Fiber Laser-Generated Silver-109 Nanoparticles for Laser Desorption/Ionization Mass Spectrometry of Illicit Drugs.

Cannabinoids and opioids are the most prominently used drugs in the world, with fentanyl being the main cause of drug overdose-related deaths. Monitoring drug use in groups as well as in individuals is an important forensic concern. Analytical methods, such as mass spectrometry (MS), have been found most useful for the identification of drug abuse on a small and large scale. Pulsed fiber laser 2D galvoscanner laser-generated nanomaterial (PFL 2D GS LGN) was obtained from monoisotopic silver-109. Nanomaterial was used for laser desorption/ionization mass spectrometry of selected illicit drug standards with standard high-resolution reflectron-based time-of-flight MALDI apparatus. Δ9-THC, 11-OH-THC, 11-COOH-THC, fentanyl, codeine, 6-monoacetylmorphine (6-MAM), heroin, tramadol, and methadone were chosen as test compounds. Illicit drugs were tested in a concentration range from 100 µg/mL to 10 pg/mL, equating to 50 µg to 50 fg per measurement spot. For all analyzed compounds, identification and quantification by silver-109-assisted laser desorption/ionization (LDI) MS was possible, with uncommon [M + 109Ag3]+ and [M - H]+ ions present for certain structures. The results of the quantitative analysis of drugs using silver-109 PFL 2D GS LGN for LDI MS are presented. Laser-generated NPs are proven to be useful for the analysis of selected drugs, with exceptionally good results for fentanyl monitoring in a broad range of concentrations.

Untargeted metabolomics of bladder tissue using liquid chromatography and quadrupole time-of-flight mass spectrometry for cancer biomarker detection.

Bladder cancer (BC) ranks among the most common cancers globally, with an increasing occurrence, particularly in developed nations. Utilizing tissue metabolomics presents a promising strategy for identifying potential biomarkers for cancer detection. In this study, we utilized ultra-high-performance liquid chromatography coupled with ultra-high-resolution mass spectrometry (UHPLC-UHRMS), incorporating both C18-silica and HILIC columns, to comprehensively analyze both polar and non-polar metabolite profiles in tissue samples from 99 patients with bladder cancer. By utilizing an untargeted approach with external validation, we identified twenty-five tissue metabolites that hold promise as potential indicators of BC. Furthermore, twenty-five characteristic tissue metabolites that exhibit discriminatory potential across bladder cancer tumor grades, as well as thirty-nine metabolites that display correlations with tumor stages were presented. Receiver operating characteristics analysis demonstrated high predictive power for all types of metabolomics data, with area under the curve (AUC) values exceeding 0.966. Notably, this study represents the first report in which human bladder normal tissues adjacent to cancerous tissues were analyzed using UHPLC-UHRMS. These findings suggest that the metabolite markers identified in this investigation could serve as valuable tools for the detection and monitoring of bladder cancer stages and grades.

Metabolomic profiling of human bladder tissue extracts.

INTRODUCTION: Bladder cancer is a common malignancy affecting the urinary tract and effective biomarkers and for which monitoring therapeutic interventions have yet to be identified. OBJECTIVES: Major aim of this work was to perform metabolomic profiling of human bladder cancer and adjacent normal tissue and to evaluate cancer biomarkers. METHODS: This study utilized nuclear magnetic resonance (NMR) and high-resolution nanoparticle-based laser desorption/ionization mass spectrometry (LDI-MS) methods to investigate polar metabolite profiles in tissue samples from 99 bladder cancer patients. RESULTS: Through NMR spectroscopy, six tissue metabolites were identified and quantified as potential indicators of bladder cancer, while LDI-MS allowed detection of 34 compounds which distinguished cancer tissue samples from adjacent normal tissue. Thirteen characteristic tissue metabolites were also found to differentiate bladder cancer tumor grades and thirteen metabolites were correlated with tumor stages. Receiver-operating characteristics analysis showed high predictive power for all three types of metabolomics data, with area under the curve (AUC) values greater than 0.853. CONCLUSION: To date, this is the first study in which bladder human normal tissues adjacent to cancerous tissues are analyzed using both NMR and MS method. These findings suggest that the metabolite markers identified in this study may be useful for the detection and monitoring of bladder cancer stages and grades.

