A Prospective Study on the Impact of Clinical Factors and Adjusted Triple D System for Success Rate of ESWL.

Objective: Our study aimed to evaluate the success rate of ESWL and identify relevant treatment-specific factors affecting treatment outcomes, as well as to assess the accuracy of the updated Triple D scoring system and compare it with older systems. Material and Methods: A prospective study of 71 patients who received ESWL treatment for renal stones that were 5-15 mm in size was completed. The patient having no residual stones or residual stones lesser than 4 mm after ESWL was identified as a treatment success. Univariate and multivariate logistic regression and ROC curves were used to identify important factors for treatment outcomes. Results: Successful treatment was achieved for 66.2% of patients. The stone volume (SV), mean stone density (MD), and delivered power to the stone volume unit ratio (SMLI/SV) were defined as the most critical factors influencing ESWL success. An updated Triple D score system with a, SMLI/SV ratio could be an alternative to older systems and reach an even higher accuracy. A limitation of this study is the limited sample size due to the COVID-19 pandemic. Conclusions: Our results show that the three factors that most influence the success of ESWL are the stone size, mean stone density, and SMLI/SV ratio. Based on this, we present a simple updated triple D score system to predict ESWL success, which could be implemented in future clinical practice.

Structural studies of 1,1-dimethyl-2-oxy-1-silacyclohexane by means of matrix isolation infrared absorption spectroscopy.

Infrared spectra of gaseous, liquid, and matrix-isolated samples of newly synthesized 1,1-dimethyl-2-oxy-1-silacyclohexane were recorded. Raman spectra of 1,1-dimethyl-2-oxy-1-silacyclohexane in liquid and solid states were obtained in the temperature range from 170 to 340 K. Ab initio HF and DFT B3LYP calculations were performed in order to determine the possible conformations of 1,1-dimethyl-2-oxy-1-silacyclohexane and to make accurate assignment of the vibrational spectral bands. The study confirms the existence of only one chair-type conformer of 1,1-dimethyl-2-oxy-1-silacyclohexane.

Monitoring Ti3C2Tx MXene Degradation Pathways Using Raman Spectroscopy.

Extending applications of Ti3C2Tx MXene in nanocomposites and across fields of electronics, energy storage, energy conversion, and sensor technologies necessitates simple and efficient analytical methods. Raman spectroscopy is a critical tool for assessing MXene composites; however, high laser powers and temperatures can lead to the materials' deterioration during the analysis. Therefore, an in-depth understanding of MXene photothermal degradation and changes in its oxidation state is required, but no systematic studies have been reported. The primary aim of this study was to investigate the degradation of the MXene lattice through Raman spectroscopic analysis. Distinct spectral markers were related to structural alterations within the Ti3C2Tx material after subjecting it to thermal- and laser-induced degradation. During the degradation processes, spectral markers were revealed for several specific steps: a decrease in the number of interlayer water molecules, a decrease in the number of -OH groups, formation of C-C bonds, oxidation of the lattice, and formation of TiO2 nanoparticles (first anatase, followed by rutile). By tracking of position shifts and intensity changes for Ti3C2Tx, the spectral markers that signify the initiation of each step were found. This spectroscopic approach enhances our understanding of the degradation pathways of MXene, and facilitating enhanced and dependable integration of these materials into devices for diverse applications, from energy storage to sensors.

Differentiation of Urothelial Carcinoma and Normal Bladder Tissues by Means of Fiber-Based ATR IR Spectroscopy.

Surgical treatment is widely applied curative approach for bladder cancer. White light cystoscopy (WLC) is currently used for intraoperative diagnostics of malignant lesions but has relatively high false-negative rate. Here we represent an application of label free fiber-based attenuated total reflection infrared spectroscopy (ATR IR) for freshly resected human bladder tissue examination for 54 patients. Defined molecular spectral markers allow to identify normal and urothelial carcinoma tissues. While methods of statistical analysis (Hierarchical cluster analysis (HCA) and Principal component analysis (PCA)) used for spectral data treatment allow to discriminate tissue types with 91% sensitivity and 96-98% specificity. In the present study the described method was applied for tissue examination under ex vivo conditions. However, after method validation the equipment could be translated from laboratory studies to in situ or even in vivo studies in operating room.

A Novel Infrared Spectroscopy Method for Analysis of Stone Dust for Establishing Final Composition of Urolithiasis.

