Spectroscopic and Thermographic Qualities of Praseodymium-Doped Oxyfluorotellurite Glasses.

The thermal stability of oxyfluorotellurite glass systems, (65-x)TeO2-20ZnF2-12PbO-3Nb2O5-xPr2O3, doped with praseodymium was examined. The different concentrations of praseodymium oxide (x = 0.5 and 2 mol%) were applied to verify the thermal, optical and luminescence properties of the materials under study. The relatively high values of the Dietzel (ΔT) and Saad-Poulain (S or H') thermal stability factors determined using a differential thermal analysis (DTA) indicate the good thermal stability of the glass matrix, which gradually improves with the content of the active dopant. The temperature dependence of optical spectra in the temperature range 300-675 K for the VIS-NIR region was investigated. The involved Pr3+ optical transition intensities and relaxation dynamic of the praseodymium luminescent level were determined. The ultrashort femtosecond pulses were utilized to examine a dynamic relaxation of the praseodymium luminescent levels. Although the measured emission of the Pr3+ active ions in the studied glass encompasses the quite broad spectral region, the observed luminescence may only be attributed to 3PJ excited states. As a result, the observed decrease in the experimental lifetime for the 3P0 level along with the increasing activator content was identified as an intensification of the Pr-Pr interplay and the associated self-quenching process. The maximum relative sensitivities (Sr) estimated over a relatively wide temperature range are ~0.46% K-1 (at 300 K) for FIR (I530/I497) and 0.20% K-1 (at 600 K) for FIR (I630/I497), which seems to confirm the possibility of using investigated glasses in optical temperature sensors.

UVC Stokes and Anti-Stokes Emission of Ca9Y(PO4)7 Polycrystals Doped with Pr3+ Ions.

The recent COVID-19 pandemic has made everyone aware of the threat of viruses and the growing number of antibiotic-resistant bacteria. It has become necessary to find new methods to combat these hazards. One tool that could be used is UVC radiation, i.e., 100-280 nm. Currently, the available sources of this light are mercury vapor lamps. However, the modern world requires more compact, mercury-free, and less energy-consuming light sources. This work presents the results of our research on a new material in which efficient UVC radiation was obtained. Here, we present the results of research on Ca9Y(PO4)7 polycrystals doped with Pr3+ ions prepared using the solid-state method. The absorption, excitation, emission, and emission decay profiles of praseodymium(III) ions were measured and analyzed. The upconversion emission in the UVC region excited by blue light was observed. Parameters such as energy bandgap, refractive index, and thermal stability of luminescence were determined. The studied phosphate-based phosphor possesses promising characteristics that show its potential in luminescent applications in future use in medicine or for surface disinfection.

UVC Up-Conversion and Vis-NIR Luminescence Examined in SrO-CaO-MgO-SiO2 Glasses Doped with Pr3.

The application of ultraviolet-C light in the field of surface treatment or photodynamic therapy is highly prospective. In this regard, the stable fluorescent silicate SrO-CaO-MgO-SiO2-Pr2O3 glasses able to effectively convert visible excitation on the ultraviolet praseodymium emission were fabricated and examined. An unusual wide-range visible-to-UVC up-conversion within 240-410 nm has been achieved in Pr3+-doped glasses, revealing their potential advantage in different sophisticated disinfection technologies. The integrated emission intensity was studied as a function of light excitation power to assess a mechanism attributed to UVC luminescence. Especially, it was revealed that the multicomponent silicate glass qualities and praseodymium 3PJ excited state peculiarities are favorable to obtaining useful broadband ultraviolet up-converted luminescence. The glass dispersion qualities were determined between 450-2300 nm. The impact of praseodymium concentration on Vis-NIR spectroscopic glass qualities was evaluated employing absorption spectra, emission spectra, and decay curves of luminescence associated with two involved praseodymium excited states. Especially, efficient interionic interactions can be inferred by investigating the decrease in 1D2 state experimental lifetime in the heavily doped samples. Examination of absorption spectra as a function of temperature implied that excitation at 445 nm should be quite effective up to T = 625 K. Contrary to this, temperature elevation gives rise to a moderate lowering of the visible praseodymium luminescence.

