Engineering Metal Halide Perovskite Nanocrystals with BODIPY Dyes for Photosensitization and Photocatalytic Applications.

The sensitization of surface-anchored organic dyes on semiconductor nanocrystals through energy transfer mechanisms has received increasing attention owing to their potential applications in photodynamic therapy, photocatalysis, and photon upconversion. Here, we investigate the sensitization mechanisms through visible-light excitation of two nanohybrids based on CsPbBr3 perovskite nanocrystals (NC) functionalized with borondipyrromethene (BODIPY) dyes, specifically 8-(4-carboxyphenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BDP) and 8-(4-carboxyphenyl)-2,6-diiodo-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (I2-BDP), named as NC@BDP and NC@I2-BDP, respectively. The ability of I2-BDP dyes to extract hot hole carriers from the perovskite nanocrystals is comprehensively investigated by combining steady-state and time-resolved fluorescence as well as femtosecond transient absorption spectroscopy with spectroelectrochemistry and quantum chemical theoretical calculations, which together provide a complete overview of the phenomena that take place in the nanohybrid. Förster resonance energy transfer (FRET) dominates (82%) the photosensitization of the singlet excited state of BDP in the NC@BDP nanohybrid with a rate constant of 3.8 ± 0.2 × 1010 s-1, while charge transfer (64%) mediated by an ultrafast charge transfer rate constant of 1.00 ± 0.08 × 1012 s-1 from hot states and hole transfer from the band edge is found to be mainly responsible for the photosensitization of the triplet excited state of I2-BDP in the NC@I2-BDP nanohybrid. These findings suggest that the NC@I2-BDP nanohybrid is a unique energy transfer photocatalyst for oxidizing α-terpinene to ascaridole through singlet oxygen formation.

The role of the oxime group in the excited state deactivation processes of indirubin.

The introduction of an oxime group into indirubin (INR) derivatives, including INROx, MINROx, and 6-BrINROx, and its impact on the spectral and photophysical properties of INR was investigated using a combination of fast-transient absorption (fs-TA/fs-UC) and steady-state fluorescence techniques. The oxime group introduces structural modifications that promote a rapid keto-enol tautomeric equilibrium and enhance the excited-state proton transfer (ESPT) process compared to its analogue, INR. In the oxime-indirubin derivatives investigated, the ESPT process is notably more efficient than what is observed in INR and indigo, occurring extremely fast (<1 ps) in all solvents, except for the viscous solvent glycerol. The more rapid deactivation mechanism precludes the formation of an intermediate species (syn-rotamer), as observed with INR. These findings are corroborated by time-dependent density functional theory (TDDFT) calculations. The work demonstrates that introducing an oxime group to INR, whether in nature or in the laboratory, results in an enhancement of its photostability.

Bromine indirubin FLIM/PLIM sensors to measure oxygen in normoxic and hypoxic PDT conditions.

BACKGROUND: The induction of phototoxicity during photodynamic therapy (PDT) is dependent on oxygen availability. For this reason, the development of sensors to measure oxygen and oxygen consumption is extremely important. APPROACH: In this project we have used Fluorescence Lifetime imaging (FLIM) and Phosphorescence Lifetime Imaging/ delayed Fluorescence Lifetime Imaging (PLIM/dFLIM) to investigate the ability of bromine indirubin derivatives as oxygen sensors. RESULTS: The oxygen sensitivity of bromine indirubins was detected through PLIM/dFLIM. Moreover, we have observed, by measuring nicotinamide adenine dinucleotide (NADH) FLIM, that bromine indirubin has a significant impact on cellular metabolism by shifting the SCC-4 Cells metabolism from oxidative phosphorylation (OXPHOS) to glycolysis. CONCLUSIONS: In conclusion, this study successfully achieves its goals and provides important insights into the use of indirubin as a potential oxygen consumption sensor with the capability to identify and differentiate between normoxic and hypoxic regions within the cells.

Effect of Co Doping on the Physical Properties and Organic Pollutant Photodegradation Efficiency of ZnO Nanoparticles for Environmental Applications.

