Papers by Halina Abramczyk
This paper presents a non-invasive approach to study redox status of cytochromes in vitro human b... more This paper presents a non-invasive approach to study redox status of cytochromes in vitro human brain cells of normal astrocytes (NHA), astrocytoma (CRL-1718), glioblastoma (U87- MG) and medulloblastoma (Daoy), and human breast cells of normal cells (MCF10A), slightly malignant cells (MCF7) and highly aggressive cells (MDA-MB-231), in vivo animal models, and ex vivo brain and breast tissues surgically resected human specimens by means of Raman microspectroscopy at 355 nm, 532 nm, 785 nm and endospectroscopic Raman probe at 785 nm. Here we show that the amount of reduced cytochrome becomes abnormally high in human brain tumors and breast cancers. In contrast, the amount of reduced cytochrome c is lower in cancer cells when compared to the normal one at in vitro conditions when the effect of microenvironment is eliminated. Mitochondrial dysfunction and alterations in the chemical composition of the nucleus, mitochondria, lipid droplets, cytoplasm in single cells have been detected by ...
Molecules, 2020
Photodynamic therapy is a clinically approved alternative method for cancer treatment in which a ... more Photodynamic therapy is a clinically approved alternative method for cancer treatment in which a combination of nontoxic drugs known as photosensitizers and oxygen is used. Despite intensive investigations and encouraging results, zinc phthalocyanines (ZnPcs) have not yet been approved as photosensitizers for clinical use. Label-free Raman imaging of nonfixed and unstained normal and cancerous colon human tissues and normal human CCD18-Co and cancerous CaCo-2 cell lines, without and after adding ZnPcS4 photosensitizer, was analyzed. The biochemical composition of normal and cancerous colon tissues and colon cells without and after adding ZnPcS4 at the subcellular level was determined. Analyzing the fluorescence/Raman signals of ZnPcS4, we found that in normal human colon tissue samples, in contrast to cancerous ones, there is a lower affinity to ZnPcS4 phthalocyanine. Moreover, a higher concentration in cancerous tissue was concomitant with a blue shift of the maximum peak position ...
Cancers, 2019
(1) Background: Novel methods are required for analysing post-translational modifications of prot... more (1) Background: Novel methods are required for analysing post-translational modifications of protein phosphorylation by visualizing biochemical landscapes of proteins in human normal and cancerous tissues and cells. (2) Methods: A label-free Raman method is presented for detecting spectral changes that arise in proteins due to phosphorylation in the tissue of human breasts, small intestines, and brain tumours, as well as in the normal human astrocytes and primary glioblastoma U-87 MG cell lines. Raman spectroscopy and Raman imaging are effective tools for monitoring and analysing the vibrations of functional groups involved in aberrant phosphorylation in cancer without any phosphorecognition of tag molecules. (3) Results: Our results based on 35 fresh human cancer and normal tissues prove that the aberrant tyrosine phosphorylation monitored by the unique spectral signatures of Raman vibrations is a universal characteristic in the metabolic regulation in different types of cancers. Overexpressed tyrosine phosphorylation in the human breast, small intestine and brain tissues and in the human primary glioblastoma U-87 MG cell line was monitored by using Raman biomarkers. (4) We showed that the bands at 1586 cm −1 and 829 cm −1 , corresponding to phosphorylated tyrosine, play a pivotal role as a Raman biomarker of the phosphorylation status in aggressive cancers. We found that the best Raman biomarker of phosphorylation is the 1586/829 ratio showing the statistical significance at p Values of ≤ 0.05. (5) Conclusions: Raman spectroscopy and imaging have the potential to be used as screening functional assays to detect phosphorylated target proteins and will help researchers to understand the role of phosphorylation in cellular processes and cancer progression. The abnormal and excessive high level of tyrosine phosphorylation in cancer samples compared with normal samples was found in the cancerous human tissue of breasts, small intestines and brain tumours, as well as in the mitochondria and lipid droplets of the glioblastoma U-87 MG cell line. Detailed insights are presented into the intracellular oncogenic metabolic pathways mediated by phosphorylated tyrosine.
