. The radiographic studies evidenced an instable posterior fracture-dislocation with inverted Hill-Sachs lesion associated that involved the 30% of the articular surface. The patient was surgically treated, opting for a reconstructive technique for humeral head. After six months, the range of motion is almost symmetrical with regard to the healthy shoulder, without any clinic of instability.

Methods for Improving Image Quality and Reducing Data Load of NIR Hyperspectral Images.

Near Infrared Hyperspectral Imaging (NIRHSI) is an emerging technology platform that integrates conventional imaging and spectroscopy to attain both spatial and spectral information from an object. Two important problems in NIRHSI are those of data load and unserviceable pixels in the NIR sensor. Hyperspectral imaging experiments generate large amounts of data (typically > 50 MB per image), which tend to overwhelm the memory capacity of conventional computer systems. This inhibits the utilisation of NIRHSI for routine online industrial application. In general, approximately 1% of pixels in NIR detectors are unserviceable or 'dead', containing no useful information. While this percentage of pixels is insignificant for single wavelength imaging, the problem is amplified in NIRHSI, where > 100 wavelength images are typically acquired. This paper describes an approach for reducing the data load of hyperspectral experiments by using sample-specific vector-to-scalar operators for real time feature extraction and a systematic procedure for compensating for 'dead' pixels in the NIR sensor. The feasibility of this approach was tested for prediction of moisture content in carrot tissue.