This paper presents a comprehensive investigation of the synthesis and characterization of Zn1-xCoxO (0 ≤ x ≤ 0.05) nanopowders using a chemical co-precipitation approach. The structural, morphological, and vibrational properties of the resulting ZnO nanostructures were assessed through X-ray diffraction, scanning electronic microscopy, and Raman spectroscopy to examine the influence of cobalt doping. Remarkably, a notable congruence between the experimental results and the density functional theory (DFT) calculations for the Co-doped ZnO system was achieved. Structural analysis revealed well-crystallized hexagonal wurtzite structures across all samples. The SEM images demonstrated the formation of spherical nanoparticles in all the samples. The vibrational properties confirmed the formation of a hexagonal wurtzite structure, with an additional Raman peak corresponding to the F2g vibrational mode characteristic of the secondary phase of ZnCo2O4 observed at a 5% cobalt doping concentration. Furthermore, a theoretical examination of cobalt doping's impact on the elastic properties of ZnO demonstrated enhanced mechanical behavior, which improves stability, recyclability, and photocatalytic activity. The photocatalytic study of the synthesized compositions for methylene blue (MB) dye degradation over 100 min of UV light irradiation demonstrated that Co doping significantly improves photocatalytic degradation. The material's prolonged lifetime, reduced rate of photogenerated charge carrier recombination, and increased surface area were identified as pivotal factors accelerating the degradation process. Notably, the photocatalyst with a Zn0.99Co0.01O composition exhibited exceptional efficiency compared to that reported in the literature. It demonstrated high removal activity, achieving an efficiency of about 97% in a shorter degradation time. This study underscores the structural and photocatalytic advancements in the ZnO system, particularly at lower cobalt doping concentrations (1%). The developed photocatalyst exhibits promise for environmental applications owing to its superior photocatalytic performance.

Botulinum toxin in the treatment of residual limb hyperhidrosis: A systematic review / Toxina botulínica para el tratamiento de la hiperhidrosis del miembro residual: revisión sistemática

The aim of the study was to analyze the current evidence regarding the effect of intradermal injections of botulinum toxin on residual limb hyperhidrosis. A comprehensive search of the MEDLINE and Scopus databases from inception until December 2021 was performed according to the PRISMA guidelines. The search terms used were “botulinum toxins”, “botulinum toxins, Type A”, “rimabotulinumtoxinB”, “amputees”, “amputation stumps”, “amputation” and “residual limbs”. The specific controlled vocabulary of each database was also used (e.g., MeSH). One hundred and thirty-one different studies met this search criteria and were reviewed. Two independent reviewers assessed the quality of the manuscripts. Eight studies met the inclusion criteria for this review. The results demonstrated an improvement in residual limb hyperhidrosis in all studies. Botulinum toxin A or B can be regarded as safe and effective for the treatment of residual limb hyperhidrosis, as well as improving prosthesis use and quality of life.(AU)

El objetivo de este estudio fue analizar la evidencia actual relacionada con el efecto de las inyecciones intradérmicas de toxina botulínica en la hiperhidrosis del miembro residual. Se realizó una búsqueda amplia en las bases de datos MEDLINE y Scopus desde su inicio hasta diciembre de 2021 con arreglo a las guías PRISMA. Los términos de la búsqueda utilizados fueron «botulinum toxins», «botulinum toxins, type A», «rimabotulinumtoxin B», «amputees», «amputation stumps», «amputation» y «residual limbs». También se utilizó el vocabulario controlado específico de cada base de datos (ej.: MeSH). Cumplieron estos criterios de búsqueda 131 estudios diferentes, que fueron revisados. Dos revisores independientes evaluaron la calidad de los documentos y 8 estudios cumplieron los criterios de inclusión. Los resultados demostraron la mejora de la hiperhidrosis del miembro residual en todos los estudios. La toxina botulínica A o B puede considerarse segura y efectiva para el tratamiento de la hiperhidrosis del miembro residual y mejora el uso de la prótesis y la calidad de vida.(AU)

Highly Selective Fluorescent Sensors: Polyethylenimine Derivatives of Triphenylamine and Coumarin for GTP and ATP Interaction via Fluorescence Lifetime Imaging Microscopy.