International Journal of Molecular Sciences, 2019
Noninvasive Raman imaging of non-fixed and unstained human colon tissues based on vibrational pro... more Noninvasive Raman imaging of non-fixed and unstained human colon tissues based on vibrational properties of noncancerous and cancerous samples can effectively enable the differentiation between noncancerous and tumor tissues. This work aimed to evaluate the biochemical characteristics of colon cancer and the clinical merits of multivariate Raman image and spectroscopy analysis. Tissue samples were collected during routine surgery. The non-fixed, fresh samples were used to prepare micrometer sections from the tumor mass and the tissue from the safety margins outside of the tumor mass. Adjacent sections were used for typical histological analysis. We have found that the chemical composition identified by Raman spectroscopy of the cancerous and the noncancerous colon samples is sufficiently different to distinguish pathologically changed tissue from noncancerous tissue. We present a detailed analysis of Raman spectra for the human noncancerous and cancerous colon tissue. The multivaria...
Analytical Methods, 2016
Raman imaging can ‘upgrade’ cancer epigenetic tests and answer many questions by monitoring the b... more Raman imaging can ‘upgrade’ cancer epigenetic tests and answer many questions by monitoring the biochemistry of cancer cells.
Journal of Photochemistry and Photobiology A: Chemistry, 2017
Zinc tetrasulfonated phthalocyanine (ZnPcS 4), was studied in aqueous solutions, films and at the... more Zinc tetrasulfonated phthalocyanine (ZnPcS 4), was studied in aqueous solutions, films and at the biological interfaces of noncancerous and cancerous human breast tissues by using steady state and time resolved spectroscopy methods, including IR, Raman, UV vis, fluorescence and transient absorption femtosecond pump probe spectroscopy. The pump probe transient absorption spectra were recorded on time scales from femtoseconds to nanoseconds providing insight into the molecular mechanisms of energy dissipation and primary events occurring in solution, film, and at the interface of the biological tissues. The nature of the rapid processes and competing relaxation pathways resulting from the initially excited electronic states of ZnPcS 4 in aqueous solutions, films and at the biological interfaces of cancerous and noncancerous human breast tissues was studied. The results provide evidence that the sulfonated zinc phthalocyanine dissipates energy through different pathways in the environment of the noncancerous tissue and of the cancerous tissue. A detailed understanding of the paths of energy dissipation will reveal the mechanisms underlying light induced signal transduction and the role of photoreceptors in photostability of living cells. Here, we showed that both the dynamics of the ground state S 0 recovery and the dynamics of the first excited state S 1 decay at the interfacial regions of the noncancerous tissue is markedly faster than that in the cancerous tissue, suggesting that the molecular mechanisms responsible for harvesting the light energy in photosensitizers can be used for practical applications in cancer diagnostics. The paper bridges the fundamentals of cancer research with the femtosecond technologies of high temporal resolution for studying dynamics of photosensitizers in noncancerous and cancerous human breast tissues.
The Journal of Physical Chemistry, 1991
The absorption spectra of solvated electrons in ammonia, methylamine, and trimethylamine are calc... more The absorption spectra of solvated electrons in ammonia, methylamine, and trimethylamine are calculated in terms of the theory presented in our previous paper' and compared with the experimental data. The theory reproduces very well the experimental absorption spectra, their bandwidths, and the band shapes with the characteristic asymmetric tail on the high-frequency side. The role of the H bond in stabilization and spectroscopic properties of the solvated electron in amines are discussed.
The Journal of Physical Chemistry, 1991
Optical absorption band-shape theory of the solvated electron in condensed media is presented. Th... more Optical absorption band-shape theory of the solvated electron in condensed media is presented. The solvated electron motion occurs in the Born-oppenheimer energy potential well and is coupled to the intramolecular vibrational modes of the solvent. Both the energy potential well and the anharmonic coupling are randomly modulated with time. The time evolution of the anharmonic coupling constant is governed by the resonance energy exchange between the vibrational mode and the bath. The fluctuations of the energy potential arising from the direct coupling to the bath obey the stochastic Liouville equation.
