Structure, optoelectronic properties and thermal stability of the triple organic cation GAxFAxMA1-2xPbI3 system prepared by mechanochemical synthesis.

Halide perovskites are a well-known class of materials with many interesting applications. Great attention has been devoted to investigating halide perovskites containing triple methylammonium (MA+), formamidinium (FA+), and guanidinium (GA+) cations. Despite presenting very good applied perspectives so far, the lack of fundamental information for this system, such as its structural, thermal, and optoelectronic characteristics, prompts a step back before any technological leap forward. In the present work, we investigate the physical properties of mechanochemically solvent-free synthesized GAxFAxMA1-2xPbI3 halide perovskite powders with compositions of 0.00 ≤ x ≤ 0.15. We demonstrate that the synthesis of the powders can be performed by a simple manual mechanical grinding of the precursors for about 40 minutes, leading to solid solutions with an only minor content of unreacted precursors. X-ray diffraction, differential scanning calorimetry, and infrared spectroscopy techniques were used to investigate the structure, tetragonal-to-cubic phase transition, and vibrational characteristics of the organic cations with increasing GA+ and FA+ contents, respectively. The band gap and Urbach energies, obtained from ultraviolet-visible spectroscopy analyses, ranged from 1.58 to 1.65 eV and 23 to 36 meV, respectively, depending on the composition. These parameters demonstrate a non-random variation with x composition, which offers the possibility of a rational composition design for a given set of desired properties, demonstrating potential for optoelectronic applications. Finally, the system appears to have adequately tolerated heating for 12 hours at 120 °C in an ambient atmosphere, indicating high thermal stability and low ionic conductivity, which are desirable characteristics for solar cell applications.

Guanidinium substitution-dependent phase transitions, ionic conductivity, and dielectric properties of MAPbI3.

Despite the proven enhancement of MAPbI3 optoelectronic properties and stability by guanidinium substitution, divergences persist regarding fundamental knowledge on this system. This work shows that GAxMA1-xPbI3 solid solutions have guanidinium content-dependent phase transitions, dielectric permittivities, ionic conductivities, activation energies, and relaxation times.

DC bias electric field effects on ac electrical conductivity of MAPbI3suggesting intrinsic changes on structure and charge carrier dynamics.

Methylammonium lead iodide (MAPbI3) emerges as a promising halide perovskite material for the next generation of solar cells due to its high efficiency and flexibility in material growth. Despite intensive studies of their optical and electronic properties in the past ten years, there are no reports on dc bias electric field effects on conductivity in a wide temperature range. In this work, we report the combined effects of frequency, temperature, and dc bias electric field on the ac conductivity of MAPbI3. We found that the results of dc bias electric fields are very contrasting in the tetragonal and cubic phases. In the tetragonal phase, sufficiently high dc bias electric fields induce a conductivity peak appearance ∼290 K well evidenced at frequencies higher than 100 kHz. Excluding possible degradation and extrinsic factors, we propose that this peak suggests a ferroelectric-like transition. In the absence of a dc bias electric field, the ac conductivity in the tetragonal phase increases with temperature while decreases with temperature in the cubic phase. Also, ac activation energies for tetragonal and cubic phases were found to be inversely and directly proportional to the dc bias electric field, respectively. This behavior was attributed to the ionic conduction, possibly of MA+and I-ions, for the tetragonal phase. As for the cubic phase, the ac conduction dynamics appear to be metallic-like, which seems to change to a polaronic-controlled charge transport to increased dc bias electric fields.

Rapid and accurate assessment of the activity measurements in Brazilian hospitals and clinics.

Traceability in Nuclear Medicine Service (NMS) measurements was checked by the Institute of Radioprotection and Dosimetry (IRD) through the Institute of Energy and Nuclear Research (IPEN). In 2016, IRD ran an intercomparison program and invited Brazilian NMS authorized to administer 131I to patients. Sources of 131I were distributed to 33 NMSs. Three other sources from the same solution were sent to IRD, after measurement at IPEN. These sources were calibrated in the IRD reference system. A correction factor of 1.013 was obtained. Ninety percent of the NMS comparisons results are within ±10% of the National Laboratory of Metrology of Ionizing Radiation (LNMRI) value, the Brazilian legal requirement.

Preparation of [In-111]-labeled-DTPA-bombesin conjugates at high specific activity and stability: evaluation of labeling parameters and potential stabilizers.