Chemical derivatives of polyethylenimine (PEI) receptors with either triphenylamine (TPA) or 7-hydroxy-4-methyl-coumarin (Cou) form stable complexes with adenine and guanine nucleotides in water. The host-guest complex modulation is found to be based on noncovalent molecular interactions such as π-π stacking and hydrogen bonding, which are dependent on the aromatic moieties attached to the polyaminic (PEI) backbone. PEI-TPA acts as a chemosensor with a recognition driving force based on aggregation-induced emission (AIE), involving π-π interaction between the nucleic base and TPA. It detects GTP by a chelation enhancement quenching effect of fluorescence (CHEQ) with a measured logarithm stability constant, log ß = 7.7. By varying the chemical characteristics of the fluorophore, as in the PEI-Cou system, the driving force for recognition changes from a π-π interaction to an electrostatic interaction. The coumarin derivative detects ATP with a log ß value one order of magnitude higher than that for GTP, allowing for the selective recognition of the two nucleotides in a 100% aqueous solution. Furthermore, fluorescence lifetime imaging microscopy (FLIM) allows for a correlation between the selectivity of PEI-TPA toward nucleotides and the morphology of the structures formed upon ATP and GTP recognition. This study offers valuable insights into the design of receptors for the selective recognition of nucleotides in water.

Volatile compounds from soybeans under multiple on herbivores infestations attract the predatory mite Neoseiulus californicus (Acari: Phytoseiidae).

Plant-induced resistance can be an important component of soybean mites biological control programs. This work evaluates the preference of predatory mite Neoseiulus californicus (Acari: Phytoseiidae) to soybean plants under single and multiple herbivory conditions by two-spotted spider mite Tetranychus urticae (Acari: Tetranychidae), and velvetbean caterpillar Anticarsia gemmatalis (Lepidoptera: Noctuidae). Using a Y olfactometer, the following scenarios were evaluated: soybean with no infestation and soybean infested with A. gemmatalis; soybean infested with T. urticae and A. gemmatalis, and soybean infested with T. urticae and with both T. urticae and A. gemmatalis. Volatile compounds released by plants were analyzed and identified by a Trace GC Ultra gas chromatograph coupled to a mass spectrometer with a solid phase micro-extraction ion-trap. The predatory mite N. californicus preferred soybean plants infested with T. urticae compared to those infested with A. gemmatalis. Multiple infestation did not interfere with its preference to T. urticae. Multiple herbivory of T. urticae and A. gemmatalis modified the chemical profile of volatile compounds emitted by soybean plants. However, it did not interfere with the search behavior of N. californicus. Out of the 29 identified compounds only five promoted predatory mite response. Thus, regardless of single or multiple herbivory by T. urticae with or without A. gemmatalis, the indirect induced resistance mechanisms operate similarly. As such, this mechanism contributes to an increase in the encounter rate between predator and prey for N. Californicus and T. urticae, and the efficacy of biological control of mites on soybean.

On the structural, electronic, and optical properties of L-histidine crystal: a DFT study.

CONTEXT: The monoclinic L-histidine crystal is critical for protein structure and function and is also found in the myelin of brain nerve cells. This study numerically examines its structural, electronic, and optical properties. Our findings indicate that the L-histidine crystal has an insulating band gap of approximately 4.38 eV. Additionally, electron and hole effective masses range between 3.92[Formula: see text]-15.33[Formula: see text] and 4.16[Formula: see text]-7.53[Formula: see text], respectively. Furthermore, our investigation suggests that the L-histidine crystal is an excellent UV collector due to its strong optical absorption activity for photon energies exceeding 3.5 eV. METHODS: To investigate the structural, electronic, and optical properties of L-histidine crystals, we used the Biovia Materials Studio software to conduct Density Functional Theory (DFT) simulations as implemented in the CASTEP code. Our DFT calculations were performed using the generalized gradient approximation (GGA) as parameterized by the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional, with an additional dispersion energy correction (PBE [Formula: see text] TS) based on the model proposed by Tkatchenko and Scheffler to describe van der Waals interactions. Additionally, we employed the norm-conserving pseudopotential to treat core electrons.