Luminescence Properties of an Orthorhombic KLaF4 Phosphor Doped with Pr3+ Ions under Vacuum Ultraviolet and Visible Excitation.

Fluorides have a wide bandgap and therefore, when doped with the appropriate ions, exhibit emissions in the ultraviolet C (UVC) region. Some of them can emit two photons in the visible region for one excitation photon, having a quantum efficiency greater than 100%. In a novel exploration, praseodymium (Pr3+) ions were introduced into KLaF4 crystals for the first time. The samples were obtained according to a high-temperature solid-state reaction. They exhibited an orthorhombic crystal structure, which has not been observed for this lattice yet. The optical properties of the material were investigated in the ultraviolet (UV) and visible ranges. The spectroscopic results were used to analyze the Pr3+ electronic-level structure, including the 4f5d configuration. It has been found that KLaF4:Pr3+ crystals exhibit intense luminescence in the UVC range, corresponding to multiple 4f → 4f transitions. Additionally, under vacuum ultraviolet (VUV) excitation, distinct transitions, specifically 1S0 → 1I6 and 3P0 → 3H4, were observed, which signifies the occurrence of photon cascade emission (PCE). The thermal behavior of the luminescence and the thermometric performance of the material were also analyzed. This study not only sheds light on the optical behavior of Pr3+ ions within a KLaF4 lattice but also highlights its potential for efficient photon management and quantum-based technologies.

Conformation of the hydrazo bond in new 2-methyl-3,5-dinitro-6-(2-phenylhydrazinyl)pyridine and its influence on the structural and optic properties - Quantum chemical DFT calculations.

A new methyl-dinitro-phenylhydrazinyl-pyridine derivative [2-methyl-3,5-dinitro-6-(2-phenylhydrazinyl)pyridine] was synthesised and characterised by means of structural and spectroscopic measurements. The X-ray diffraction studies revealed that the compound crystallises in the centrosymmetric monoclinic space group P21/n, with two symmetry-independent molecules in the asymmetric unit with Z = 8. Hydrazo bridge C-NH-NH-C links two fragments composed of phenyl ring and pyridine unit substituted with methyl and nitro groups. Such a structure was confirmed by 1H and 13C NMR studies as well as IR, Raman, UV-Vis, and emission spectra. The results were analysed using the quantum-chemical DFT calculations. The paper reports the vibrational characteristics and discusses dynamical properties of this moiety. The full set of the normal modes typical of the hydrazo bridge was identified and assigned to respective IR and Raman bands. The results of structural and spectroscopic studies were used to find the dependence between the conformation of the θ-NH-NH-ϕ system and its optic properties. The experimental UV-Vis and emission spectra were discussed in terms of the calculated singlet and triplet states that allowed assigning the unique spectral pattern originating from the electrons of the hydrazo-bridge system.

Chitosan and Its Carboxymethyl-Based Membranes Produced by Crosslinking with Magnesium Phytate.

Membranes produced by crosslinking chitosan with magnesium phytate were prepared using highly deacetylated chitosan and its N-carboxymethyl, O-carboxymethyl and N,O-carboxymethyl derivatives. The conditions of the membrane production were described. IR, Raman, electron absorption and emission spectra were measured and analyzed for all the substrates. It was found that O-carboxymethyl chitosan derivative is the most effectively crosslinked by magnesium phytate, and the films formed on this substrate exhibit good mechanical parameters of strength, resistance and stability. Strong O-H···O hydrogen bonds proved to be responsible for an effective crosslinking process. Newly discovered membrane types produced from chitosan and magnesium phytate were characterized as morphologically homogenous and uniform by scanning electron microscopy (SEM) and IR measurements. Due to their good covering properties, they do not have pores or channels and are proposed as packaging materials.

Spectroscopic and optical properties of 1,2,4-triazolo[4,3-a]pyridin-3(2H)-one as a component of herbicides.

