МЕТОДЫ ПОСТРОЕНИЯ ОБУЧАЮЩЕГО НАБОРА ДЛЯ КАЛИБРОВКИ С ПОМОЩЬЮ ФЛУОРЕСЦЕНТНОЙ СПЕКТРОСКОПИИ НЕБОЛЬШИХ ВЫБОРОК ОБРАЗЦОВ

A limited number of samples and an impossible a priori control of a desired parameter value stipulate how it is important to solve the problem of selecting a training set for calibration by the multivariate spectral analysis in order to reduce a calibration error. Possible variants of a training subset selection from small data sets are shown for temperature calibration with fluorescence spectra of Yb3+:CaF2 recorded in the range of 880–1120 nm with a resolution of about 0.2 nm for the temperature range from 66 to 150 °C and at a step of 2 °C. The methods applied are the uniform distribution, the Kennard and Stone algorithm and the cluster analysis in principal component space. The effect of the method choice on the calibration accuracy has been evaluated. The application of the principal component analysis gives the possibility to select spectra without a priori knowledge of a temperature, to which the fluorescence spectra correspond. The root-mean-square error of the predicted temperature value is shown to be 3.98 ° C for the uniform distribution of the training subset samples over the space of the first principal component and 1.07 ° C for the Kennard and Stone algorithm. The minimum root-mean-square prediction error of 0.98 °C is shown to be achieved with the training subset selection by the hierarchical cluster analysis in the space of the principal components of the spectra studied.При проведении калибровки с помощью многопараметрического спектрального анализа ограниченность количества образцов и невозможность априорного контроля величины искомого параметра обусловливают важность решения задачи построения обучающего набора с целью уменьшения ошибки калибровки. На примере калибровки температуры с помощью проекции на латентные структуры в диапазоне от 66 до 150 °C по спектрам флуоресценции Yb3+:CaF2 , зарегистрированным в диапазоне 880–1120 нм с разрешением около 0,2 нм и шагом по температуре 2 °C, продемонстрированы возможные варианты построения обучающего набора из небольших по количеству образцов выборок с применением равномерного распределения, алгоритма Кеннарда – Стоуна и методов кластерного анализа в пространстве главных компонент, показано их влияние на точность калибровки. Применение метода главных компонент позволяет проводить отбор спектров без привлечения априорных знаний о температуре, которой соответствуют спектры флуоресценции. Показано, что среднеквадратичная ошибка предсказанной величины температуры при равномерном распределении образцов обучающего набора по пространству первой главной компоненты составляет 3,98 °C, при использовании алгоритма Кеннарда – Стоуна – 1,07 °C. Минимальная среднеквадратичная ошибка 0,98 °C может быть достигнута с помощью иерархического кластерного анализа пространства главных компонент исследуемых спектров.

Применение многопараметрического анализа широкополосных спектров пропускания для калибровки физико-химических показателей вин

The use of multivariate processing of spectral information has recently been favored due to the express nature of this method, the ease of use of mathematical packages, and the lack of the need to add chemical reagents. The aim of the work is using the methods of multivariate analysis of broadband transmission spectra to calibrate the physicochemical parameters of wines and to improve the accuracy of this calibration by selecting spectral variables.Using the interval projection to latent structures of the transmission spectra in the range of 220– 2500 nm, the physicochemical characteristics of the varietal unblended Moldovan wine are calibrated. Interval methods of multivariate data analysis allow signifi reducing the root mean square calibration error in comparison with the broadband multivariate methods. Residual predictive deviations exceed the threshold value of 2.5 for K, Ca, Mg, oxalic, malic and succinic acids, 2,3-butylene glycol, ash and phenolic compounds for red wines and Mg, tartaric, citric and lactic acids, 2,3-butylene glycol, ash, phenolic compounds and soluble salts for white wines. These values demonstrate good calibration quality.The application of the proposed method for calibrating the physicochemical parameters of wines makes it possible to replace traditional methods with spectral measurements, which are available not only in laboratory but also in the fi and characterized by small values of the root mean square error of calibration.Использованию многопараметрической обработки спектральной информации в последнее время отдается предпочтение в связи с экспрессным характером этого метода, простотой применения математических пакетов, отсутствием необходимости введения дополнительных реагентов. Целью работы являлось применение методов многопараметрического анализа широкополосных спектров пропускания для калибровки физико-химических показателей вин и повышение точности этой калибровки с помощью выбора спектральных переменных.На примере некупажированных сортовых молдавских вин показано, что применение метода интервальной проекции на латентные структуры по комбинации движущихся окон в спектрах пропускания вин в диапазоне 220–2500 нм позволяет существенно уменьшить среднеквадратичную ошибку калибровки по сравнению с широкополосными многопараметрическими методами. Величины остаточного отклонения предсказания, превышающие пороговое значение 2,5 для содержания K, Ca, Mg, щавелевой, яблочной и янтарной кислот, 2,3-бутиленгликоля, золы и фенольных соединений для красных вин и Mg, винной, лимонной и молочной кислот, 2,3-бутиленгликоля, золы, фенольных соединений и растворимых солей для белых вин, демонстрируют хорошее качество калибровки.Применение предложенного метода калибровки физико-химических параметров вин позволяет заменить традиционные методы на проведение спектральных измерений, доступное не только в лабораторных, но и в полевых условиях, и характеризующееся малыми величинами среднеквадратичной ошибки калибровки