Background: The introduction of the holmium laser for lithotripsy and minimally invasive techniques in endoscopy increased the popularity of stone dusting techniques. Retrieving stone pieces for an analysis increases the economic burden of surgery and operative time. Novel methods are needed for the analysis of convenient urolithiasis composition. Objective: This study aims to assess the efficacy of the stone dust Fourier transform infrared spectroscopy coupled with attenuated total reflection (FTIR ATR) method for accurate stone composition determination from the dust specimens compared with simultaneously retrieved standard stone fragments. Design setting and participants: From July 2021 to March 2022, a total of 75 patients who received endoscopic treatment for urolithiasis were included in this study. Outcome measurements and statistical analysis: The accuracy of the FTIR ATR method was assessed via estimates of sensitivity, specificity, negative predictive value (NPV), and positive predictive value (PPV). The results were compared between samples of stone dust and the final stone composition. Results and limitations: Total or partial biochemical composition agreement was observed in 92.7% of cases and total agreement in 82.4% of cases when stone dust was compared with stone fragments. The highest accuracy rates were obtained for uric acid stones: sensitivity 100%, specificity 98.3%, PPV 90.9%, and NPV 100%. Identification of other types of stones was also of high accuracy, reaching up to 83.3% sensitivity and 100% specificity. Conclusions: The application of FTIR ATR spectroscopy for a stone dust analysis allows obtaining easy and cost-effective final composition of urolithiasis without a stone fragment analysis. This technique was shown to be feasible, and there is substantial potential for clinical practice. Patient summary: This study investigates a novel method that determines accurate stone composition without acquiring the pieces of stone during surgery. The results have shown that stone dust Fourier transform infrared spectroscopy coupled with attenuated total reflection provides accurate stone composition.

Fast and label-free intraoperative discrimination of malignant pancreatic tissue by attenuated total reflection infrared spectroscopy.

Significance: Pancreatic surgery is a highly demanding and routinely applied procedure for the treatment of several pancreatic lesions. The outcome of patients with malignant entities crucially depends on the margin resection status of the tumor. Frozen section analysis for intraoperative evaluation of tissue is still time consuming and laborious. Aim: We describe the application of fiber-based attenuated total reflection infrared (ATR IR) spectroscopy for label-free discrimination of normal pancreatic, tumorous, and pancreatitis tissue. A pilot study for the intraoperative application was performed. Approach: The method was applied for unprocessed freshly resected tissue samples of 58 patients, and a classification model for differentiating between the distinct tissue classes was established. Results: The developed three-class classification model for tissue spectra allows for the delineation of tumors from normal and pancreatitis tissues using a probability score for class assignment. Subsequently, the method was translated into intraoperative application. Fiber optic ATR IR spectra were obtained from freshly resected pancreatic tissue directly in the operating room. Conclusion: Our study shows the possibility of applying fiber-based ATR IR spectroscopy in combination with a supervised classification model for rapid pancreatic tissue identification with a high potential for transfer into intraoperative surgical diagnostics.

Label-free differentiation of human pituitary adenomas by FT-IR spectroscopic imaging.

Fourier transform infrared (FT-IR) spectroscopic imaging has been used to characterize different types of pituitary gland tumors and normal pituitary tissue. Freshly resected tumor tissue from surgery was prepared as thin cryosections and examined by FT-IR spectroscopic imaging. Tissue types were discriminated via k-means cluster analysis and a supervised classification algorithm based on linear discriminant analysis. Spectral classification allowed us to discriminate between tumor and non-tumor cells, as well as between tumor cells that produce human growth hormone (hGH+) and tumor cells that do not produce that hormone (hGH-). The spectral classification was compared and contrasted with a histological PAS and orange G stained image. It was further shown that hGH+ pituitary tumor cells show stronger amide bands than tumor cells that do not produce hGH. This study demonstrates that FT-IR spectroscopic imaging can not only potentially serve as a fast and objective approach for discriminating pituitary gland tumors from normal tissue, but that it can also detect hGH-producing tumor cells.

Abundance and characteristics of microplastics in treated organic wastes of Kaunas and Alytus regional waste management centres, Lithuania.