The aim of the present work was to obtain stabilized high specific activity (HSA) (111)In-labeled bombesin conjugates for preclinical evaluations. Parameters influencing the kinetics of labeling were investigated and the effect of stabilizers on HSA radiopeptides stability at room temperature were systematically categorized applying chromatography techniques. A SA of 174 GBq/µmol was achieved with high radiochemical purity, but the labeled compounds exhibited low stability. The addition of stabilizers avoided their radiolysis and significantly increased their stability.

Novel series of (177)Lu-labeled bombesin derivatives with amino acidic spacers for selective targeting of human PC-3 prostate tumor cells.

AIM: Bombesin (BBN) has demonstrated the ability to bind with high affinity and specificity to GRP receptor, overexpressed on human prostate cancer. A large number of BBN derivatives have been synthesized for this purpose but most of them exhibit high abdominal accumulation, which may represent a problem in their clinical use due to serious side effects to patients. In this study we describe the results of radiolabeling with lutetium-177, stability and in vivo studies of novel phenyl-glycine-extended bombesin derivatives. The spacers were inserted to improve bombesin in vivo properties and to reduce its target to non-tumor sites. METHODS: Preliminary studies were done to establish the ideal conditions for labeling bombesin derivatives. Chromatography systems were applied to determine free lutetium and the stability of the preparations was evaluated either after storing at 2-8 ºC or incubation in human serum at 37 ºC. In vivo experiments included biodistribution, pharmacokinetics and SPECT images and were performed in Balb-c and Nude mice bearing PC-3 xenografts. RESULTS: The derivatives were labeled with high yield and kept stable at 2-8 ºC and are metabolized by human serum enzymes. In vivo studies showed fast blood clearance of labeled peptides and rapid excretion, performed mainly by renal pathway. In addition, biodistribution and imaging studies showed low abdominal accumulation and significant and specific tumor uptake of (177)Lu-labeled derivatives. CONCLUSIONS: The derivative with longer spacer holds a higher potential as radiopharmaceutical for prostate tumor diagnosis and the derivatives with shorter spacers are potential radiopharmaceuticals for prostate tumor treatment.

In vivo comparative study of hydroxyapatite labeled with different radioisotopes: evaluation of the scintigraphic images.

Radyosinovectomy (RSV) is a radiotherapeutic modality where a beta-emitting radionuclide is administered locally by intra-articular injection on the form of a colloid or radiolabeled particulate. RSV is a well-accepted therapeutic procedure in inflammatory joint diseases and has been successfully employed for more than 50 years as a viable alternative to surgical and chemical synovectomy. The aim of this work is to compare the in vivo stability of hydroxyapatite labelled with (177)Lu, (90)Y and (153)Sm. All radionuclides were labelled with high yield and were retained in the joint for 7 days, showing stability and usefulness as tools in the RSV treatment. A similar retention of the products in the muscle was observed when the particles were administrated in the muscle. However, the pure form of the radionuclides were rapidly cleared from the blood and accumulated in the liver when injected i.v.. Although (153)Sm-HA is already available for nuclear medicine procedures and clinical studies with (90)Y-HA have been developed, (177)Lu-labeled RSV agents will be economically more viable and has not been studied yet. Its favorable characteristics contribute to follow, to predict and asses the success of RSV by bone scintigraphy studies.

Radiolabeling of substance P with lutetium-177 and biodistribution study in rat pancreatic tumor xenografted nude mice.

Pancreatic tumor (PT) is a neuroendocrine neoplasm that usually origin metastases in the respiratory and gastrointestinal tract. The presence of peptide receptors at the cell membrane of PT constitutes the basis of the clinical use of specific radiolabeled ligands for its diagnosis and targeted therapy. Substance P (SP), an 11-amino acid peptide which has an important role in modulating pain transmission trough neurokinin type 1 (NK1r) and 2 receptors (NK2r), may play a role in the pathogenesis of PT, because approximately 10% of these tumors overexpress NK1r. The aim of the present work was to produce a pure and stable SP analog (DOTA-SP) radiolabeled with lutetium-177 ((177)Lu), and to evaluate its in vivo target to AR42J pancreatic tumor cells in Nude mice, in other to verify if SP can be used in this pancreatic tumor detection and treatment. Substance P was successfully labeled with high yield (>99%) at optimized conditions and kept stable for more than 72 hours at 2-8 degrees C and 4 hours in human plasma. Biodistribution studies showed that SP excretion was mainly performed by renal pathway. In addition, (177)Lu-DOTA-SP showed higher uptake by tumor than normal pancreas, indicating the presence of NK receptors in AR42J pancreatic tumor.

