Novel phthalocyaninates of terbium, erbium and lutetium, bearing 3-(ethylthio)phenyl peripheral groups, were synthesised with high yields. The complexes obtained were characterised by 1H nuclear ...magnetic resonance spectroscopy, Fourier-transform infrared spectroscopy and high-resolution mass spectrometry. Thermal stability of the lanthanide complexes was examined using thermogravimetric analysis combined with fourier-transform infrared spectroscopy. Strong upfield (up to −59.06) and downfield (up to 22.32) lanthanide-induced shifts of signals of aromatic protons were observed in nuclear magnetic resonance spectra of terbium and erbium complexes respectively. It was shown, that comparing to phenyl-substituted analogues the introduction of ethylthio-moieties in the meta-positions of phenyl substituents does not affect the Q band maxima. Hybrid gold nanoparticles coated with molecules of the lutetium complex were obtained and their optical properties were studied. The formation of phthalocyanine shell and its composition were proven using atomic force and transmission electron microscopy. Absorption cross-sections of ground and the first excited states were calculated using the data of open-aperture z-scan measurements for lutetium complex and hybrid gold nanoparticles on its basis.
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•3-(Ethylthio)phenyl-substituted phthalocyaninates of lanthanides were synthesised.•Strong up- and downfield lanthanide-induced shifts of protons were observed.•Au nanoparticles coated with molecules of lutetium phthalocyaninate were obtained.•Presence of Au particles leads to aggregation of phthalocyanines around Au core.•Absorption cross-sections of ground and first excited states were calculated.
Selective synthetic approaches to novel single- and multiple-decker terbium(III) phthalocyaninates, bearing peripheral phenyl groups, were developed. The compounds were identified by nuclear magnetic ...resonance spectroscopy, high resolution mass spectrometry, Fourier-transform infrared and UV–Vis spectroscopy. From the X-ray data for initial 1,2-dicyano-4,5-diphenylbenzene it was shown that phenyl groups are not in the same plane, and dihedral angle between them equals 64°. Strong upfield shifts of the aromatic proton signals up to −131.62 ppm in the case of a triple-decker complex were found in the nuclear magnetic resonance spectra due to paramagnetic nature of terbium(III) ion. Stronger intramolecular interactions are observed for the sandwich-type phenyl-substituted terbium complexes comparing to tert-butyl-substituted analogs, earlier described in literature. In the case of the double-decker compound, this results in 142 nm hypsochromic shift of the intervalence absorption band. DC conductivity measurements were carried out for terbium(III) phthalocyaninates. The formation of the ring-shaped self-assembled aggregates with a diameter of 400 nm was observed in thin solid films of the prepared terbium(III) compounds by atomic force microscopy.
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•Synthetic approaches to phenyl-substituted Tb phthalocyaninates were developed.•Strong upfield lanthanide-induced shifts of protons were observed.•Nano-coffee ring effect was found for Tb trisphthalocyanine using AFM technique.•Strong intramolecular interactions were observed for sandwich-type Tb complexes.•It was shown that dihedral angle between phenyl groups equals 64°.
Direct metallation of 2-hydroxyphthalocyanine J-type slipped-cofacial dimeric ligand by Mg, Zn, Cu, Ni and Co salts has been carried out to obtain corresponding metal complexes selectively without ...any noticeable dissociation or polymerization of the starting ligand. Integrated analysis of aggregation properties in the synthesized series has been conducted with the involvement of AFM microscopy, UV/Vis spectroscopy and theoretical assessment. As a result, a nonlinear relationship between absorption and concentration was found, with aggregation beginning to appear at concentrations above 3.3 × 10−5 mol L−1 with predominant formation of trimers from the dimeric molecules in THF solutions.
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•The point of deviation from Beer's law is the beginning of aggregation processes.•For phthalocyanine J-dimers, aggregation develops in a small concentration ranges.•AFM and UV/Vis investigations constitute the basis for studying the aggregation.•Structural parameters of J-dimers significantly affect the aggregation.
Improving the accuracy of cash flow forecasting in the TSA is the key to fulfilling government payment obligations, minimizing the cost of maintaining the cash reserve, providing the absence of ...outstanding debt accumulation, and ensuring investment in various financial instruments to obtain additional income. The article describes a method for improving the accuracy of forecasting a time series composed of daily budgetary fund balances in the TSA, based on its preliminary decomposition using a discrete wavelet packet transform of the Daubechies family. This makes it possible to increase the accuracy of traditional forecasting methods from 80% to more than 96%. The decomposition level varied from one to eight to minimize the mean absolute error and improve the forecasting accuracy. Calculations of statistical tests for adequacy confirm the effectiveness of the proposed method for improving forecasting accuracy. The scientific novelty of the proposed method for improving the forecasting accuracy of time series from daily budgetary fund balances in the TSA lies in proving the need for preliminary timeseries decomposition and subsequent construction of forecasts for the obtained parts, resulting in high forecasting accuracy. The result differs significantly from traditional econometric methods (ARIMA/SARIMA), characterized by a much lower accuracy (50-80%) and a decrease in forecasting accuracy with an increase in the forecast horizon. This article is novel, as it forms a new approach to solving the problem of increasing the efficiency of using budgetary funds, associated with improving the accuracy of forecasting daily budgetary fund balance in the TSA.
