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Despite invaluable advances in cervical cancer therapy, treatment regimens for recurrent or persistent cancers and low-toxicity alternative treatment options are scarce. In recent years, substances classified as adaptogens have been identified as promising drug sources for preventing and treating cancer-based diseases on their ability to attack multiple molecular targets. This paper establishes the effectiveness of inhibition of the neoplastic process by a withaferin A (WFA), an adaptogenic substance, based on an in vitro model of cervical cancer. This study explores for the first time the potential of high-definition vibrational spectroscopy methods, i.e. Fourier-transform infrared (FT-IR) and Raman spectroscopic (RS) imaging at the single-cell level to evaluate the efficacy of the adaptogenic drug. HeLa cervical cancer cells were incubated with various concentrations of WFA at different incubation times. The multimodal spectroscopic approach combined with partial least squares (PLS) regression allowed the identification of molecular changes (e.g., lipids, protein secondary structures, or nucleic acids) induced by WFA at the cellular level. The results clearly illustrate the enormous potential of WFA in inhibiting the proliferation of cervical cancer cells. WFA inhibited the growth of the studied cancer cell line in a dose-dependent manner. Such studies provide comprehensive information on the sensitivity of cells to adaptogenic drugs. This is a fundamental step towards determining the rate and nature of adaptogen-induced changes in cancer cells.

The electronic structure of transition-metal oxides is a key component responsible for material's optical and chemical properties. Specifically for metal-oxide structures, the crystal-field interaction determines the shape, strength, and occupancy of electronic orbitals. Consequently, the crystal-field splitting and resulting unoccupied state populations can be foreseen as modeling factors of the photochemical activity. Herein, we study the formation of crystal-field effects during thermal oxidation of titanium in an ambient atmosphere and range of temperatures. The X-ray absorption spectroscopy is employed for quantitative analysis of average t2g-eg crystal-field splitting (Δoct) and relative t2g/eg bands occupancy. The obtained result shows that Δoct changes as a function of temperature from 1.97 eV for a passive oxide layer created on a Ti metal surface at room temperature to 2.41 eV at 600 °C when the material changes into the TiO2 rutile phase. On the basis of XAS data analysis, we show that the Δoct values determined from L2 and L3 absorption edges are equal, indicating that the 2p1/2 and 2p3/2 core holes screen the t2g and eg electronic states in a similar manner.

The application of metal nanoparticles as an efficient drug delivery system is one of the directions of cancer therapy development. However, this strategy requires precise information about how the drug interacts with the applied nanocarrier. In this study, atomic force microscopy combined with infrared spectroscopy (AFM-IR) was used for the first time to investigate the erlotinib adsorption structure on two different types of 15 nm metal nanoparticle mono-layers, namely, silver nanoparticle (AgNP) and gold nanoparticle (AuNP) mono-layers. Because the metal nanoparticles are loosely bound samples, only the tapping AFM-IR mode is suitable for the collection of IR maps and spectra for such a system. The obtained results indicated the relevance of the AFM-IR technique for characterizing drug interactions with a metal mono-layer surface. The investigated drug interacts with the AgNPs mainly through phenyl rings and methoxy moieties, while quinazoline, amino, and ethoxy moieties appear to be farther from the surface. For the AuNPs, the interaction occurs through both the phenyl ring and the quinazoline moiety. Additionally, the aliphatic groups of erlotinib directly participate in this interaction. The novelty of the present work is also related to the use of the tapping AFM-IR mode to study metal NP mono-layers with a drug adsorbed on them. The collected IR maps for the most enhanced erlotinib bands show specific areas with very high signal intensity. The connection between these areas and the “hot spots” typical for the surface plasmon resonance phenomenon of metals is considered.

The recent emergence of High Definition (HD) FT-IR and Quantum Cascade Laser (QCL) Microscopes elevated the IR imaging field very close to clinical timescales. However, the speed of acquisition and data quality are still the critical factors in reaching the clinic. Denoising offers aide in both aspects if performed properly. However, there is a lack of a direct comparison of the efficiency of denoising techniques in IR imaging in general. To achieve such comparison within a rigorous framework and obtaining the critical information about signal loss, a simulated dataset strongly bound by experimental parameters was created. Using experimental structural and spectral information and experimental noise levels data as an input for the simulation, a direct comparison of spatial (Fourier transform, Mean Filter, Weighted Mean Filter, Gauss Filter, Median Filter, spatial Wavelets and Deep Neural Networks) and spectral (Savitzky-Golay, Fourier transform, Principal Component Analysis, Minimum Noise Fraction and spectral Wavelets) denoising schemes was enabled. All of these techniques were compared on the simulated dataset, taking into account SNR gain, signal distortion and sensitivity to tuning parameters as comparison metrics. Later, the best techniques were applied to experimental data for validation. The results presented here clearly show the benefit of using hyperspectral denoising schemes such as PCA and MNF which outperform other methods.