Biological Effect of Continuous, Quasi-Continuous and Pulsed Laser Radiation

In this work, for the first time, comparative studies of biological activity of low intensity continuous, quasi-continuous and pulsed laser radiation of nano- and picosecond time ranges with the same average power density are carried out. It is shown, that, despite the significant differences in peak values of intensity of acting factor, both continuous and quasi-continuous radiation and radiation of nano- and picosecond ranges are able to have both stimulating and inhibiting effects on all investigated parameters of functional activity of biological systems in a certain range of dose rates. The ability of laser radiation of near infra-red spectral region (800 - 1340 nm) located out the absorption bands of main chromophores of cells to have regulatory effect on biochemical processes that control the hatching of branchiopod crustaceans Artemia salina L. upon irradiation of their cysts is revealed. The role of molecular oxygen and water as acceptors of laser radiation is discussed. Keywords: Low intensity laser radiation, Laser activation, Biological activity, Zooplankton Artemia salina L., Sturgeon sperm

ИСПОЛЬЗОВАНИЕ МЕТОДОВ СПЕКТРОСКОПИИ УФ-, ВИДИМОГО И БЛИЖНЕГО ИК-ДИАПАЗОНОВ ДЛЯ ОПРЕДЕЛЕНИЯ ОРИГИНАЛЬНОСТИ ВЫДЕРЖАННЫХ ВИННЫХ ДИСТИЛЛЯТОВ

Ultraviolet, visible and near infra-red spectroscopy is used for identification of the authenticity of matured wine distillates. The use of principal component analysis, the discriminant analysis, the classification trees and projection latent structures to broad-band transmission spectra of wine distillates allowed determining manufacturer and aging of wine distillates.Спектроскопия УФ-, видимого и ближнего ИК-диапазонов применена для определения оригинальности выдержанных винных дистиллятов. Использование метода главных компонент, дискриминантного анализа, построения деревьев классификации и регрессии на латентные структуры к широкополосным спектрам пропускания винных дистиллятов позволило определить производителя и возраст выдержки объектов исследования

Nanostructured Silver Substrates With Stable and Universal SERS Properties: Application to Organic Molecules and Semiconductor Nanoparticles

Nanostructured silver films have been prepared by thermal deposition on silicon, and their properties as SERS substrates investigated. The optimal conditions of the post-growth annealing of the substrates were established. Atomic force microscopy study revealed that the silver films with relatively dense and homogeneous arrays of 60–80-nm high pyramidal nanoislands are the most efficient for SERS of both organic dye and inorganic nanoparticles analytes. The noticeable enhancement of the Raman signal from colloidal nanoparticles with the help of silver island films is reported for the first time

ПРИМЕНЕНИЕ МНОГОПАРАМЕТРИЧЕСКОГО АНАЛИЗА ШИРОКОПОЛОСНЫХ СПЕКТРОВ ПРОПУСКАНИЯ ДЛЯ ИДЕНТИФИКАЦИИ ВИН С ГЕОГРАФИЧЕСКИМ НАИМЕНОВАНИЕМ ПРОИСХОЖДЕНИЯ

The simulation is carried out of physical and chemical characteristics of the unblended varietal young Moldovan wine harvested in 2014 by the projection to latent structures of the transmission spectra in the range of 220–2500 nm. The achieved accuracy of the regression determining the parameters is appropriate for practical application purposes (from 5 % for alcohol strength to 30 % for tartaric acid content in red wines). The possibility is shown of solving the problem of verification of the protected geographical indication of wines (IGP – Indication Géographique Protégée) by the multivariate analysis of broadband transmission spectra. Проведено моделирование физико-химических характеристик молодых некупажированных сортовых молдавских вин урожая 2014 г. с помощью проекции на латентные структуры спектров пропускания в диапазоне 220–2500 нм. Достигнутая погрешность регрессионного определения параметров является приемлемой для целей практического применения (от 5 % для спиртуозности до 30 % для содержания винной кислоты в красных винах). Показана возможность решения задачи подтверждения общности географического наименования вин (IGP – Indication Géographique Protégée) с помощью проведения многопараметрического анализа широкополосных спектров пропускания