The herbicides azafenidin [(2-(2,4-dichloro-5-prop-2-ynoxyphenyl)-5,6,7,8-tetrahydro-[1,2,4]triazolo[4,3-a]pyridin-3-one)] and flumetsulam [(N-(2,6-difluorophenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-2-sulfonamide)] were subjected to IR, Raman, UV-Vis and emission studies. As triazolopyridine is the most prominent and active component of these herbicides, this molecule was characterised by XRD studies, FTIR, Raman, UV-Vis and emission spectra. The experimental data were compared to the results of the DFT quantum chemical calculations carried out for its optimised structure, IR intensities and Raman activities, HOMO-LUMO transitions, and energies of the singlet and triplet states. The characteristics for triazolopyridine quantities were used in the analysis of the studied herbicides.

Exploring Structure-Sensitive Factors Relevant to Cryogenic Laser Operation in Oxide Crystals Doped with Er3+ Ions.

Crystals of Gd3Al2.5Ga2.5O12:Er3+, (Lu0.3Gd0.7)2SiO5:Er3+ and LiNbO3:Er3+ compounds differing in origin and the nature of their inherent structural disorder were crystalized. Optical absorption and luminescence spectra for transitions between the 4I15/2 and the 4I13/2 multiplets of Er3+ ions for the crystal samples were recorded versus temperatures in the region of 80-300 K. Gathered data were analyzed thoroughly providing the in-depth knowledge of the effects of temperature on intensities, wavelengths and bandwidths of Er3+ transitions. The information acquired together with the knowledge of significant structural dissimilarities of the host crystals chosen made it possible to propose an interpretation of the impact of a structural disorder in Er3+-doped crystals on their spectroscopic properties, and to determine their lasing ability at cryogenic temperatures upon resonant (in-band) optical pumping.

Enhanced Emission of Tellurite Glass Doped with Pr3+/Ho3+ and Their Applications.

The shielding and spectroscopic properties of Pr+3 and Pr3+/Ho3+-codoped tellurite glass were investigated. The intensity parameters (Ω2 = 3.24-, Ω4 = 1.64-, Ω6 = 1.10 × 10-20 cm2) as well as the radiative lifetimes of 3F4 + 5S2 and 5I6 excited states of Ho3+ ions were equal to 301 µs and 3.0 µs, respectively. The former value appears to be much higher than that obtained from the lifetime measurement, indicating the presence of various energy transfer processes. The NIR spectrum of Pr3+/Ho3+-co-doped tellurite glass is dominated by strong Ho3+: 5I6 emission at around 1200 nm, being the result of the energy transfer from Pr3+ to Ho3+ ions. The shielding effectiveness of the prepared glasses showed good performance against high-energy photons. These findings suggest that the prepared glasses could be used in laser technology such as photodynamic therapy (PDT) treatment procedures and as shielding for radiation protection.

Examining the Spectroscopic and Thermographic Qualities of Er3+-doped Oxyfluoride Germanotellurite Glasses.

Novel ternary fluoro-germano-tellurite (GTS) glasses doped with Er3+ ions with 0.5 mol% and 1.0 mol% were fabricated by a conventional melt and quenching method and investigated using methods of optical spectroscopy. The room-temperature absorption spectrum was recorded and analyzed to determine radiative transition rates, radiative lifetimes, and branching ratios of Er3+ luminescence. Decay curves of Er3+ luminesccence were recorded and analyzed. Temperature dependences of emission spectra and absorption spectra in the region from RT (room-temperature) up to 675 K were studied in detail. The contribution of competing radiative and nonradiative processes to the relaxation of luminescent levels of Er3+ was assessed. Absolute and relative sensitivity were established utilizing the comprehensive model based on thermally coupled 2H11/2/4S3/2 excited states of erbium. The high quantum efficiency of the first erbium-excited state and value of gain coefficient indicate that GTS:Er glass system can be considered as conceivable NIR (near infrared) laser material as well.

The Structural and Optical Properties of 1,2,4-Triazolo[4,3-a]pyridine-3-amine.