Herein, it has been demonstrated how resonant X-ray emission spectroscopy can be employed to study the charge transfer dynamics in real-time during the temperature-induced oxidation of metallic tungsten. Application of high energy resolution schemes allowed distinguishing charge transfer to separate orbitals resulting from crystal field splitting. Based on the time-resolved studies, it was possible to determine the corresponding charge transfer rates. From the experimental data, we determined that the electron transfer during the thermal oxidation of the metal dominates in the temperature range of 470-570 °C, reaching a maximum of 0.036 electrons per °C.

Multiple sclerosis (MS) is a chronic, neurodegenerative disease of central nervous system, characterized by inflammation, demyelination, and gliosis. It is commonly known the rapid and accurate diagnosis of MS determines treatment success. The standard diagnosis contains clinical symptoms observation, magnetic resonance imaging (MRI) of central nervous system (CNS), and analysis of cerebrospinal fluid (CSF). Nonetheless, since CSF sampling is considered invasive and not all individuals are eligible for MRI we have decided to propose other diagnostic tool such as spectroscopy. Unlike lumbar puncture, blood collection is a routine procedure regarded as low-invasive; therefore, we used Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy. This technique was combined with chemometrics and detailed spectral assay to analyse blood plasma and serum samples collected from MS patients and healthy individuals. The results revealed a clear identification pattern of MS, suggesting the conformation changes of amide III collagen-like proteins in plasma and the dominance of amide I β-sheet structures. Those changes in serum spectra seem to be useful for sample differentiation.

The cellular prion protein (PrPC) is a mainly α-helical 208-residue protein located in the pre- and postsynaptic membranes. For unknown reasons, PrPC can undergo a structural transition into a toxic, β-sheet rich scrapie isoform (PrPSc) that is responsible for transmissible spongiform encephalopathies (TSEs). Metal ions seem to play an important role in the structural conversion. PrPC binds Zn(II) ions and may be involved in metal ion transport and zinc homeostasis. Here, we use multiple biophysical techniques including optical and NMR spectroscopy, molecular dynamics simulations, and small angle X-ray scattering to characterize interactions between human PrPC and Zn(II) ions. Binding of a single Zn(II) ion to the PrPC N-terminal domain via four His residues from the octarepeat region induces a structural transition in the C-terminal α-helices 2 and 3, promotes interaction between the N-terminal and C-terminal domains, reduces the folded protein size, and modifies the internal structural dynamics. As our results suggest that PrPC can bind Zn(II) under physiological conditions, these effects could be important for the physiological function of PrPC.

In this study, we provide the first Fourier-transform infrared absorption spectroscopy (FTIR) and Raman spectroscopy (RS) analysis of a vibrational fingerprint of erlotinib, a drug which is applied in non-small cell lung cancer therapy, in solid state and solution in different pH conditions. Additionally, the performed DFT theoretical calculations in vacuum and PCM models support the interpretation of vibrational spectra and give insight into an optimized spatial configuration of the investigated drug. The present considerations show vibrational structure of erlotinib and details of its molecular geometry. Furthermore, we discuss the pH condition where the protonated –NH+ and C=N+ forms occur and indicate the spectral changes characteristic for the erlotinib protonation. It is of great of importance to better understand biological activity of the drug and to develop new tyrosine kinase inhibitors.

Currently, there is great interest in bringing the application of IR spectroscopy into the clinic. This however will require a significant reduction in measurement time as Fourier Transform Infrared (FT-IR) imaging takes hours to days to scan a clinically relevant specimen. A potential remedy for this issue is the use of Quantum Cascade Laser Infrared (QCL IR) microscopy performed in Discrete Frequency (DF) mode for maximum speed gain. This gain could be furthermore improved by applying a proper denoising algorithm that takes into account the specific data structure. We have recently compared spectral and spatial denoising techniques in the context of Fourier Transform IR (FT-IR) imaging and showed that the optimal methods depend heavily on the exact data structure. In general multivariate denoising methods such as Principal Component Analysis (PCA) and Minimum Noise Fraction (MNF) are the most effective for a dataset containing multiple bands. Histologic classification of QCL IR images of pancreatic tissue using Random Forest was therefore performed to investigate which denoising schemes are the most optimal for such experimental data structure. This work is the first to show the effects of denoising on classification accuracy of QCL data and is likely to be transferable to other QCL microscopes and other modalities using DF imaging, e.g. AFM-IR or CARS/SRS imaging.