The widespread use of plastic without the sustainable management of the plastic waste has led to its accumulation in the environment. The presence of microplastics even in drinking water and food products is of immense concern. This situation is getting even more complicated due to the limited knowledge about the sources of microplastics and their impact on the environment and human health. This article focuses on a poorly understood but potentially significant source of microplastic-treated organic waste. Quantitative and qualitative analyses of microplastics down to 50 µm in the stabilised organic waste (SOW) output after mixed municipal solid waste (MSW) processing and green and food composts are presented in the article. Nile Red staining and FTIR analysis were adopted for the identification of microplastics. The highest average microplastic abundance was found in the SOW: 17407 ± 1739 particles kg-1 in autumn and 15400 ± 1217 particles kg-1 in winter. Nevertheless, even separately collected treated organic waste contained a significant amount of microplastics. Green compost contained 5733 ± 850 particles kg-1 in autumn and 6433 ± 751 particles kg-1 in winter, while food compost 3783 ± 351 particles kg-1 in autumn and 4066 ± 658 particles kg-1 in winter. Microplastics < 1 mm accounted for 83.8-94.9% of all microplastics, which reflects the need to control not only large but also small microplastics in organic waste fertilisers to prevent soil pollution. The dominant shape of microplastics in compost samples was films, while in the SOW, it was fragments. Based on morphological and FTIR analyses, the majority of microplastics in green and food composts were considered as the residuals of plastic bags and packaging materials.

Toward a SERS Diagnostic Tool for Discrimination between Cancerous and Normal Bladder Tissues via Analysis of the Extracellular Fluid.

Vibrational spectroscopy provides the possibility for sensitive and precise detection of chemical changes in biomolecules due to development of cancers. In this work, label-free near-infrared surface enhanced Raman spectroscopy (SERS) was applied for the differentiation between cancerous and normal human bladder tissues via analysis of the extracellular fluid of the tissue. Specific cancer-related SERS marker bands were identified by using a 1064 nm excitation wavelength. The prominent spectral marker band was found to be located near 1052 cm-1 and was assigned to the C-C, C-O, and C-N stretching vibrations of lactic acid and/or cysteine molecules. The correct identification of 80% of samples is achieved with even limited data set and could be further improved. The further development of such a detection method could be implemented in clinical practice for the aid of surgeons in determining of boundaries of malignant tumors during the surgery.

Gender determination of fertilized unincubated chicken eggs by infrared spectroscopic imaging.

Each year, billions of day-old layer chicks are produced in the world. Since only female chicks are reared for egg production, the chicks must be sexed and the unwanted male layer chicks are culled. The culling of male chicks is a serious problem, both in terms of animal welfare and waste disposal. The germinal disc in fertilized but unincubated eggs contains already several thousands of blastoderm cells. The cellular DNA in birds is different for male and female chicks. The difference in DNA content between male and female chicks is around 2% and is measurable by Fourier transform infrared (FT-IR) spectroscopy. In this study, small amounts of blastoderm cells from 22 chicken eggs were characterized by attenuated total reflection FT-IR spectroscopic imaging and classified by linear discriminant analysis. Polymerase chain reaction (PCR) was used as a reference method to determine the gender. The spectroscopic results demonstrate that male blastoderm cells exhibit a higher content of DNA than cells from female blastoderm. The spectroscopic-based gender determination led to the same result as the PCR analysis. FT-IR spectroscopic imaging allows the gender determination of unincubated eggs within a few seconds based on the accurate determination of the different DNA contents in blastoderm cells of both sexes.

Detection of caffeine intake by means of EC-SERS spectroscopy of human saliva.

This work presents the application of EC-SERS spectroscopy for the detection of caffeine consumption from human saliva. Caffeine and paraxanthine as the major metabolite of caffeine were tested. Model samples of saliva spiked with caffeine were investigated, and detection of caffeine in real-life saliva samples was tested in order to ensure the viability of the method for clinical applications. Two doses of caffeine (2 mg/kg and 3.5 mg/kg) were ingested by volunteers, and their saliva samples were taken at different time periods ranging from 1 h to 10 h after the consumption. Density functional theory calculations of caffeine and paraxanthine adsorbed on the silver surface were performed in order to better understand the adsorption of the investigated molecules and to make a correct assignment of the experimental spectral bands of the EC-SERS spectra. It was determined that a low dose caffeine consumption can be detected by the appearance of the SERS spectral marker band of caffeine and paraxanthine at 692 cm-1. The intensity of this band is mostly reasoned by the paraxanthine concentration since the intensity changes of the band over time correlates to the concentration changes of paraxanthine determined by the pharmacokinetic studies of paraxanthine and caffeine in the human saliva. It was found that the limit of detection paraxanthine in saliva by means of EC-SERS is as low as 15 µM and can be further improved.

Understanding Escherichia coli damages after chlorophyllin-based photosensitization.