Vibrational Spectroscopy, 1993
A comparison was made between the theories of IR absorption in hydrogen-bonded complexes and near... more A comparison was made between the theories of IR absorption in hydrogen-bonded complexes and near-IR and visible absorption of an excess electron in hydrogen-bonded solvents. The near-IR and visible absorption spectra of excess electrons in water, alcohols, amines and alkanes were calculated in terms of electron-vibron coupling. The role of the hydrogen bond on electron stabilization and solvation is discussed.
Journal of Biophysical Chemistry, 2011
The paper presents the results for water confined in a human breast cancerous tissue, a single st... more The paper presents the results for water confined in a human breast cancerous tissue, a single stranded DNA, a double stranded DNA and in phospholipids (DPPC-D--Phosphatidylcholine, dipalmitoyl). The interfacial water in DNA and lipids is represented by a double band in the region of the OH stretching mode of water corresponding to the symmetric and asymmetric vibrational modes, in contrast to water confined in the cancerous breast tissue where only one band at 3311 cm-1 has been recorded. The marked red-shift of the maximum peak position of the OH stretching mode confirms that the vibrational properties of the interfacial water observed in restricted biological environment differ drastically from those in bulk water. The change of vibrational pattern of behavior may be due to the decoupling of the vibrations of the OH bonds in water molecule or change of the vibrational selection rules at biological interfaces. According to our knowledge Raman vibrational properties of water confined in the normal and cancerous breast tissue of the same patient have not been reported in literature yet. Here we have also presented the first Raman 'optical biopsy' images of the non-cancerous and cancerous (infiltrating ductal cancer) human breast tissues.
The Analyst, 2014
Raman microspectroscopy and confocal Raman imaging combined with confocal fluorescence were used ... more Raman microspectroscopy and confocal Raman imaging combined with confocal fluorescence were used to study the distribution and aggregation of aluminum tetrasulfonated phthalocyanine (AlPcS4) in breast tissues.
The Journal of Physical Chemistry A, 2006
Ultrafast time-resolved electronic spectra of the primary events induced in the copper tetrasulfo... more Ultrafast time-resolved electronic spectra of the primary events induced in the copper tetrasulfonated phthalocyanine Cu(tsPc) 4-) in aqueous solution has been measured by femtosecond pump-probe transient absorption spectroscopy. The primary events initiated by the absorption of a photon occurring within the femtosecond time scale are discussed on the basis of the electron transfer mechanism between the adjacent phthalocyanine rings proposed recently in our laboratory. The femtosecond transient absorption results are compared with the low temperature emission spectra obtained with Raman spectroscopy and the voltammetric curves.
The Journal of Physical Chemistry A, 2012
A promising material in medicine, electronics, optoelectronics, electrochemistry, catalysis, and ... more A promising material in medicine, electronics, optoelectronics, electrochemistry, catalysis, and photophysics, tetrasulphonated aluminum phthalocyanine (AlPcS 4), is investigated by means of steady state and time resolved pump−probe spectroscopies. Absorption and steady state fluorescence spectroscopy indicate that AlPcS 4 is essentially monomeric. Spectrally resolved pump−probe data are recorded on time scales ranging from femtoseconds to nanoseconds. The nature of these fast processes and pathways of the competing relaxation processes from the initially excited electronic states in aqueous and organic (dimethyl sulfoxide) solutions are discussed. The decays and bleaching recovery have been fitted in the ultrafast window (0−10 ps) and later time window extending to nanoseconds (0−1 ns). While the excited state dynamics have been found to be sensitive to the solvent environment, we were able to show that the fast dynamics is described by three time constants in the ranges of 115−500 fs, 2−25 ps, and 150−5 0 0p s .W ew e r ea b l et oa s c r i b e t h e s et h r e e t i m e c o n s t a n t st od i fferent processes. The shortest time constants have been assigned to vibrational wavepacket dynamics. The few picosecond components have been assigned to vibrational relaxation in the excited electronic states. Finally, the 150−500pscomponentsrepresent thedecay from S 1 to the ground state. The experimental and theoretical treatment proposed in this paper provides a basis for a substantial revision of the commonly accepted interpretation of the Soret transition (B transition) that exists in the literature.