Human prion protein is a subject of extensive study, related in particular to the molecular basis of neurodegenerative disease development and prevention. This protein has two main domains: the membrane C-terminal, structured domain as well as the unstructured N-terminal domain. While PrPC (23–231) has up to eight Cu(ii) binding sites in the N-terminal domain, it includes a characteristic, conservative octarepeat region PHGGGWGQ, which was studied by means of X-ray absorption near edge spectroscopy. The measurements were conducted at the SuperXAS beamline (SLS, PSI, Villigen). For the initial 1 : 1 protein-to-Cu(ii) ratio, the two main Cu(ii) binding modes were identified using linear combination fitting and ab initio FEFF calculations for X-ray spectra. Their electronic structures indicated that Cu(ii) coordinated by strong π-donors could effectively suppress the pre-edge structure due to the filling of empty Cu(ii) d-states. The suppression was correlated with the charge transfer effect and filling of the virtual electronic Cu(ii) states. What is more, we showed that the 1s → 4p + LMCT (Ligand-to-Metal-Charge-Transfer) multielectron transition relation with the main edge transition could be used as a marker for preliminary comparison of an unknown organic compound to a reference. The presented results permitted a possible explanation of the mechanism of choosing the preferred Cu(ii) modes in PrPC–Cu(ii) coordination processes and of the complex stability from the electronic point of view.

Fourier transform infrared spectroscopy (FT-IR) is widely used in the analysis of the chemical composition of biological materials and has the potential to reveal new aspects of the molecular basis of diseases, including different types of cancer. The potential of FT-IR in cancer research lies in its capability of monitoring the biochemical status of cells, which undergo malignant transformation and further examination of spectral features that differentiate normal and cancerous ones using proper mathematical approaches. Such examination can be performed with the use of chemometric tools, such as partial least squares discriminant analysis (PLS-DA) classification and partial least squares regression (PLSR), and proper application of preprocessing methods and their correct sequence is crucial for success. Here, we performed a comparison of several state-of-the-art methods commonly used in infrared biospectroscopy (denoising, baseline correction, and normalization) with the addition of methods not previously used in infrared biospectroscopy classification problems: Mie extinction extended multiplicative signal correction, Eiler’s smoothing, and probabilistic quotient normalization. We compared all of these approaches and their effect on the data structure, classification, and regression capability on experimental FT-IR spectra collected from five different prostate normal and cancerous cell lines. Additionally, we tested the influence of added spectral noise. Overall, we concluded that in the case of the data analyzed here, the biggest impact on data structure and performance of PLS-DA and PLSR was caused by the baseline correction, therefore, much attention should be given, especially to this step of data preprocessing.

Infrared (IR) imaging can be used for fast, accurate and non-destructive pathology recognition of biopsies when supported by machine learning algorithms. Transflection mode of measurements has the potential to be translated into the clinic due to economic reasons of large-scale imaging with the need for inexpensive substrates. Unfortunately, in this mode spectral distortions originating from light interference appear. Due to this fact transmission measurement mode is more frequently used in pathology recognition. Nevertheless, this measurement mode also is not devoid of spectral distortion effects like scattering. However, this effect is better understood and there are preprocessing algorithms to minimize it. In this work, we investigated the influence of interference effects on spectral quality of pancreatic tissues measured in transmission and transflection mode with Fourier tranform IR (FT-IR) microscopy using samples embedded with and without paraffin. The removal of paraffin leads to an altered magnitude of interference in transflection and provides a platform for a detailed analysis of its effect on the spectra of biological material, since the same sample is measured with different interference conditions. Moreover, the potential of transflection mode measurements in histological classification of analyzed samples was investigated and compared with classification results for transmission mode.

Nanomechanical properties of living cells, as measured with atomic force microscopy (AFM), are increasingly recognized as criteria that differentiate normal and pathologically altered cells. Locally measured cell elastic properties, described by the parameter known as Young's modulus, are currently proposed as a new diagnostic parameter that can be used at the early stage of cancer detection. In this study, local mechanical properties of normal human prostate (RWPE-1) cells and a range of malignant (22Rv1) and metastatic prostate cells (LNCaP, Du145 and PC3) were investigated. It was found that non-malignant prostate cells are stiffer than cancer cells while the metastatic cells are much softer than malignant cells from the primary tumor site. Next, the biochemical properties of the cells were measured using confocal Raman (RS) and Fourier-transform infrared (FT-IR) spectroscopies to reveal these cells' biochemical composition as malignant transformation proceeds. Nanomechanical and biochemical profiles of five different prostate cell lines were subsequently analyzed using partial least squares regression (PLSR) in order to identify which spectral features of the RS and FT-IR spectra correlate with the cell's elastic properties. The PLSR-based model could predict Young's modulus values based on both RS and FT-IR spectral information. These outcomes show not only that AFM, RS and FT-IR techniques can be used for discrimination between normal and cancer cells, but also that a linear correlation between mechanical response and biomolecular composition of the cells that undergo malignant transformation can be found. This knowledge broadens our understanding of how prostate cancer cells evolve thorough the multistep process of tumor pathogenesis.