The structural and spectroscopic properties of a new triazolopyridine derivative (1,2,4-triazolo[4,3-a]pyridin-3-amine) are described in this paper. Its FTIR spectrum was recorded in the 100-4000 cm-1 range and its FT-Raman spectrum in the range 80-4000 cm-1. The molecular structure and vibrational spectra were analyzed using the B3LYP/6-311G(2d,2p) approach and the GAUSSIAN 16W program. The assignment of the observed bands to the respective normal modes was proposed on the basis of PED calculations. XRD studies revealed that the studied compound crystallizes in the centrosymmetric monoclinic space group P21/n with eight molecules per unit cell. However, the asymmetric unit contains two 1,2,4-triazolo[4,3-a]pyridin-3-amine molecules linked via N-H⋯N hydrogen bonds with a R22(8) graph. The stability of the studied molecule was considered using NBO analysis. Electron absorption and the luminescence spectra were measured and discussed in terms of the calculated singlet, triplet, HOMO and LUMO electron energies. The Stokes shifts derived from the optical spectra were equal to 9410 cm-1 for the triazole ring and 7625 cm-1 for the pyridine ring.

Laser Refrigeration by an Ytterbium-Doped NaYF4 Microspinner.

Thermal control of liquids with high (micrometric) spatial resolution is required for advanced research such as single molecule/cell studies (where temperature is a key factor) or for the development of advanced microfluidic devices (based on the creation of thermal gradients at the microscale). Local and remote heating of liquids is easily achieved by focusing a laser beam with wavelength adjusted to absorption bands of the liquid medium or of the embedded colloidal absorbers. The opposite effect, that is highly localized cooling, is much more difficult to achieve. It requires the use of a refrigerating micro-/nanoparticle which should overcome the intrinsic liquid heating. Remote monitoring of such localized cooling, typically of a few degrees, is even more challenging. In this work, a solution to both problems is provided. Remote cooling in D2 O is achieved via anti-Stokes emission by using an optically driven ytterbium-doped NaYF4 microparticle. Simultaneously, the magnitude of cooling is determined by mechanical thermometry based on the analysis of the spinning dynamics of the same NaYF4 microparticle. The angular deceleration of the NaYF4 particle, caused by the cooling-induced increase of medium viscosity, reveals liquid refrigeration by over -6 K below ambient conditions.

Clinical Significance of Peritoneal Fluid Examination for Free Cancer Cells in Patients Qualified for Surgery for Gastric Cancer.

Background: Peritoneal lavage cytology in patients with gastric cancer may correlate with an unfavorable prognosis. This study evaluated the presence of free cancer cells in the peritoneal lavage of a population of patients with gastric cancer and its correlation with the outcome of surgical treatment. Methods: One hundred patients diagnosed with gastric or gastrointestinal junction adenocarcinoma underwent surgery. In all patients, a cytological and immunohistochemical analysis of peritoneal lavage was performed. Based on the presence of free cancer cells (fcc) at the cytological and immunohistochemical examination of peritoneal lavage, patients undergoing surgery for gastric cancer were divided into two groups: fcc (+) and fcc (-). Results: A total of 100 patients, 37 women, and 63 men with a median age of 65 years were included in the study. In the entire study group, 16 (16%) patients were positive for the presence of free cancer cells (fcc +) at peritoneal lavage examination. However, in the group of patients who underwent gastrectomy, fcc (+) was found in 10 out of 77 (13%) patients. The presence of cancer cells in peritoneal lavage was a strong predictive factor in an unfavorable outcome after surgery, and 1-year and 2-year patient survival was 34 and 0% in fcc (+) patients and 79 and 59% in fcc (-), respectively. Moreover, the presence of free cancer cells was associated with a five-fold increased risk of death within 2 years after surgery. When analyzing the group of patients undergoing R0/R1 surgery, this difference was even more significant (p < 0.0001). Conclusions: The presence of free cancer cells in peritoneal lavage may significantly affect the outcome of patients with gastric cancer. Radical surgery in patients with free cancer cells in the peritoneal lavage did not result in a survival advantage. Identification of free cancer cells could help for a better stratification of gastric cancer patients, identifying those patients who could better benefit from a radical surgical treatment, finally improving long-term survival.

Broadband Near-Infrared Luminescence in Lead Germanate Glass Triply Doped with Yb3+/Er3+/Tm3.