Pathogenic strains of bacteria are causing various illnesses all around the world and have a major socio-economic impact. Thus, fast- and low-cost methods for the microbial control of foods are needed. One of them might be photosensitization. This study looks deeper into the mechanism of Escherichia coli damage by chlorophyllin-based photosensitization. Fluorimetric data indicate that after 15 minute incubation with chlorophyllin (Chl) (1.5 × 10-5 M Chl) 0.73 ± 0.03 µM of this compound was associated with E. coli cell surface. After photoactivation (405 nm, 6-30 J/cm2 ) significant reduction (88.2%) of bacterial viability was observed. Higher concentration of Chl (5 × 10-4 M Chl) reduced viability of bacteria more than by 98%. Results indicated that reactive oxygen species (ROS) took place in this inactivation. Colloidal surface enhanced Raman scattering (SERS) spectroscopy was employed to detect the molecular changes in the treated bacteria. It was found that Chl-based based photosensitization triggers multiple surface structure changes in E. coli what induce lethal unrepairable damages and inactivation of pathogen.

Conformational diversity of the THF molecule in N2 matrix by means of FTIR matrix isolation experiment and Car-Parrinello molecular dynamics simulations.

Tetrahydrofuran (THF) is a widely used chemical compound, in particular as a solvent in organic and inorganic synthesis. The THF molecule has also an interesting property, namely, undergoes pseudorotation, similar to the case of the cyclopentane. Low energy difference between the envelope (Cs symmetry) and twisted (C2 symmetry) conformations of the THF molecule leads to the interconversion between the two conformers. We study the influence of the molecular environment (N2) on the Cs-C2 equilibrium of tetrahydrofuran in the THF@N2 system utilizing nitrogen matrix isolation infrared spectroscopy. We observe a different ratio between envelope (Cs) and twisted (C2) conformations with respect to a change of the temperature. FTIR experimental studies are supported by the results of the static density functional theory calculations and Car-Parrinello molecular dynamics simulations. We focus on the dynamics of the pseudorotation process, in particular, the lifetime of the THF conformations and their mutual rearrangements. On the basis of the THF@N2 matrix model, with explicit nitrogen molecules, the anharmonic infrared spectra are generated from the Fourier transformation of the dipole moment autocorrelation function.

Fiber attenuated total reflection infrared spectroscopy of kidney tissue during live surgery.

More than 90% of solid kidney tumors are cancerous and have to be treated by surgical resection where surgical outcomes and patient prognosis are dependent on the tumor discrimination. The development of alternative approaches based on a new generation of fiber attenuated total reflection (ATR) probes could aid tumor identification even under intrasurgical conditions. Herein, fiber ATR IR spectroscopy is employed to distinguish normal and cancerous kidney tissues. Freshly resected tissue samples from 34 patients are investigated under nearly native conditions. Spectral marker bands that allow a reliable discrimination between tumor and normal tissue are identified by a supervised classification algorithm. The absorbance values of the bands at 1025, 1155 and 1240 cm-1 assigned to glycogen and fructose 1,6-bisphosphatase are used as the clearest markers for the tissue discrimination. Absorbance threshold values for tumor and normal tissue are determined by discriminant analysis. This new approach allows the surgeon to make a clinical diagnosis.

PM-IRRAS mapping of ultrathin molecular films with high spatial resolution.

Polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) is a very sensitive technique to characterize the degree of molecular ordering in thin films on metallic surfaces. This is the first report of the coupling of a PM-IRRAS microscope to a free electron laser (FEL), a light source of highest brilliance. Some FELs emit in the infrared region and permit the mapping of molecular properties at high lateral resolution. We studied the molecular orientation of octadecanephosphonic acid (OPA) attached to a gold surface with microstructured aluminum oxide islands on the gold. The spatial resolution achieved is 12 microm which corresponds to the diffraction limit of the infrared light used in this study. This is a substantial improvement compared to previous studies using a PM-IRRA accessory together with a commercial Fourier transform infrared spectrometer, where the lateral resolution is noise-limited rather than diffraction-limited. The spectral maps reveal that OPA is preferably attached to the aluminum oxide islands via the bidentate binding mode whereas the tridentate mode is dominating in case of OPA attached to the gold areas.

Rapid intra-operative diagnosis of kidney cancer by attenuated total reflection infrared spectroscopy of tissue smears.

Herein, a technique to analyze air-dried kidney tissue impression smears by means of attenuated total reflection infrared (ATR-IR) spectroscopy is presented. Spectral tumor markers-absorption bands of glycogen-are identified in the ATR-IR spectra of the kidney tissue smear samples. Thin kidney tissue cryo-sections currently used for IR spectroscopic analysis lack such spectral markers as the sample preparation causes irreversible molecular changes in the tissue. In particular, freeze-thaw cycle results in degradation of the glycogen and reduction or complete dissolution of its content. Supervised spectral classification was applied to the recorded spectra of the smears and the test spectra were classified with a high accuracy of 92% for normal tissue and 94% for tumor tissue, respectively. For further development, we propose that combination of the method with optical fiber ATR probes could potentially be used for rapid real-time intra-operative tissue analysis without interfering with either the established protocols of pathological examination or the ordinary workflow of operating surgeon. Such approach could ensure easier transition of the method to clinical applications where it may complement the results of gold standard histopathology examination and aid in more precise resection of kidney tumors.