Improving the accuracy of cash flow forecasting in the TSA is key to fulfilling government payment obligations, minimizing the cost of maintaining the cash reserve, providing the absence of ...outstanding debt accumulation and ensuring investment in financial instruments to obtain additional income. This study aims to improve the accuracy of traditional methods of forecasting the time series compiled from the daily remaining balances in the TSAbased on prior decomposition using a discrete wavelet transform. The paper compares the influence of selecting a mother wavelet out of 570 mother wavelet functions belonging to 10 wavelet families (Haar;Dabeshies; Symlet; Coiflet; Biorthogonal Spline; Reverse Biorthogonal Spline; Meyer; Shannon; Battle-Lemarie; and Cohen–Daubechies–Feauveau) and the decomposition level (from 1 to 8) on the forecast accuracy of time series compiled from the daily remaining balances in the TSA in comparison with the traditional forecasting method without prior timeseries decomposition. The model with prior time series decomposition based on the Reverse Biorthogonal Spline Wavelet 5.5 mother wavelet function, upon the eighth iteration, features the highest accuracy, significantly higher than that of the traditional forecasting models. The choice of the mother wavelet and the decomposition level play an important role in increasing the accuracy of forecasting the daily remaining balances in the TSA.
The modifications of the microstructure of myoglobin deposited onto SERS-active Ag-based substrates by drying a drop of aqueous solution with and without laser irradiation and the corresponding ...surface-enhanced Raman scattering (SERS) spectra are studied. It is shown that drying with laser irradiation leads to the formation of protein aggregates of various types, including crystal-like aggregates. It is also shown that after such drying, the aggregates generally have SERS spectra characterized by a change in the position of the vibration bands and the ratios of their amplitudes compared to the spectra of proteins dried without additional treatment. In particular, parts of the SERS spectra of aggregates formed under laser irradiation are characterized by an additional enhancement (up to 100×) compared to the SERS spectra of myoglobin dried in air at room temperature. The crystallization processes were modeled using the results of atomic force microscopy morphology studies of dried myoglobin on the SERS-active substrates to determine the conditions under which crystal-like aggregates start to grow at surface irregularities, specifically those with a volume close to that of the critical-size nucleus, and where the lowest energy of formation occurs. A correlation is established between surface irregularities, the amplitude, and the change in the SERS spectra during the drying of a myoglobin solution sample on a nanostructured Ag-based surface.
In this study, a non-labeled sensor system for direct determining human glycated albumin levels for medical application is proposed. Using machine learning methods applied to surface-enhanced Raman ...scattering (SERS) spectra of human glycated albumin and serum human albumin enabled the avoidance of complex sample preparation. By implementing linear discriminant analysis and regularized linear regression, classification and regression problems were solved based on the spectra obtained as a result of the experiment. The results show that, coupled with data augmentation and a special cross-validation procedure, the methods we employed yield better results in the corresponding tasks in comparison with popular random forest methods and the support vector method. The results show that SERS, in combination with machine learning methods, can be a powerful and effective tool for the simple and direct assay of protein mixtures.
Surface-enhanced Raman spectroscopy (SERS) has been intensely studied as a possible solution in the fields of analytical chemistry and biosensorics for decades. Substantial research has been devoted ...to engineering signal enhanced SERS-active substrates based on semi-continuous nanostructured silver and gold films, or agglomerates of micro- and nanoparticles in solution. Herein, we demonstrate the high-amplitude spectra of myoglobin precipitated out of ultra-low concentration solutions (below 10 μg/mL) using e-beam evaporated continuous self-assembled silver films. We observe up to 105 times Raman signal amplification with purposefully designed SERS-active substrates in comparison with the control samples. SERS-active substrates are obtained by electron beam evaporation of silver thin films with well controlled nanostructured surface morphology. The characteristic dimensions of the morphology elements vary in the range from several to tens of nanometers. Using optical confocal microscopy we demonstrate that proteins form a conformation on the surface of the self-assembled silver film, which results in an effective enhancement of giant Raman scattering signal. We investigate the various SERS substrates surface morphologies by means of atomic force microscopy (AFM) in combination with deep data analysis with Gwyddion software and a number of machine learning techniques. Based on these results, we identify the most significant film surface morphology patterns and evaporation recipe parameters to obtain the highest amplitude SERS spectra. Moreover, we demonstrate the possibility of automated selection of suitable morphological parameters to obtain the high-amplitude spectra. The developed AFM data auto-analysis procedures are used for smart optimization of SERS-active substrates nanoengineering processes.