The Journal of Physical Chemistry A, 1998
Raman spectra of the ν S (CtC) stretching mode of phenylacetylene (PA) dissolved in acetonitrile ... more Raman spectra of the ν S (CtC) stretching mode of phenylacetylene (PA) dissolved in acetonitrile and methylcyclohexane have been recorded at 77 K and compared with spectra in the liquid solutions at room temperature [Kołodziejski, M.
The Journal of Physical Chemistry A, 2004
Photochemical and photophysical behavior of copper(II) phthalocyanine-3,4′,4′′,4′′′-tetrasulfonat... more Photochemical and photophysical behavior of copper(II) phthalocyanine-3,4′,4′′,4′′′-tetrasulfonate anion Cu(tsPc) 4irradiated with the visible light from the range 465-514 nm (vis) has been studied by resonance Raman spectroscopy. The photochemistry of monomers and dimers of Cu(tsPc) 4has been studied in liquid solutions of H 2 O and dimethyl sulfoxide (DMSO) as well as in crystal and glassy frozen matrixes as a function of temperature in the range 293-77 K. We have identified the transient species of the photoredox dissociation as ligand radicals Cu II (tsPc •) 3and Cu II (tsPc •) 5-. We have shown that the photoinduced dissociation with the electron transfer between the molecules of phthalocyanine is determined mainly by the molecular structure. The electron transfer that leads to the generation of the ligand-centered radicals may occur only for the ringstacked structures with strong overlapping between the π-electronic clouds of the macrocycle rings of the adjacent molecules. These structures exist in highly concentrated aqueous solutions and in the crystal phases. The photoinduced electron transfer does not occur for the monomers of Cu(tsPc) 4in DMSO solution and in the glassy phases. We have assigned the emission at 527 nm for Cu(tsPc) 4in DMSO and at 556 nm in H 2 O to the T n f T 1 fluorescence. Competitively, the higher excited triplet state T n state (or the first excited singlet state S 1) participates in photoinduced redox dissociation Cu(tsPc) 4-hν f Cu II (tsPc •) 3-+ Cu II (tsPc •) 5-. The vis irradiation of the Cu II (tsPc •) 3and Cu II (tsPc •) 5radicals excites them to the lowest lying excited states that emit fluorescence at 682 nm after undergoing to the ground states.
Pure and Applied Chemistry, 2004
The role played by the peripheral substituent and the solvent on the aggregation and photochemica... more The role played by the peripheral substituent and the solvent on the aggregation and photochemical properties of copper(II) phthalocyanine and copper(II)phthalocyanine-3,4',4'',4'''-tetrasulfonic anion [Cu(tsPc)-4] in aqueous solution has been studied by resonance Raman spectroscopy (RRS). The vibrational mode ν4 (1530 cm-1) and the symmetric and antisymmetric stretching modes of water have been used as a probe of interactions and aggregation in resonance Raman measurements. It has been shown that the Cu(tsPc)-4 molecules have a tremendous influence on water properties in solutions. In contrast, the influence of water on the Cu(tsPc)-4 properties appears to be weak.
Molecular Cancer, 2013
Background One of the most important areas of Raman medical diagnostics is identification and cha... more Background One of the most important areas of Raman medical diagnostics is identification and characterization of cancerous and noncancerous tissues. The methods based on Raman scattering has shown significant potential for probing human breast tissue to provide valuable information for early diagnosis of breast cancer. A vibrational fingerprint from the biological tissue provides information which can be used to identify, characterize and discriminate structures in breast tissue, both in the normal and cancerous environment. Results The paper reviews recent progress in understanding structure and interactions at biological interfaces of the human tissue by using confocal Raman imaging and IR spectroscopy. The important differences between the noncancerous and cancerous human breast tissues were found in regions characteristic for vibrations of carotenoids, fatty acids, proteins, and interfacial water. Particular attention was paid to the role played by unsaturated fatty acids and t...