Head and neck tumors can be very challenging to treat because of the risk of problems or complications after surgery. Therefore, prompt and accurate diagnosis is extremely important to drive appropriate treatment decisions, which may reduce the chance of recurrence. This paper presents the original research exploring the feasibility of Fourier transform infrared (FT-IR) and Raman spectroscopy (RS) methods to investigate biochemical alterations upon the development of the pleomorphic adenoma. Principal component analysis (PCA) was used for a detailed assessment of the observed changes and to determine the spectroscopic basis for salivary gland neoplastic pathogenesis. It is implied that within the healthy margin, as opposed to the tumoral tissue, there are parts that differ significantly in lipid content. This observation shed new light on the crucial role of lipids in tissue physiology and tumorigenesis. Thus, a novel approach that eliminates the influence of lipids on the elucidation of biochemical changes is proposed. The performed analysis suggests that the highly heterogeneous healthy margin contains more unsaturated triacylglycerols, while the tumoral section is rich in proteins. The difference in protein content was also observed for these two tissue types, i.e. the healthy tissue possesses more proteins in the anti-parallel β-sheet conformation, whereas the tumoral tissue is dominated by proteins rich in unordered random coils. Furthermore, the pathogenic tissue shows a higher content of carbohydrates and reveals noticeable differences in nucleic acid content. Finally, FT-IR and Raman spectroscopy methods were proposed as very promising methods in the discrimination of tumoral and healthy tissues of the salivary gland.

Modern techniques of radiotherapy such as fractioned radiotherapy require applications of low doses of ionizing radiation (up to 10 Gy) for effective patient treatment. It is, therefore, crucial to understand the response mechanisms in cancer cells irradiated with low (clinical) doses. The cell’s response to irradiation depends on a dose and post-irradiation time. Both factors should be considered when studying the influence of ionizing radiation on cancer cells. Thus, in the present study, PC-3 prostate cancer cells were irradiated with clinical doses of X-rays to determine dose- and time-dependent response to the irradiation. Raman spectroscopy and biological methods (MTT and comet assays) were applied for the analysis of biochemical changes in the cells induced by low doses of X-ray irradiation at 0 h and 24 h post-irradiation timepoints. Due to a limited view of the biochemical changes at the subcellular level given by single spectrum Raman measurements, Raman mapping of the whole cell area was performed. The results were compared with those obtained for cell irradiation with high doses. The analysis was based on the Partial Least Squares Regression (PLSR) method for the cytoplasmic and nuclear regions separately. Additionally, for the first time, irradiation classification was performed to confirm Raman spectroscopy as a powerful tool for studies on cancer cells treated with clinical doses of ionizing radiation.

The work presents a comprehensive vibrational analysis of the process of adsorption of threonine (Thr) onto an Fe surface with deposited Cu nanoparticles (NPs) (of about 4–5 nm in size) in a corrosive environment. The application of surface-enhanced Raman spectroscopy (SERS) and surface-enhanced infrared absorption spectroscopy (SEIRA) provides the opportunity for detailed description of adsorption geometry of amino acid onto a metal surface. The combination of conventional infrared spectroscopy (IR) with atomic force microscopy (AFM) resulted in a nano-SEIRA technique which made it possible to provide a precise description of adsorbate binding to the metal surface. The studies presented confirmed that there is a very good correlation between the spectra recorded by the SERS, SEIRA, and nano-SEIRA techniques. Threonine significantly influenced the process of corrosion of the investigated surface due to the existing strong interaction between the protonated amine and carboxylate groups and the CuNPs deposited onto the Fe surface. In addition, the application of two polarization modulations (s and p) in nano-SEIRA allows subtle changes to be observed in the molecule geometry upon adsorption, with the carboxylate group of Thr being almost horizontally oriented onto the metal surface; whereas the amine group that contains nitrogen is oriented perpendicular to this surface.