Development of a new bombesin analog radiolabeled with lutetium-177: in vivo evaluation of the biological properties in Balb-C mice.

In this work we describe the first results of radiolabeling with lutetium-177 ((177)Lu) and in vivo biodistribution and pharmacokinetics studies in normal Balb-c mice of a new bombesin analog (BEFG2)--DOTA-Phe-X-BBN(6-14), where X is a spacer of two aminoacids. Bombesin (BBN) is an amphibian analog of human gastrin releasing peptide (GRP). Development of radiolabeled BBN derivatives as agents for diagnostic imaging and systemic radiotherapy has increased considerable because of the observation that GRP receptors (GRPr) are over-expressed in a variety of human tumor cells, such as prostate tumor cells. (177)Lu-labeled peptides are attractive due to the excellent radiophysical properties and commercial availability of the radiometal. BEFG2 was successfully labeled with high yield and kept stable for more than 96 hours at 2-8 degrees C and 1 hour in human plasma. Data analysis obtained from the in vivo studies showed that the amount of BEFG2 present in plasma decreased rapidly and became almost undetectable at 60 min p.i., indicating rapid peptide excretion, which is performed mainly by renal pathway. In addition, biodistribution and single photon emission tomography showed low abdominal accumulation of (177)Lu-DOTA- Phe-X-BBN(6-14), indicating that this analog is a potential candidate for tumors target therapy.

Tecnetium-99m as alternative to produce somatostatin-labeled derivatives: comparative biodistribution evaluation with 111In-DTPA-octreotide.

Synthetic somatostatin (SST) analogues have been used in the preparation of receptor-specific radiopharmaceuticals for diagnostic and therapy of neuroendocrine tumors. This work studied the labeling conditions with (99m)Tc and biological distribution in Swiss mice of two SST analogs (HYNIC-Tyr(3)-Octreotide and HYNIC-Tyr(3)-Octreotate) and compared the biodistribution pattern with (111)In-DTPA-Octreotide. Biological distribution studies were performed after injection of radiopharmaceuticals on Swiss mice. Labeling procedures resulted on high radiochemical yield for all three preparations and the labeled products presented high in vitro stability. Biological distribution studies evidenced similar general biodistribution of (99m)Tc-labeled peptides when compared with indium-labeled peptide with fast blood clearance and elimination by urinary tract. Kidneys uptake of (99m)Tc-HYNIC-TATE are similar to (111)In-DTPA-Octreotide, and both are significantly higher than (99m)Tc-HYNIC-OCT. All labeled peptides presented similar uptake on liver, but the retention in time at intestines, particularly at large intestine, was more expressive for (111)In-labeled peptide. The %ID of (99m)Tc-HYNIC-OCT and (99m)Tc-HYNIC-TATE in organs with high density of SST receptors like pancreas and adrenals were significant and similar to obtained for (111)In-DTPA-Octreotide, confirming the affinity of these radiopharmaceuticals for the receptors.

A comparative study of 131I and 177Lu labeled somatostatin analogues for therapy of neuroendocrine tumours.

This work analysed the influence of the chelating group and radioligand on somatostatin analogues in vivo and in vitro properties. The presence of DOTA in the radioiodinated peptide produced a labeled analogue with similar blood kinetics and biodistribution to (177)Lu-DOTATATE and with lower abdominal uptake than (131)I-TATE. In addition, (131)I-DOTATATE showed significative tumour uptake, despite not so persistent after 24h. (131)I-DOTATATE can represent a cost-effective alternative to lutetium labeled peptide for neuroendocrine tumours therapy.

Physico-chemical properties of MTA and a novel experimental cement.