BackgroundIdentifying potential predictive biomarkers for immune related adverse events (irAEs) following checkpoint blockade inhibition (CPI) remains an outstanding goal of immune-oncology ...translational research. Polymorphism with the T cell receptor variable gene (TRBV) has been proposed as a potential risk factor for irAEs owing to a potential link between TRBV polymorphism and chronic autoimmune disease. Efforts to interrogate the potential biomarker utility of TRBV polymorphism have been hampered by the repetitive nature of the TRB locus. Our research has demonstrated a method for inferring TRB locus haplotypes from long-amplicon TCRB chain sequencing data, which we used to identify major haplotype groups in from nucleic acid. Here we present our research for a potential automated method for haplotype group assignment from TCRB chain sequencing data.MethodsRearranged TCRB chains from 10 blood samples were amplified and sequenced from 25ng peripheral blood total RNA via the Oncomine™ TCRB-LR assay using the Genexus™ Integrated Sequencer. 12 samples were run per chip with 4 samples run in each lane. TCRB clonotyping and repertoire feature analysis was performed using Genexus™ analysis software. Automated haplotype group assignment was performed by generation and comparison of TRBV allele profiles to those presented previously.1 For context, TCR evenness, convergence, and haplotype group assignment were compared to values obtained following analysis of the same samples via the GeneStudio™ S5 platform and Ion Reporter™ 5.12 software.ResultsTCR Evenness and convergence values were highly correlated across replicates run on the Genexus™ Integrated Sequencer (Spearman correlation >0.95 and >0.70, respectively). Evenness at equivalent clone count and convergence at equivalent sequencing depth were not significantly different across platforms (Spearman correlation >0.88). Haplotype group assignments demonstrated 100% agreement across replicates on both platforms.ConclusionsOur research has demonstrated a potential automated and reproducible method for TRB haplotype group assignment via the Oncomine™ TCR-Beta LR Assay, GX run on the Genexus™ Integrated Sequencer. Future studies will be needed to evaluate the potential biomarker utility of TRB haplotyping for the prediction of irAEs.For research use only not for diagnostic procedures.ReferenceLooney T, Duose D, Lowman G, Linch E, Hajjar J, Topacio-Hall D, Xu M, Zheng J, Alshawa A, Tapia C, Stephen B, Wang L, Meric-Bernstam F, Miller L, Glavin A, Lin L, Gong J, Conroy J, Morrison C, Hyland F, Naing A. Haplotype Analysis of the T-Cell Receptor Beta (TCRB) Locus by Long-amplicon TCRB Repertoire Sequencing. J Immunother Precis Oncol 2019;2:137–143.
Department of Physiology, Stritch School of Medicine, Loyola University Chicago, Maywood, Illinois
Submitted 12 December 2005
; accepted in final form 18 May 2006
Decoding of fast cytosolic Ca 2+ ...concentration (Ca 2+ i ) transients by mitochondria was studied in permeabilized cat ventricular myocytes. Mitochondrial Ca 2+ (Ca 2+ m ) was measured with fluo-3 trapped inside mitochondria after removal of cytosolic indicator by plasma membrane permeabilization with digitonin. Elevation of extramitochondrial Ca 2+ (Ca 2+ em ) to >0.5 µM resulted in a Ca 2+ em -dependent increase in the rate of mitochondrial Ca 2+ accumulation (Ca 2+ em resulting in half-maximal rate of Ca 2+ accumulation = 4.4 µM) via Ca 2+ uniporter. Ca 2+ uptake was sensitive to the Ca 2+ uniporter blocker ruthenium red and the protonophore carbonyl cyanide p -trifluoromethoxyphenylhydrazone and depended on inorganic phosphate concentration. The rates of Ca 2+ m increase and recovery were dependent on the extramitochondrial Na + (Na + em ) due to Ca 2+ extrusion via mitochondrial Na + /Ca 2+ exchanger. The maximal rate of Ca 2+ extrusion was observed with Na + em in the range of 2040 mM. Rapid switching (0.251 Hz) of Ca 2+ em between 0 and 100 µM simulated rapid beat-to-beat changes in Ca 2+ i (with Ca 2+ i transient duration of 100500 ms). No Ca 2+ m oscillations were observed, either under conditions of maximal rate of Ca 2+ uptake (100 µM Ca 2+ em , 0 Na + em ) or with maximal rate of Ca 2+ removal (0 Ca 2+ em , 40 mM Na + em ). The slow frequency-dependent increase of Ca 2+ m argues against a rapid transmission of Ca 2+ signals between cytosol and mitochondria on a beat-to-beat basis in the heart. Ca 2+ m changes elicited by continuous or pulsatile exposure to elevated Ca 2+ em showed no difference in mitochondrial Ca 2+ uptake. Thus in cardiac myocytes fast Ca 2+ i transients are integrated by mitochondrial Ca 2+ transport systems, resulting in a frequency-dependent net mitochondrial Ca 2+ accumulation.
mitochondrial Ca 2+ ; excitation-contraction coupling; cardiomyocytes
Address for reprint requests and other correspondence: L. A. Blatter, Dept. of Physiology, Loyola Univ. Chicago, 2160 S. First Ave., Maywood, IL 60153 (e-mail: lblatte{at}lumc.edu )
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