Fourier transform infrared spectroscopy has emerged as a powerful tool for tissue specimen investigation. Its nondestructive and label-free character enables direct determination of biochemical composition of samples. Furthermore, the introduction of polarization enriches this technique by the possibility of molecular orientation study apart from purely quantitative analysis. Most of the molecular orientation studies focused on polymer samples with a well-defined molecular axis. Here, a four-polarization approach for Herman’s in-plane orientation function and azimuthal angle determination was applied to a human tissue sample investigation for the first time. Attention was focused on fibrous tissues rich in collagen because of their cylindrical shape and established amide bond vibrations. Despite the fact that the tissue specimen contains a variety of molecules, the presented results of molecular ordering and orientation agree with the theoretical prediction based on sample composition and vibration directions.

Metabolic stress, such as lipotoxicity, affects the DNA methylation profile in pancreatic &beta, cells and thus contributes to &beta, cell failure and the progression of type 2 diabetes (T2D). Stearoyl-CoA desaturase 1 (SCD1) is a rate-limiting enzyme that is involved in monounsaturated fatty acid synthesis, which protects pancreatic &beta, cells against lipotoxicity. The present study found that SCD1 is also required for the establishment and maintenance of DNA methylation patterns in &beta, cells. We showed that SCD1 inhibition/deficiency caused DNA hypomethylation and changed the methyl group distribution within chromosomes in &beta, cells. Lower levels of DNA methylation in SCD1-deficient &beta, cells were followed by lower levels of DNA methyltransferase 1 (DNMT1). We also found that the downregulation of SCD1 in pancreatic &beta, cells led to the activation of adenosine monophosphate-activated protein kinase (AMPK) and an increase in the activity of the NAD-dependent deacetylase sirtuin-1 (SIRT1). Furthermore, the physical association between DNMT1 and SIRT1 stimulated the deacetylation of DNMT1 under conditions of SCD1 inhibition/downregulation, suggesting a mechanism by which SCD1 exerts control over DNMT1. We also found that SCD1-deficient &beta, cells that were treated with compound c, an inhibitor of AMPK, were characterized by higher levels of both global DNA methylation and DNMT1 protein expression compared with untreated cells. Therefore, we found that activation of the AMPK/SIRT1 signaling pathway mediates the effect of SCD1 inhibition/deficiency on DNA methylation status in pancreatic &beta, cells. Altogether, these findings suggest that SCD1 is a gatekeeper that protects &beta, cells against the lipid-derived loss of DNA methylation and provide mechanistic insights into the mechanism by which SCD1 regulates DNA methylation patterns in &beta, cells and T2D-relevant tissues.

Exposure to ionizing radiation significantly affects biochemistry of cancer cells. The effect of irradiation can be divided into two stages, that is, the physicochemical stage and the biological response. Both effects induce different biochemical changes in the cells and should be analyzed as two separate phenomena. Thus, in the current study, Raman spectroscopy of prostate cancer cells fixed before (the physicochemical damage model) and just after (the biological response model) irradiation was undertaken to compare biochemical composition of irradiated cancer cells at both stages. Spectroscopic analysis of the cells was performed separately for cytoplasmic and nuclear regions. Biochemical changes of irradiated cells were analyzed using partial least squares regression (PLSR) method on the basis of the collected Raman spectra. Regression coefficients were therefore used to describe differences and similarities between biochemical composition of cancer cells undergoing the physicochemical stage and biological response. Additionally, PLSR models of both phenomena were compared for linear dose-dependence and a cross prediction.

Background The process of malignant transformations of many tumour cases is still unclear and more specific experimental approaches are necessary. The detailed identification of the pathological changes may help in the therapy progression through the development of drugs with more selective action. Methods In this study, the AFM-IR nanospectroscopy was applied for the first time to the pleomorphic adenoma (TM) and the marginal tissue characterizations. In order to verify the obtained spectral information, conventional FT-IR investigations were also performed. Results The AFM-IR data (topographies, intensity maps, and spectra) show structural changes observed for the margin and TM samples. Additionally, within the tumour tissue the fibril-like areas, characteristic for amyloid diseases, were distinguished. Conclusions The application of AFM-IR allows to determine changes in the protein secondary structures between the fibrils and the regions outside them. It has been proved that, for the former areas, the α-helix/random coil/ β-sheet components dominate, while for the latter regions the α-helix/random coil indicate the main contribution to the protein composition. General significance The FT-IR results remain in good agreement with the AFM-IR data recorded for the areas outside the fibrils of the TM. This observation confirms that by means of the conventional FT-IR method the identification of the considered fibrils structure would be impossible. Only application of the AFM-IR nanospectroscopy allow for characterization and visualization of the fibrillization process occurring within the investigated tumour tissue.