This paper deals with broadband near-infrared luminescence properties of lead germanate glass triply doped with Yb3+/Er3+/Tm3+. Samples were excited at 800 nm and 975 nm. Their emission intensities and lifetimes depend significantly on Er3+ and Tm3+ concentrations. For samples excited at 800 nm, broadband emissions corresponding to the overlapped 3H4 → 3F4 (Tm3+) and 4I13/2 → 4I15/2 (Er3+) transitions centered at 1.45 µm and 1.5 µm was identified. Measurements of decay curves confirm reduction of 3H4 (Tm3+), 2F5/2 (Yb3+) and 4I13/2 (Er3+) luminescence lifetimes and the presence of energy-transfer processes. The maximal spectral bandwidth equal to 269 nm for the 3F4 → 3H6 transition of Tm3+ suggests that our glass co-doped with Yb3+/Er3+/Tm3+ is a good candidate for broadband near-infrared emission. The energy transfer from 4I13/2 (Er3+) to 3F4 (Tm3+) and cross-relaxation processes are responsible for the enhancement of broadband luminescence near 1.8 µm attributed to the 3F4 → 3H6 transition of thulium ions in lead germanate glass under excitation of Yb3+ ions at 975 nm.

Exploring the Impact of Structure-Sensitivity Factors on Thermographic Properties of Dy3+-Doped Oxide Crystals.

Optical absorption spectra and luminescence spectra were recorded as a function of temperature between 295 K and 800 K for single crystal samples of Gd2SiO5:Dy3+, Lu2SiO5:Dy3+, LiNbO3:Dy3+, and Gd3Ga3Al2O12:Dy3+ fabricated by the Czochralski method and of YAl3(BO3)4:Dy3+ fabricated by the top-seeded high temperature solution method. A thermally induced change of fluorescence intensity ratio (FIR) between the 4I15/2→ 6H15/2 and 4F9/2 → 6H15/2 emission bands of Dy3+ was inferred from experimental data. It was found that relative thermal sensitivities SR at 350 K are higher for YAl3(BO3)4:Dy3+ and Lu2SiO5:Dy3+than those for the remaining systems studied. Based on detailed examination of the structural peculiarities of the crystals it was ascertained that the observed difference between thermosensitive features cannot be attributed directly to the dissimilarity of structural factors consisting of the geometry and symmetry of Dy3+ sites, the number of non-equivalent Dy3+ sites, and the host anisotropy. Instead, it was found that a meaningful correlation between relative thermal sensitivity SR and rates of radiative transitions of Dy3+ inferred from the Judd-Ofelt treatment exists. It was concluded that generalization based on the Judd-Ofelt parameters and luminescence branching ratio analysis may be useful during a preliminary assessment of thermosensitive properties of new phosphor materials.

Synergy between NIR luminescence and thermal emission toward highly sensitive NIR operating emissive thermometry.

There are many figures of merit, which determine suitability of luminescent thermometers for practical applications. These include thermal sensitivity, thermal accuracy as well as ease and cost effectivness of technical implementation. A novel contactless emission thermometer is proposed, which takes advantage of the coexistence of photoluminescence from Nd3+ doping ions and black body emission in transparent Nd3+ doped-oxyfluorotellurite glass host matrix. The opposite temperature dependent emission from these two phenomena, enables to achieve exceptionally high relative sensitivity SR = 8.2%/°C at 220 °C. This enables to develop new type of emissive noncontact temperature sensors.

Phonon Sideband Analysis and Near-Infrared Emission in Heavy Metal Oxide Glasses.

In this work, spectroscopic properties of europium and erbium ions in heavy metal oxide glasses have been studied. The phonon energy of the glass host was determined based on Eu3+ excitation spectra measurements. Near-IR emission spectra at 1550 nm related to 4I13/2 → 4I15/2 transition of erbium in heavy metal glasses were examined with special regards to luminescence bandwidth and measured lifetime. In particular, correlation between phonon energy and the measured lifetime 4I13/2 (Er3+) was proposed. The luminescence lifetime for the 4I13/2 upper laser state of erbium decreases with increasing phonon energy in glass matrices. Completely different results were obtained glass samples with europium ions, where the 5D0 lifetime increases with increasing phonon energy. Our investigations suggest that the values of measured 5D0 lifetime equal to radiative lifetimes for all heavy metal oxide glasses.