Solvent-Driven Self-Organization of Meso-Substituted Porphyrins: Morphological Analysis from Fluorescence Lifetime Imaging Microscopy.

A morphological analysis of different thin films of meso-tetra-p-(di-p-phenylamino)phenylporphyrin, H2T(TPA)4P, was made by fluorescence lifetime imaging microscopy (FLIM) and scanning electron microscopy (SEM). A comprehensive study of H2T(TPA)4P was undertaken through UV/vis absorption and fluorescence techniques in different solvents, solvent mixtures and in thin films. In solution, occurrence of intramolecular energy transfer from the triphenylamine (TPA) moieties to the porphyrin core, with quenching efficiencies in the order of 94-97%, is observed. The energy transfer rate constants are determined assuming Förster's dipole-dipole and Dexter's electron exchange mechanisms. In drop-cast-prepared thin films, from samples with different solvent mixtures, the photoluminescence (PL) quantum yield (ΦPL) decreases ∼1 order of magnitude compared to the solution behavior. FLIM and SEM experiments showed the self-organization and morphology of H2T(TPA)4P in thin films to be highly dependent on the solvent mixture used to prepare the film. In chloroform, the solvent's evaporation results in the formation of elongated and overlapped microrod structures. Introduction of a cosolvent, namely, a polar cosolvent, promotes changes in the morphology of the self-assembled structures, with the formation of three-dimensional spherical structures and hollow spheres. H2T(TPA)4P dispersed in a polymer matrix shows enhanced ΦPL values when compared to the drop-cast films. FLIM images showed coexistence of three different states or domains: aggregated, interface, and nonaggregated or less-aggregated states. This work highlights the importance of FLIM in the morphological characterization of heterogeneous films, together with the photophysical characterization of nano- and microdomains.

The role of solvents and concentrations in the properties of oxime bearing A2B corroles.

A comprehensive study on the electronic spectral, photophysical and acid-base properties of phenyl- and methyl-oxime corrole derivatives and of triphenylcorrole (model corrole) has been performed, aiming to shed light on the existing species in the ground and excited states. Solvents and corrole concentration are found to govern the properties of the studied compounds and are determinants of their applicability in in vivo studies. In THF, the neutral corrole has two tautomeric forms (T1 and T2). In DMSO, the deprotonated form shows a characteristic long-wavelength Q band slightly shifted to blue when compared with the T1 tautomer and a higher fluorescence quantum yield. In ACN, with the increase of the corrole concentration formation of an aggregate due to homoconjugation (with dimer characteristics) is observed, and pioneeringly reported using UV-Vis and fluorescence studies and confirmed by carrying out titrations with TFA. The effect of the oxime group on the pK values of a corrole is found to influence the formation of a homoconjugate, namely by precluding its formation (at higher concentrations) when compared with the model corrole. TDDFT electronic quantum calculations support the experimental observations, namely the existence of tautomers and deprotonated species, with their respective electronic spectral features, further allowed proposing a structure for the homoconjugate complex in ACN. The characteristics of the oxime-corroles, namely a pK of ∼ 5, absorption and emission at ca. 650 nm and solvent dependent properties, make them good candidates for their use in biological systems either as probes, sensors, or as new sensitizers for photodynamic therapy.

Botulinum toxin in the treatment of residual limb hyperhidrosis: A systematic review.

The aim of the study was to analyze the current evidence regarding the effect of intradermal injections of botulinum toxin on residual limb hyperhidrosis. A comprehensive search of the MEDLINE and Scopus databases from inception until December 2021 was performed according to the PRISMA guidelines. The search terms used were "botulinum toxins", "botulinum toxins, Type A", "rimabotulinumtoxinB", "amputees", "amputation stumps", "amputation" and "residual limbs". The specific controlled vocabulary of each database was also used (e.g., MeSH). One hundred and thirty-one different studies met this search criteria and were reviewed. Two independent reviewers assessed the quality of the manuscripts. Eight studies met the inclusion criteria for this review. The results demonstrated an improvement in residual limb hyperhidrosis in all studies. Botulinum toxin A or B can be regarded as safe and effective for the treatment of residual limb hyperhidrosis, as well as improving prosthesis use and quality of life.