Label free molecular sexing of monomorphic birds using infrared spectroscopic imaging.

The absence of sexual dimorphism in many birds often makes sex determination difficult. In particular immature birds and adults of monomorphic species show no external sex characteristics. Molecular techniques based on DNA hybridization or polymerase chain reaction (PCR) are standard methods for sex identification. However, these methods are expensive and time consuming procedures and require special sample preparation. Noninvasive methods for a rapid determination of bird's gender are of increasing importance for ornithologists, breeders as well as for successful captive-breeding programs. Fourier transform infrared (FT-IR) spectroscopy is one such technique that can provide gender specific information. In this study, using the example of domestic pigeons (Columba livia f. dom.) we demonstrate that only a small amount of the feather pulp is needed to determine the gender. FT-IR spectroscopic images of feather pulp suspensions were recorded in transmission mode. Principal component analysis (PCA) and linear discriminant analysis (LDA) were performed to identify the sex. The gender related information are described by 2nd and 4th principal component principle component (PC). The 2nd PC represents different amounts of proteins while the 4th PC shows variations within the amide I and amide II bands as well as in the region of phosphate vibrations of nucleic acids. Blood cells of male pigeons exhibit a significantly higher amount of proteins and nucleic acids than those of female pigeons. Feather pulp samples of male species were assigned with 100% accuracy. Seven from eight female samples were assigned correctly while one sample could not be classified. This study demonstrates that the sex of domestic pigeons can be accurately and and rapidly identified by infrared spectroscopic imaging.

Biochemical Monitoring of Spinal Cord Injury by FT-IR Spectroscopy--Effects of Therapeutic Alginate Implant in Rat Models.

Spinal cord injury (SCI) induces complex biochemical changes, which result in inhibition of nervous tissue regeneration abilities. In this study, Fourier-transform infrared (FT-IR) spectroscopy was applied to assess the outcomes of implants made of a novel type of non-functionalized soft calcium alginate hydrogel in a rat model of spinal cord hemisection (n = 28). Using FT-IR spectroscopic imaging, we evaluated the stability of the implants and the effects on morphology and biochemistry of the injured tissue one and six months after injury. A semi-quantitative evaluation of the distribution of lipids and collagen showed that alginate significantly reduced injury-induced demyelination of the contralateral white matter and fibrotic scarring in the chronic state after SCI. The spectral information enabled to detect and localize the alginate hydrogel at the lesion site and proved its long-term persistence in vivo. These findings demonstrate a positive impact of alginate hydrogel on recovery after SCI and prove FT-IR spectroscopic imaging as alternative method to evaluate and optimize future SCI repair strategies.

On the stability of the hydrogen chloride complexes with ethylene and acetylene. A high resolution gas phase and ab initio study.

The temperature dependencies of the intensities of the HCl stretching bands of the hydrogen chloride complexes with acetylene and ethylene have been used to obtain estimates of the dissociation enthalpies of the two complexes. Quantum chemical calculations on the Hartree Fock and DFT/B3LYP levels of theory have been combined with experimental data to give estimates of the intensities of the HCl stretching vibration in the two complexes.

Identification of kidney tumor tissue by infrared spectroscopy of extracellular matrix.

Fourier transform infrared (FT-IR) spectroscopy was applied to characterize the extracellular matrix (ECM) of kidney tumor tissue and normal kidney tissue. Freshly resected tissue samples from 31 patients were pressed on a CaF2 substrate. FT-IR spectra obtained from ECM of tumor tissue exhibit stronger absorption bands in the spectral region from 1000 to 1200 cm⁻¹ and around 1750 cm⁻¹ than those obtained from normal tissue. It is likely that the spectra of ECM of kidney tumor tissue with large increases in the intensities of these bands represent a higher concentration of fatty acids and glycerol. Amide I and amide II bands are stronger in the spectra of ECM from normal tissue, indicating a higher level of proteins. Our results suggest that FT-IR spectroscopy of the ECM is an innovative emerging technology for real-time intraoperative tumor diagnosis, which may improve margin clearance in renal cancer surgery.