Infrared pulsed fiber laser-produced gold and silver-109 nanoparticles for laser desorption/ionization mass spectrometry of steroid hormones.

RATIONALE: Hormones are compounds that perform many important functions in the human body, but above all their task is to maintain homeostasis by adapting them to the constantly changing environmental conditions. Even minor hormonal disorders have a negative effect on the body, leading to physical or mental changes. Therefore, monitoring these changes and precise quantification of hormones are essential for the early diagnosis of diseases related to hormonal disorders. METHODS: Application of monoisotopic silver-109 and gold nanoparticles obtained by PFL (pulsed fiber laser) 2D GS (galvo-scanner) LGN (laser-generated nanomaterial) for high-resolution laser desorption/ionization mass spectrometry (LDI-MS) and mass spectrometry imaging (MSI) of steroid hormones is presented. Four steroid hormones, estrone, prednisolone, corticosterone and progesterone, were used as test compounds for quantitative analysis with matrix-assisted LDI time-of-flight MS apparatus. Moreover, comparison of manual measurements and semiautomatic MSI with both types of nanoparticles was performed. Methods were also tested on spiked human blood serum for quantification of steroid hormones and for estimation of the matrix effect. RESULTS: Hormones were directly tested in 1 000 000-fold concentration change conditions ranging from 1 mg/mL to 1 ng/mL which equates to 300 ng to 300 fg of hormone per measurement spot. For almost all tested hormones MSI allowed one to obtain equal or lower limit of detection value than manual LDI-MS. The best results judged by lowest limit of detection values are found for silver-109 nanoparticles. CONCLUSION: The results of the quantitative analysis of steroid hormones using silver-109 and gold nanoparticles prepared with PFL 2D GS LGN for LDI-MS and semiautomatic LDI-MSI are presented. It has been proven that nanoparticles obtained by laser synthesis can be successfully used for the analysis of steroid hormones in a wide range of concentrations.

Surgical treatment results of parapharyngeal space tumors: a report of 22 cases.

INTRODUCTION: Parapharyngeal space (PPS) is the anatomical area lateral to the upper pharynx and clinically important due to PPS tumors. They account for less than 1% of head and neck neoplasms. Both benign and malignant neoplasms may arise there and typical for this localization is diversity of histological origin. Complete surgical excision is still the basis of treatment. AIM OF THE STUDY: Evaluation of the results of surgical treatment of PPS tumors in the Department of Otolaryngology at the Medical University over the period 2015-2017. MATERIAL AND METHODS: A retrospective analysis of medical records including complaints, physical examination, results of imaging studies, surgical approach, postoperative complication and histopathological results in 22 patients with a diagnosis of a PPS tumors. RESULTS: The most frequent complaints reported by the patients were: discomfort in the throat, dysphagia, hearing disorders and a palpable tumor on the neck. Asymptomatic course of the disease was demonstrated in 4 cases. All patients were treated surgically: 2 with transoral approach, 9 with transparotid-transcervical approach, 11 with transcervical approach. In most cases the tumor was removed radically. In 2 patients intracapsular tumor resection was performed. Based on histopathological examination the benign lesions dominated (18/22). In 4 cases malignant neoplasms were diagnosed: carcinoma ex pleomorphic adenoma, adenoid cystic carcinoma and two cases of squamous cell carcinoma. The most common origin of PPS tumors was deep lobe of parotid gland and for this group 11 patients had diagnosis of pleomorphic adenoma. Other diagnosis included: paraganglioma, neurofibroma, hemangioma, lymphangioma and rhabdomyoma. Postoperative complications occurred in 9 patients and presented as hoarseness and dysphagia due to paresis of the lower group of cranial nerves (IX, X, XII). Significant intraoperative bleeding during surgery occurred in 2 cases and ligation of the external carotid artery was necessary. CONCLUSION: Due to the anatomical topography of PPS and its content with the essential vessels and the lower group of cranial nerves, the surgical treatment of pathology of this area is still a challenge for head and neck surgeons. The decrease of voice quality and impaired speech and swallowing should always be considered as complications post the surgical resection in PPS.