OLED technology beyond small or expensive devices requires light-emitters, luminophores, based on earth-abundant elements. Understanding and experimental verification of charge transfer in luminophores are needed for this development. An organometallic multicore Cu complex comprising Cu–C and Cu–P bonds represents an underexplored type of luminophore. To investigate the charge transfer and structural rearrangements in this material, we apply complementary pump-probe X-ray techniques: absorption, emission, and scattering including pump-probe measurements at the X-ray free-electron laser SwissFEL. We find that the excitation leads to charge movement from C- and P- coordinated Cu sites and from the phosphorus atoms to phenyl rings; the Cu core slightly rearranges with 0.05 Å increase of the shortest Cu–Cu distance. The use of a Cu cluster bonded to the ligands through C and P atoms is an efficient way to keep structural rigidity of luminophores. Obtained data can be used to verify computational methods for the development of luminophores., Nature Communications, 11 (1), ISSN:2041-1723

Herein we report on the hydrolysis mechanism of [Pt{N(p-HC 6 F 4 )CH 2 } 2 (NC 5 H 5 ) 2 (OH) 2 ], a platinum(IV) complex that exhibits anti-cancer properties. Atomic telemetry, an in situ technique based on electron structure sensitive X-ray spectroscopy, revealed that hydrolysis preceded any reduction of the metal center. The obtained results are complemented with 19 F NMR measurements and theoretical calculations and support the observation that this Pt IV complex does not reduce spontaneously to Pt II in HEPES buffer solution at pH 7.4 and after 24 h incubation. These results are of importance for the design of novel Pt-based coordination complexes as well as understanding their behavior under physiological conditions.

The recent emergence of High Definition (HD) FT-IR and Quantum Cascade Laser (QCL) Microscopes elevated the IR imaging field very close to clinical timescales. However, the speed of acquisition and data quality are still the critical factors in reaching the clinic. Denoising offers aide in both aspects if performed properly. However, there is a lack of a direct comparison of the efficiency of denoising techniques in IR imaging in general. To achieve such comparison within a rigorous framework and obtaining the critical information about signal loss, a simulated dataset strongly bound by experimental parameters was created. Using experimental structural and spectral information and experimental noise levels data as an input for the simulation, a direct comparison of spatial (Fourier transform, Mean Filter, Weighted Mean Filter, Gauss Filter, Median Filter, spatial Wavelets and Deep Neural Networks) and spectral (Savitzky-Golay, Fourier transform, Principal Component Analysis, Minimum Noise Fraction and spectral Wavelets) denoising schemes was enabled. All of these techniques were compared on the simulated dataset, taking into account SNR gain, signal distortion and sensitivity to tuning parameters as comparison metrics. Later, the best techniques were applied to experimental data for validation. The results presented here clearly show the benefit of using hyperspectral denoising schemes such as PCA and MNF which outperform other methods.

OBJECTIVES To assess the relationships of clinical and laboratory parameters, with erythrocyte oxygen concentration. METHODS The study group consisted of 47 healthy adults out of which 16 showed slightly higher blood pressure and were classified as individuals with prehypertension. For each individual, data were obtained on: systolic and diastolic blood pressure (SBP, DBP), blood morphology, lipids profile, fibrinogen, hs-CRP. The erythrocyte oxygen concentration was assessed with the Raman spectroscopy technique. Arithmetic means for all laboratory parameters were estimated by oxygen concentration tertiles and tested for statistical significance of linear trends across tertiles. RESULTS The multivariate regression analysis showed statistically significant negative relationship of triglycerides level with oxygen concentration. CONCLUSIONS A hypothesis has been formulated that triglycerides level is an indicator of the erythrocyte ability to transport oxygen to the tissues.

A novel approach of combining conventional infrared spectroscopy (IR) and atomic force microscopy (AFM) is presented to better understand the behavior of a drug adsorbed on a metal substrate at the nanoscale level. Tip-enhanced infrared nanospectroscopy (TEIRA) was used for the first time to investigate Lu AA33810, a selective brain-penetrating Y5 receptor antagonist, after immobilization on gold nanoparticles (GNPs). Here, a gold coated AFM tip and gold substrate were used to obtain the near-field electromagnetic field trapping effect. Because of the huge signal enhancement, it was possible to obtain the spectral information regarding the self-assembled monolayer of the investigated molecule. The effect of two orthogonal polarizations (p- and s-polarization modulations) of the excitation laser beam on the spectral patterns is also discussed. The results show that there is a strong relationship between the state of polarization of the incident radiation and the relative infrared band intensities. Another factor affecting the observed spectral differences is the topology of the metal substrate, which may result in the induction of a cross-polarization effect. The performed analysis indicates that the C–C bond from the cyclohexyl group is oriented almost parallel to the metal surface. Conversely, the p- and s-polarized spectral variations suggest that the O=S=O angle is high enough to enable the simultaneous interaction of both oxygen atoms with the GNPs.

