Expedient Synthesis of Oxaboracyclic Compounds Based on Naphthalene and Biphenyl Backbone and Phase-Dependent Luminescence of their Chelate Complexes.

The approach to a series of six- and seven-membered oxaboraheterocycles based on naphthalene or biphenyl backbones was developed. The key synthetic step involved Br/Li exchange in respective potassium (bromoaryl)trifluoroborates followed by quenching with selected electrophiles (CO2 , DMF, Me2 Si(H)Cl) and hydrolytic workup. Two ring-expanded benzoxaborole congeners were obtained by an additional reduction step with LiAlH4 or NaBH4 . The obtained boracyclic compounds were characterized in detail by NMR spectroscopy and single-crystal X-ray diffraction. Specifically, biphenyl-based systems show dynamic behaviour interpreted in terms of inversion of non-planar seven-membered boraheterocycles. The acidity of the obtained compounds varies very strongly (pKa ranges from 3.1-9.6) depending on their structure. Due to the enhanced boron Lewis acidity, selected compounds were used as a basis for luminescent complexes with 8-hydroxyquinoline. A strong phase-dependent variation of emission-band maximum (480-527 nm) and photoluminescence quantum yield (10-95 %) was observed, which was rationalized in terms of specific aggregation effects.

Instrument-model refinement in normalized reciprocal-vector space for X-ray Laue diffraction.

A simple yet efficient instrument-model refinement method for X-ray diffraction data is presented and discussed. The method is based on least-squares minimization of differences between respective normalized (i.e. unit length) reciprocal vectors computed for adjacent frames. The approach was primarily designed to work with synchrotron X-ray Laue diffraction data collected for small-molecule single-crystal samples. The method has been shown to work well on both simulated and experimental data. Tests performed on simulated data sets for small-molecule and protein crystals confirmed the validity of the proposed instrument-model refinement approach. Finally, examination of data sets collected at both BioCARS 14-ID-B (Advanced Photon Source) and ID09 (European Synchrotron Radiation Facility) beamlines indicated that the approach is capable of retrieving goniometer parameters (e.g. detector distance or primary X-ray beam centre) reliably, even when their initial estimates are rather inaccurate.

Seed-skewness algorithm for X-ray diffraction signal detection in time-resolved synchrotron Laue photocrystallography.

A one-dimensional seed-skewness algorithm adapted for X-ray diffraction signal detection is presented and discussed. The method, primarily designed for photocrystallographic time-resolved Laue data processing, was shown to work well for the type of data collected at the Advanced Photon Source and European Synchrotron Radiation Facility. Nevertheless, it is also applicable in the case of standard single-crystal X-ray diffraction data. The reported algorithm enables reasonable separation of signal from the background in single one-dimensional data vectors as well as the capability to determine small changes of reflection shapes and intensities resulting from exposure of the sample to laser light. Otherwise, the procedure is objective, and relies only on skewness computation and its subsequent minimization. The new algorithm was proved to yield comparable results to the Kruskal-Wallis test method [Kalinowski, J. A. et al. (2012). J. Synchrotron Rad. 19, 637], while the processing takes a similar amount of time. Importantly, in contrast to the Kruskal-Wallis test, the reported seed-skewness approach does not need redundant input data, which allows for faster data collections and wider applications. Furthermore, as far as the structure refinement is concerned, the reported algorithm leads to the excited-state geometry closest to the one modelled using the quantum-mechanics/molecular-mechanics approach reported previously [Jarzembska, K. N. et al. (2014). Inorg. Chem. 53, 10594], when the t and s algorithm parameters are set to the recommended values of 0.2 and 3.0, respectively.

Lung surgery for metastatic epithelial tumours.

INTRODUCTION: The aim of this study is to evaluate outcomes following the surgical treatment of pulmonary metastases in patients with different types of epithelial cancers, as well as to identify prognostic factors after metastasectomy. MATERIAL/METHODS: We retrospectively reviewed data for 61 patients who underwent 76 curative resections of pulmonary metastases from epithelial tumours during 1997-2002 at our department. Potential prognostic factors affecting survival after lung metastasectomy were analysed: disease-free interval (DFI), gender, age, the size and number of metastases, mono- or bilateral tumour, number of operations and the extent of pulmonary resection. RESULTS: The median survival was 36 months. Three factors were identified as prognostic for survival after metastasectomy: DFI<24 (p=0.0045), unilateral pulmonary metastases (p=0.0062) and no more than one operation (p=0.0065). CONCLUSIONS: We concluded that: i) Resection of epithelial pulmonary metastases may offer a significant survival benefit for selected patients. ii) Good surgical candidates for pulmonary resection are those with a disease-free interval greater than 24 months. iii) The total number of thoracotomies, and metastases confined to one lung are factors defining patients who experience a better outcome after surgery. iv) Lung metastasectomy by conventional surgery is a safe procedure with low perioperative morbidity and mortality rates.

Can we improve the dose distribution for single or multi-lumen breast balloons used for Accelerated Partial Breast Irradiation?