Enhanced thermal and photo-stability of a para-substituted dicumyl ketone intercalated in a layered double hydroxide.

A ketodiacid, 4,4'-dicarboxylate-dicumyl ketone (3), has been intercalated into a Zn, Al layered double hydroxide (LDH) by a coprecipitation synthesis strategy. The structure and chemical composition of the resultant hybrid material (LDH-KDA3) were characterized by powder X-ray diffraction (PXRD), FT-IR, FT-Raman and solid-state 13C{1H} NMR spectroscopies, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA), and elemental analysis (CHN). PXRD showed that the dicarboxylate guest molecules assembled into a monolayer to give a basal spacing of 18.0 Å. TGA revealed that the organic guest starts to decompose at a significantly higher temperature (ca. 330°C) than that determined for the free ketodiacid (ca. 230°C). Photochemical experiments were performed to probe the photoreactivity of the ketoacid in the crystalline state, in solution, and as a guest embedded within the photochemically-inert LDH host. Irradiation of the bulk crystalline ketoacid results in photodecarbonylation and the exclusive formation of the radical-radical combination product. Solution studies employing the standard myoglobin (Mb) assay for quantification of released CO showed that the ketoacid behaved as a photoactivatable CO-releasing molecule for transfer of CO to heme proteins, although the photoreactivity was low. No photoinduced release of CO was found for the LDH system, indicating that molecular confinement enhanced the photo-stability of the hexasubstituted ketone. To better understand the behavior of 3 under irradiation, a more comprehensive study, involving excitation of this compound in DMSO-d6 followed by 1H NMR, UV-Vis and fluorescence spectroscopy, was undertaken and further rationalized with the help of time-dependent density functional theory (TDDFT) electronic quantum calculations. The photophysical study showed the formation of a less emissive compound (or compounds). New signals in the 1H NMR spectra were attributed to photoproducts obtained via Norrish type I α-cleavage decarbonylation and Norrish type II (followed by CH3 migration) pathways. TDDFT calculations predicted that the formation of a keto-enol system (via a CH3 migration step in the type II pathway) was highly favorable and consistent with the observed spectral data.

Excited state deactivation mechanisms in Shikonin rationalized from its naphthoquinone parent structures.

Shikonin, a naphthoquinone dye, is a molecule of colour of natural origin, whose peculiar properties have not yet been fully rationalized. Its core structure consists of a di-hydroxy-naphthoquinone with an additional non-aromatic hydroxy group. From a comprehensive study involving fast spectroscopic techniques (fs-TA and fs-UC) and TDDFT electronic structure calculations on shikonin (Shk) and its derivatives 5-hydroxy-1,4-naphthoquinone (5HNQ), 5,8-diacetoxy-1,4-naphthoquinone (DiAc), 5,8-dihidroxy-1,4-naphthoquinone (DHNQ) and acetylshikonin, AcShk, it is shown that intramolecular excited state proton transfer (ESIPT) is present and is determinant in the deactivation of the hydroxy containing molecules. This is mirrored by the dominance of the internal conversion deactivation channel. In Shk, the non-aromatic hydroxy group determines the preferred conformer in both the ground- and excited-state, as reflected in the doubling of the fluorescence quantum yield value of this molecule relative to DHNQ. From fs-UC, a kinetic isotopic effect of 1.7 was obtained for DHNQ.

Ring-Fused meso-Tetraarylchlorins as Auspicious PDT Sensitizers: Synthesis, Structural Characterization, Photophysics, and Biological Evaluation.