This study presents a multianalytical approach for surface-enhanced infrared absorption spectroscopy (SEIRA) and tip-enhanced infrared nanospectroscopy (TEIRA) studies of the α-methyl-dl-tryptophan adsorption geometry on a gold nanoparticle surface. Comparison of SEIRA spectra obtained in the transmission, attenuated total reflection and reflection modes verified the reproducibility of the adsorption. The application of the AutoSeagull (Harrick Scientific) accessory enabled us to track the dependence of the incident angle on the relative band intensity in the same area of the sample. Furthermore, the effect of two polarization modulations (p and s) in TEIRA was examined to deduce the adsorption geometry and to better understand the molecule/metal interaction. The nanogap between a gold-coated atomic force microscopy (AFM) tip and the gold surface induced electromagnetic enhancement in the optical field intensity. This is associated with the additional near-field electromagnetic field trapping effect. The local field intensity reinforcement significantly increased the infrared absorption cross-section of the compound under the tip with simultaneous improvement in spatial resolution. The originality of this study lies in the combination of various measurement modes and incident angles in SEIRA and two orthogonal polarizations in TEIRA to provide comprehensive characterization of the adsorption phenomenon. The results give important insights into tracking subtle changes in molecule geometry upon adsorption.

The International Conference on X-ray Absorption Fine Structure (XAFS) has a well-established tradition dating back to the first conference held in 1981 in Daresbury. Since then, it took place alte...

Neurodegenerative diseases are one of the malfunctions of human nervous system, being a class of complex and prominent pathologies. The human prion Protease Resistant Protein (PrP) is protein regulating copper metabolism in mammalian cells through binding of Cu(II) ions to specific fragments. Nowadays misfolding of this protein is associated with development of prion diseases. Therefore, it is crucial to obtain structural information about coordination of Cu(II) by PrP protein. Herein, we report X-ray absorption spectroscopy (XAS) measurements, carried out on SuperXAS beamline (SLS, PSI Villigen) on PrPC-Cu(II) complexes. Obtained results were compared with theoretical predictions done by FEFF 9.6 software. Complementary to XAS data, Atomic Force Microscopy (AFM) measurements were conducted to obtain low resolution structural information about prepared sample that allow to develop protocol of fixing PrPC molecules on solid substrate used for further experiments. It has been established that folded C-terminal domain of PrPC protein has around 5 nm in diameter. Presented results showed that both XAS and AFM methods are useful tools in detailed examination of complexes of human PrPC either with Cu(II) or with other divalent metal ions.

This article presents the first physical insights into the binding interaction between the electrochemically roughened silver electrode and CBR-5884, an anticancer drug. The work gives a comprehensive account of the influence of applied electrode potential and excitation wavelength on the molecular adsorption on the metal surface. This type of research, based on the unique surface phenomena, may lead to a far-reaching improvement in biosensing and bioimaging applications, which may result in significant improvement in combined cancer chemo-immunotherapy. The main concern of the paper was to explore the possibility of surface-enhanced Raman spectroscopy (SERS) to understand physicochemical interactions at the nano-bio interface. Simultaneously, the molecular geometry in the equilibrium state and Raman frequencies were calculated based on the density functional theory (DFT) at the B3LYP 6-311G(d,p) level of theory. The highest SERS signal amplification is observed at the potential of –0.3 V for lower excitation wavelength, while at more negative electrode potential the molecule slowly desorbs or decomposes from the metal surface. At higher wavelengths, the enhancement of the SERS of individual bands is observed, which confirms the selective contribution of the charge-transfer mechanism in the SERS spectra along with the detection of different metal complexes adsorbed on the surface.

An investigation of a numismatic collection of silver denarii from the early Piast dynasty was conducted using Fourier-transform infrared spectroscopy. The studied coins, minted between 995 and 1020 ad under the rules of Boleslaus the Brave and Mieszko II Lambert, belong to the collection of the National Museum in Krakow. Fourier-transform infrared spectroscopy imaging and mapping have been used for recording a visual image of the surface chemistry based on vibrational spectra and accurately representing the distribution of chemical compounds, respectively. Additionally, scanning electron microscopy coupled to energy-dispersive X-ray analysis was used to study the surface topography of the coins and characterize their elemental composition. Differences in the distribution of the identified chemical compounds were detected in heterogeneous areas of the denarii. Corrosion effects, associated to many factors including the alloy composition, the metallographic structure, the manufacturing processes, and the environment were also observed and identified.