PURPOSE: The aim of the study was to verify dose distribution parameters for multi-lumen, and artificially created single-lumen balloon applicator used for the same patient with two optimization algorithms: inverse planning simulated annealing (IPSA) and dose point optimization with distance option. MATERIAL AND METHODS: Group of 24 patients with multi-lumen balloon applied were investigated. Each patient received 10 fractions of 3.4 Gy (2 fractions daily). For every patient, four treatment plans were prepared. Firstly, for five-lumen balloon optimized with IPSA algorithm and optimization parameters adjusted for each case. Secondly, for the same applicator optimized with dose point optimization and distant option. Two other plans were prepared for single-lumen applicator, created by removing four peripheral lumens, optimized with both algorithms. RESULTS: The highest D95 parameter was obtained for plans optimized with IPSA algorithm, mean value 99.3 percent of prescribed dose, and it was significantly higher than plans optimized with dose point algorithm (mean = 83.50%, p < 0.0001), IPSA single-lumen balloon plan (mean = 83.50%, p = 0.0037) and optimized to dose point single-lumen balloon (mean = 85.51%, p < 0.0001). There were no statistically significant differences concerning maximum doses distributed to skin surface for neither application nor optimization method. Volumes receiving 200% of prescribed dose in PTV were higher for multi-lumen balloon dose point optimized plans (mean = 8.78%), than for other plans (IPSA multi-lumen balloon plan: mean = 7.37%, p < 0.0001, single-lumen IPSA: mean = 7.20%, p < 0.0001, single-lumen dose point: mean = 7.19%, p < 0.0001). CONCLUSIONS: Basing on performed survey, better dose distribution parameters are obtained for patients with multi-lumen balloon applied and optimized using IPSA algorithm with individualized optimization parameters.

Surgical approach to pulmonary metastases from breast cancer.

One of the main characteristics of breast cancer is its capability to disseminate. Solitary pulmonary metastases from breast cancer occur rarely (0.4%). The aim of this study is to check whether or not the outcome following the surgical treatment of pulmonary metastases in patients with breast cancer is in accordance with the data in the literature and based on it to identify prognostic factors. We have reviewed retrospectively data for 33 patients who underwent 43 curative resections of breast cancer pulmonary metastases between 1997 and 2002 at our department. Potential prognostic factors affecting survival, namely survival after lung metastasectomy, assessed were disease-free interval (DFI), the number and location of lung metastases, the diameter in mm of metastases and the extent of pulmonary resection. The median survival for 33 patients with pulmonary breast cancer metastatic lesions after metastasectomy was 73.2 months. Mean 5-year survival was 54.5%. There was a statistically significant difference in survival time with better prognosis for patients with DFI > 36 months (p = 0.0007), complete metastasectomy (p = 0.0153), unilateral pulmonary metastases (p=0.0267) and for patients who underwent multiple operations (p = 0.0211). In multivariate analysis there was significant influence for long-term prognosis for patients with DFI > 36 months (p = 0.0446) and for complete resection of the metastases (p = 0.0275). Analysis of the survival rates for patients with solitary pulmonary metastasis, with different size of tumors and after different types of pulmonary resection showed no significant differences. It was concluded that resection of lung metastases from breast cancer may offer a significant survival benefit for selected patients. The identified prognostic factor for survival after metastasectomy is DFI longer than 36 months and complete resection of the metastases. In our group of patients, DFI longer than 36 months, unilateral pulmonary metastases and number of operations significantly influenced survival. Also, the results showed that lung metastasectomy by conventional surgery is a safe procedure with low perioperative morbidity and mortality rate.

Selected elements of socio-demographic status and lifestyle as factors determining subjective assessment of life in women after mastectomy.

AIM OF THE STUDY: The main objective of the study is to specify whether socio-demographic factors and physical activity result in differences in subjective assessment of life in women diagnosed with breast cancer. MATERIAL AND METHODS: The study group consisted of 145 women who had been diagnosed with breast cancer. The women had undergone radical surgery, chemotherapy and radiotherapy. The participants filled in an anonymous questionnaire which contained a number of detailed questions relating to their socio-demographic standing, life style, condition and the current self-assessment of life after breast cancer. In order to assess the differences between groups made on the basis of socio-economic variables, the Kruskal-Wallis rank test was used. For a comprehensive assessment of relations, multiple correspondence analysis on the basis of Burt tables was used. RESULTS: Their mean age at the time of the study was 57.1 years. The analysis of the effect of education and marital status on differences in the assessment of quality of life showed that these variables resulted in differences in the sphere related to social contacts (better educated women more often avoided social contacts) and in feeling of fatigue and exhaustion (the participants who were in a relationship indicated less fatigue and exhaustion). CONCLUSIONS: Mastectomy caused by breast cancer in women and related chemotherapy and radiotherapy negatively affect the physical and emotional condition of patients involving mental stress. Selected socio-demographic factors and elements of life style co-exist with each other, interpenetrating; thus the assessment of quality of life should comprise a set of factors and take into consideration their mutual interrelations.