Journal of Molecular Structure, 2005
The aggregation and photochemistry of the copper (II) 3, 4 00 , 4 00 , 4 000-tetrasulfonated phth... more The aggregation and photochemistry of the copper (II) 3, 4 00 , 4 00 , 4 000-tetrasulfonated phthalocyanine, free base phthalocyanine and copper (II) phthalocyanine have been studied by UV-VIS absorption spectroscopy and resonance Raman spectroscopy (RRS). The vibrational mode n 3 of (Cu(tsPc) 4K has been used as a probe in RRS measurements. The photochemistry of monomers and dimers of (Cu(tsPc) 4K has been studied in liquid solutions of H 2 O and DMSO as well as in frozen matrices. Low temperature Raman measurements in a broad temperature range have been carried out for free base phthalocyanine and copper (II) phthalocyanine in DMSO to identify the nature of emissive bands observed in the Raman spectra. It has been shown that the dimerization equilibrium constant K for tetrasulfonated phthalocyanine Cu(tsPc) 4K is strongly shifted towards monomeric form in DMSO solutions and in human blood compared to aqueous systems. The emission band at around 682 nm in DMSO and aqueous solutions observed at 77 K for tetrasulfonated salt of copper(II) phthalocyanine in concentrated solutions has been assigned to the radical transient species generated during the photoinduced dissociation with the electron transfer between the molecules of phthalocyanines. The emission at 527 nm in DMSO and at 556 nm in water has been preliminarily assigned to the fluorescence from the higher excited triplet state T n /T 1 .
Journal of Molecular Liquids, 2005
Raman spectra of the m s (uC-H) and m s (CuC) stretching modes as well as Raman spectra in the la... more Raman spectra of the m s (uC-H) and m s (CuC) stretching modes as well as Raman spectra in the lattice region 15-200 cm À1 of phenylacetylene (PA) dissolved in benzene in homogeneous liquid solutions, undercooled liquid state, crystal, and glassy matrices as a function of concentration, temperature, and quenching rate have been recorded in the temperature range of 77-293 K. The optical measurements were complemented by the differential scanning calorimetry (DSC) measurements. One has been demonstrated that the Raman spectroscopy combined with the DSC method is a powerful tool to obtain information about the nature of phase transitions at the molecular level. The results reveal some dramatic changes with concentration, temperature, and quenching rate and are of potential relevance both to fundamental condensed phase modelling and to liquid crystal technology. We have discussed the origin of a vibrational substructure observed for the stretching modes of phenylacetylene in benzene. We have found that the components of the vibrational structure correspond to stable, equilibrium crystal phase, and two non-equilibrium glassy crystal phases. Low temperature polymorphism of phenylacetylene-benzene mixtures in a broad temperature range of 77-293 K has been characterized. We have found that the low temperature polymorphism of phenylacetylene strongly depends on concentration, temperature, and quenching rate. We hope this paper is an important step in understanding mechanisms of nucleation and irreversible phase transitions.
The Journal of Chemical Physics, 2001
We present the result of Raman studies on vibrational dynamics and static properties of the CH2 r... more We present the result of Raman studies on vibrational dynamics and static properties of the CH2 rocking mode of methylcyclohexane as a function of temperature and cooling rate. We have found that vibrational dynamics as well as the static properties are very sensitive indicators to specify phases and phase transitions at the molecular level. It was found that methylcyclohexane in the undercooled liquid phase may form distinct thermodynamic states that strongly depend on the quenching rate. We have identified the characteristic temperature T* that is quenching rate dependent which is the no-return-point between crystallization and amorphization. Below this temperature the undercooled methylcyclohexane exists in either the liquid state that is out of equilibrium and represents nonergodic behavior that leads to glass forming or in the metastable equilibrium ergodic state that leads to crystallization.
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Papers by Halina Abramczyk