Spectroscopic and structural investigations of blue afwillite from Ma'ale Adummim locality, Palestinian Autonomy.

Until now, only the colourless crystals of mineral afwillite, Ca3(HSiO4)2·2H2O, were known from several localities around the world. Present work focuses on blue afwillite counterparts from the Ma'ale Adummim locality in Palestine. Using the wide spectrum of analytical methods we attempted to identify the causes of this unusual colour. Structural investigation confirms the presence of two tetrahedral SiO3OH units connected by hydrogen bonds. The Raman spectrum of afwillite, obtained for the first time, shows the increased number of bands in the range of 785-970 cm-1, whose assignation was correlated with the presence of two different kinds of structural units: (SiO3OH)3- and its deprotonated counterpart (SiO4)4-. The heating process at 250 °C, in addition to the colour changes from blue to pastel green, shows the intensity reduction and disappearing of some Raman bands attributed mainly to SiO3OH units. The IR investigation confirms also the presence of that unit and provides information that the position and designation of infrared bands above ∼2300 cm-1 is related to the strength of hydrogen bonds within the structure. The stretching and bending OH vibrations of afwillite sample show the partial shift to the lower spectral frequencies after the H/D isotopic exchange in OH or H2O groups. Based on the results of the electron absorption and luminescence analyses it has been proposed that the blue colour of afwillite is caused by hole oxygen defect, most probably SiO3-.

Yield of staging laparoscopy in gastric cancer is influenced by Laurén histologic subtype.

BACKGROUND: Staging laparoscopy (SL) with cytologic lavage is a useful staging procedure that allows tailoring the treatment of advanced gastric cancer (GC). The current study aimed to evaluate the total yield of SL in patients with various Laurén histo-types of GC, before planned neoadjuvant chemotherapy and gastrectomy. METHODS: After exclusion of distant metastatic disease on imaging modalities, 173 patients with primary advanced gastric adenocarcinoma who underwent SL between August 2016 and September 2018, were eligible for the analysis. Patients sex, age, Lauren histo-type, tumor location, grade, cT, and cN were assessed in bivariate analysis. Multivariable logistic regression analysis was used to identify independent factors associated with peritoneal metastases. RESULTS: Peritoneal metastases, ascites, and positive cytology were found in 39 (22.5%), 17 (9.8%) and 38 (22%) patients, respectively. The total yield of the SL in the current study was 36.4%. Multivariable logistic regression analysis revealed that serosal involvement (cT4) and diffuse histo-type were independent predictors of peritoneal metastases (OR, 15; 95% CI, 1.9-119, P = .02 and OR, 2.4; 95% CI, 1.2-4.6, P = .01, respectively). CONCLUSIONS: Although cT4 and diffuse tumors show the highest association with peritoneal metastases, SL is a valuable diagnostic procedure in all advanced GC patients.

Prognostic significance, diagnosis and treatment in patients with gastric cancer and positive peritoneal washings. A review of the literature.

Peritoneal dissemination is a common consequence of a relapse following a radical surgical treatment of gastric cancer. The development of the disease in the peritoneum depends not only on its stage, but also on free cancer cells exfoliated from the tumor mass or from involved lymph nodes, and which are capable of being implanted in the peritoneum. According to the latest TNM (7 edition; 2010) classification, patients with free cancer cells in the peritoneal washings qualify for stage IV of the disease. Patients in whom free cancer cells were found during the operation - have a recurrence of gastric cancer - mainly in the peritoneum, and the majority of them die within two years of the diagnosis. To properly assess the prognosis, it is vital to determine the stage of cancer by additionally assessing the washings for the presence of free cancer cells before taking a therapeutic decision. This also allows identifying those patients who require different medical procedures to obtain the best treatment results possible. Medical literature describes various methods of examining peritoneal washings aimed at detecting free cancer cells. The methods apply different cancer cell detection rates, sensitivity and specificity in prediction of a peritoneal relapse. Oncological Departments performing the evaluation of the washings employ non-standard methods of treatment in this group of patients and the results presented are promising.