AIM: To evaluate the release of calcium ions, pH and conductivity of a new experimental dental cement (EC) and to compare them with those of mineral trioxide aggregate (MTA-Angelus). METHODOLOGY: Five samples of each cement were prepared using plastic tubes 1 mm in diameter and 10 mm long. Each sample was sealed in a test tube containing 10 mL deionized water which was analysed after 24, 48, 72, 96, 192, 240 and 360 h for pH, electrical conductivity and calcium release. The concentration of calcium ions was obtained through atomic absorption spectroscopy technique. The data were analysed statistically using the analysis of variance (anova) and the Student's test (t-test). RESULTS: The pH of the storage solutions was not affected by the material and the interaction of material with time (P > 0.05). However, the time of immersion was significant (P < 0.01) for both materials. For the electric conductivity and calcium release, the interaction of material with time was statistically significant (P < 0.01), indicating that EC and MTA-Angelus did not behave in a similar manner. CONCLUSIONS: The experimental cement released calcium and increased the pH of the storage solutions in a similar manner to MTA-Angelus. However, EC showed significantly higher calcium release than commercial MTA-Angelus after 24 h.

Optimization of a convenient route to produce N-succinimidyl 4-radiodobenzoate for radioiodination of proteins.

The preparation of N-succinimidyl-4-[131I]iodobenzoate (SIB) has been optimized using an alternative technique employing Cu(I)-assisted radioiododebromination that produces p-[131I]iodobenzoic acid. The reaction conditions were optimized and radiochemical purity of more than 90% was obtained when using 160 degrees C, 60 min reaction time and a [CuCl]/[p-bromobenzoic acid] relation of about 10(-2). After purification, the p-[131I]iodobenzoic acid reacted with TSTU to produce the SIB in a radiochemical yield greater than 98%. Protein conjugation using SIB resulted in a relatively low radiochemical yield. Biological distribution studies evidenced the in vivo stability of the labeled protein.

Radioiodination of proteins using prosthetic group: a convenient way to produce labelled proteins with in vivo stability.

Radiolabelled peptides can provide new approaches for radiopharmaceutical development. Several prosthetic groups have been developed for radioiodination of proteins in order to minimize in vivo dehalogenation. In this work, the prosthetic group N-succinimidyl 4-[131I]iodobenzoate ([131I]SIB) was obtained by an alternative procedure that employs Cu(I) assisted radioiododebromination to produce p-[131I]iodobenzoic acid with a radiochemical yield of 92.73 +/- 1.51% (N = 6), followed by the reaction with TSTU (O-(N-succinimidyl)-N,N,N'N'-tetramethyluronium) in alkaline medium. The HPLC profile of the final product, revealed that [131I]SIB was obtained with a radiochemical purity of 98.19 +/- 1.14% (N = 6 Swiss mices (normal group) and animals with inflammation focus developed on the right thigh by tupertine injection) were injected with human immunoglobulin (IgG) radioiodinated with [131I]SIB and by direct method (Iodogen). The comparison of results showed a fast blood clearance, better target organ/background relation and low uptake in thyroid and stomach (p < 0.01) for the protein labelled with [131I]SIB, what suggests a greater in vivo stability.

Enamel color change by microabrasion and resin-based composite.

A simple technique using microabrasion with hydrochloric acid/pumice and resin-based composite to improve the esthetics of discolored anterior teeth is described.

Scintigraphic evaluation of mycetoma.

Mycetoma is a rare deep mycosis caused by certain fungi. Clinical findings include enlargement and tumefaction of the affected region accompanied by grains coming out of the lesions. The feet are the most frequently affected area. Four patients have been studied who presented with mycetoma of the feet. Gallium scintigraphy was always abnormal in the affected areas and bone scintigraphy was abnormal in three of the four patients. The patient who had a normal bone study had received effective treatment (7 years). In the other patients the results were poor. Scintigraphic findings seem to be similar to those noted in cases of acute osteomyelitis associated with cellulitis, despite long-term therapy. Bone and gallium studies may be of possible value for therapy follow-up in cases of mycetoma.

Gallium scintigraphy in Hansen's disease.

Gallium 67 imaging was used in 12 patients with documented Hansen's disease undergoing treatment or not, in an attempt to determine the pattern of the disease. Diagnosis was confirmed by histopathology in all patients. The Mitsuda reaction was seen in all patients. Specific nuclear studies were performed when needed to evaluate particular organs better. Gallium 67 images show homogeneous, diffuse and moderate accumulation over the entire skin surface (except for the face) of untreated patients with multibacillary disease. The facial skin in these cases presented homogeneous, diffuse but very marked uptake of gallium. Internal organ involvement was variable. There was a very good correlation among clinical, scintigraphic, immunological and histopathological data. The pattern of the body skin ("skin outlining") and facial skin ("beard distribution") may be distinct for untreated patients with multibacillary leprosy.