Application of Multivariate Analysis of Broadband Transmission Spectra for Calibration of Physico-Chemical Parameters of Wines

The use of multivariate processing of spectral information has recently been favored due to the express nature of this method, the ease of use of mathematical packages, and the lack of the need to add chemical reagents. The aim of the work is using the methods of multivariate analysis of broadband transmission spectra to calibrate the physicochemical parameters of wines and to improve the accuracy of this calibration by selecting spectral variables.Using the interval projection to latent structures of the transmission spectra in the range of 220– 2500 nm, the physicochemical characteristics of the varietal unblended Moldovan wine are calibrated. Interval methods of multivariate data analysis allow signifi reducing the root mean square calibration error in comparison with the broadband multivariate methods. Residual predictive deviations exceed the threshold value of 2.5 for K, Ca, Mg, oxalic, malic and succinic acids, 2,3-butylene glycol, ash and phenolic compounds for red wines and Mg, tartaric, citric and lactic acids, 2,3-butylene glycol, ash, phenolic compounds and soluble salts for white wines. These values demonstrate good calibration quality.The application of the proposed method for calibrating the physicochemical parameters of wines makes it possible to replace traditional methods with spectral measurements, which are available not only in laboratory but also in the fi and characterized by small values of the root mean square error of calibration

THE ROLE OF CHRONIC POLYPOID RHINOSINUSITIS IN OCCURRENCE OF MALIGNANT EPITHELIAL TUMORS OF THE PARANASAL SINUSES AND THE NASAL CAVITY

Growth of occurrence of malignant epithelial tumors of the nasal cavity (NC) and the paranasal sinuses (PNS) is noted. Absolute majority of patients come for treatment with the III and the IV stage of the disease. No trend for decreasing of the untreatedness parameter is observed. Increasing of the efficiency of treatment of patients with cancer depends on timely diagnostics. The main reason of late diagnostics is insufficient oncological alertness of doctors in polyclinics. The issues of therapy tactics at the stage of pre-tumor diseases of the NC and the PNS remain unsolved, while background process that precede development of cancer are morphologically revealed with 56.7 % of patients. One of the most frequently occurred background development processes of the NC and the PNS cancer is chronic polypoid rhinosinusitis (CPR). The degree of occurrence of CPR is high, and the annual growth of its incidence by 2 to 4 % has been observed for the previous 10 years. There are only certain works that view CPR as a pre-cancer disease.The objective of the study is improvement of results of early diagnostics of cancer and optimization of the surgical tactics with pre-cancer diseases of the upper jaw and the PNS.Materials and methods. Retrospective and prospective clinical and morphological analysis of data of 58 patients with benign polypous changes (BPC) and of 182 patients with malignant epithelial tumors (MET)  of the NC and the PNS treated at the Arkhangelsk Regional Clinical Oncology Dispensary from 1980 to 2010 has been performed.Results and discussion The maximum number of patients in both groups is at the age category from 40 to 59 years. Besides, the average age of patients with the BPC was lower than that of the patients with the MET (45.6 ± 2.3 and 54.0 ± 1.5 years old, respectively).Patients of working age prevailed both in the group with the BPC and the group with the MET of the NC and the PNS (19.0 / 81.0 % and 39.6 / 62.1 %, respectively). Males prevailed in the group with the BPC (53.4 % of males and 46.6 % of females), and females prevailed in the group with the MET (39.6 % of males and 60.4 % of females). However, we believe that this controversy to our hypothesis is explained with greater life expectancy of females (females are the prevailing majority in the groups of age category of 70 to 89 years old: 19.8 % are females, 5.3 % are males).The prevailing number of patients with the BPC (77.6 %) lived in cities, and such number in the group of patients with the MET was 54.9 %. The most frequent type of operative treatment of patients with the BPC was electrical maxillar ethmoidectomy that was performed in 82.9 % of cases. Relapse after performance of electrical maxillar ethmoidectomy was demostrated by 2 patients which comprised 4.3 %.In significant number of cases (70,6 % in the group with the BPC and 65.9 % in the group with the MET), the pathological process was localized in the maxillar cavity. Most frequently, glandular-fibrous polyps were revealed (42.1 %), and this morphological structure prevaled with male patients (57.9 % with males and 26.3 % with females); MET of the NC and the PNS, in their turn, also more frequently occurred with males.In 69.0 %, the CPR has been the background for severe epithelial dysplasia, and the CPR, in its turn, was reveled with 39.8 % of patients with the MET.Conclusion. We believe that the data provided prove the key role of the CPR in development of MET of the NC and the PNS