This report describes the first detailed characterization of the molecular structure of Lu AA33810, a selective Y5 receptor antagonist, and its behavior at the solid/liquid interface after conjugation with gold nanoparticles (GNPs). Physicochemical characterization, including imaging by scanning electron microscopy as well as electrophoretic mobility and dynamic light scattering measurements, was performed to determine the morphology, electrokinetic properties and range of stability of the GNPs. A comprehensive vibrational analysis, employing Raman spectroscopy, Fourier transform infrared absorption, surface-enhanced Raman spectroscopy, and surface-enhanced infrared absorption methods, is reported. The experimental data are supported by density functional theory calculations. It is implied that the Thz and Phe rings determine the adsorption geometry of Lu AA33810 on the studied GNPs and adopt a tilted orientation, exposing the interaction between the Thz free electron pair and the metallic nanosubstrates....

An extremely important aspect of planning cancer treatment is not only the drug efficiency but also a number of challenges associated with the side effects and control of this process. That is why it is worth paying attention to the promising potential of the gold nanoparticles combined with a compound treated as a potential drug. This work presents Raman (RS), infrared absorption (IR) and surface–enhanced Raman scattering (SERS) spectroscopic investigations of N–acetyl–5–methoxytryptamine (melatonin) and α–methyl– dl –tryptophan, regarding as anti breast cancer agents. The experimental spectroscopic analysis was supported by the quantum-chemical calculations based on the B3LYP hybrid density functional theory (DFT) at the B3LYP 6–311G(d,p) level of theory. The studied compounds were adsorbed onto two colloidal gold nanosensors synthesized by a chemical reduction method using sodium borohydride (SB) and trisodium citrate (TC), respectively. Its morphology characteristics were obtained using transmission electron microscopy (TEM). It has been suggested that the NH moiety from the aromatic ring, a well-known proton donor, causes the formation of hydrogen bonds with the negatively charged gold surface.

The article describes an X-ray microbeam standalone facility dedicated for irradiation of living cultured cells. The article can serve as an advice for such facilities construction, as it begins from engineering details, through mathematical modeling and experimental procedures, ending up with preliminary experimental results and conclusions. The presented system consists of an open type X-ray tube with microfocusing down to about 2 μm, an X-ray focusing system with optical elements arranged in the nested Kirckpatrick-Baez (or Montel) geometry, a sample stand and an optical microscope with a scientific digital CCD camera. For the beam visualisation an X-ray sensitive CCD camera and a spectral detector are used, as well as a scintillator screen combined with the microscope. A method of precise one by one irradiation of previously chosen cells is presented, as well as a fast method of uniform irradiation of a chosen sample area. Mathematical models of beam and cell with calculations of kerma and dose are presented. The experiments on dose-effect relationship, kinetics of DNA double strand breaks repair, as well as micronuclei observation were performed on PC-3 (Prostate Cancer) cultured cells. The cells were seeded and irradiated on Mylar foil, which covered a hole drilled in the Petri dish. DNA lesions were visualised with γ-H2AX marker combined with Alexa Fluor 488 fluorescent dye.

Lactose and saccharose have the same molecular formula; however, the arrangement of their atoms is different. A major difference between lactose and saccharose with regard to digestion and processing is that it is not uncommon for individuals to be lactose intolerant (around two thirds of the population has a limited ability to digest lactose after infancy), but it is rather unlikely to be saccharose intolerant. The pharmaceutical industry uses lactose and saccharose as inactive ingredients of drugs to help form tablets because of their excellent compressibility properties. Some patients with severe lactose intolerance may experience symptoms of many allergic reactions after taking medicine that contains this substance. People who are specifically "allergic" to lactose (not just lactose intolerant) should not use tablets containing this ingredient. Fourier Transform Infrared (FTIR) spectroscopy has a unique chemical fingerprinting capability and plays a significant important role in the identification and characterization of analyzed samples and hence has been widely used in pharmaceutical science. However, a typical FTIR spectrum collected from tablets contains a myriad of valuable information hidden in a family of tiny peaks. Powerful multivariate spectral data processing can transform FTIR spectroscopy into an ideal tool for high volume, rapid screening and characterization of even minor tablet components. In this paper a method for distinction between FTIR spectra collected for tablets with or without lactose is presented. The results seem to indicate that the success of identifying one component in FTIR spectra collected for pharmaceutical composition (that is tablet) is largely dependent on the choice of the chemometric technique applied.