Novel 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-fused meso-tetraarylchlorins, with different degrees of hydrophilicity (with methyl ester, hydroxymethyl, and carboxylic acid moieties), have been synthesized and their photophysical characterization as well as in vitro photocytotoxicity assessment against human melanoma and esophageal and bladder carcinomas was carried out. An integrated analysis of the photosensitizers' performance, considering the singlet oxygen generation data, cell internalization, and intracellular localization, allowed to establish relevant structure-photoactivity relationships and the rationalization of the observed photocytotoxicity. In the diacid and monoalcohol series, chlorins derived from meso-tetraphenylporphyrin proved to be the most efficient photodynamic therapy agents, showing IC50 values of 68 and 344 nM against A375 cells, respectively. These compounds were less active against OE19 and HT1376 cells, the diacid chlorin with IC50 values still in the nano-molar range, whereas the monohydroxymethyl-chlorin showed significantly higher IC50 values. The lead di(hydroxymethyl)-substituted meso-tetraphenylchlorin confirmed its remarkable photoactivity with IC50 values below 75 nM against the studied cancer cell lines. Subcellular accumulation of this chlorin in the mitochondria, endoplasmic reticulum, and plasma membrane was demonstrated.

Aggregation-Induced Emission with Alkynylcoumarin Dinuclear Gold(I) Complexes: Photophysical, Dynamic Light Scattering, and Time-Dependent Density Functional Theory Studies.

Aggregation-induced emission (AIE) has gained a remarkable amount of interest in the past 20 years, but the majority of the studies are based on organic structures. Herein, three dinuclear gold(I) complexes, with the general formula [PPh2XPPh2-Au2-Coum2], where the Au(I) atom is linked to three different diphosphanes [PPh2XPPh2; DPPM for X = CH2 (1.1), DPPP for X = (CH2)3 (1.2), and DPPA for X = C≡C (1.3)] and the propynyloxycoumarin precursor (1, 4-methyl-substituted coumarin), have been synthesized. The compounds present AIE characteristics, AIEgens, with high luminescence quantum yields in the solid state when they are compared to dilute solutions. Photophysical studies (steady-state and time-resolved fluorescence) were obtained, with AIE being observed with the three gold(I) complexes in acetonitrile/water mixtures. This was further corroborated with dynamic light scattering measurements. Time-dependent density functional theory (TDDFT) electronic calculations show that the compounds have different syn and anti conformations (relative to the coumarin core) with 1.1 syn and 1.2 and 1.3 both anti. From time-resolved fluorescence experiments, the augment in the contribution of the longer decay component is found to be associated with the emission of the aggregate (AIE effect) and its nature (involving a dimer) rationalized from TDDFT electronic calculations.

Cucurbituril hosts as promoters of aggregation induced emission of triphenylamine derivatives.

Three ligands bearing triphenylamine as a core and one, two or three acyclic polyamine chains, TPA1p, TPA2p and TPA3p, respectively, have been studied by potentiometric and photophysical (UV-Vis, steady-state and time-resolved fluorescence) techniques. The host-guest interaction with cucurbit[7]uril, CB7, has been investigated in aqueous solution showing aggregation induced emission behaviour when encapsulated into a CB7 cavity. From fluorescence emission it is revealed that the charged polyamine chains are the unit entering into CB7 and from the Job plots the stoichiometries are found to vary from 1 : 1 to 1 : 3 L : CB7 ratios. Interactions of the charged amines with the portals of CB7 restrict rotation of the benzene units in the triphenylamine backbone (free rotor effect), decreasing the radiationless internal conversion channel at the expense of the enhancement of fluorescence. Dynamic light scattering and resonance Rayleigh scattering experiments show that TPA3p-CB7 complexes involve formation of aggregates with a mean size of 126 ± 5 nm and a dispersity factor of 0.117, indicating a monodisperse distribution and supporting the important conclusions of this work: formation of emissive aggregates through the AIE effect.

Somatic homozygous loss of SH2B3, and a non-Robertsonian translocation t(15;21)(q25.3;q22.1) with NTRK3 rearrangement, in an adolescent with progenitor B-cell acute lymphoblastic leukemia with the iAMP21.

Intrachromosomal amplification of chromosome 21 (iAMP21) occurs in ∼2% of B-cell acute lymphoblastic leukemia (ALL) and is considered to confer a poor prognosis. The relapse risk is associated with therapy intensity, suggesting that other somatic mutations may influence iAMP21-ALL prognosis. This abnormality is characterized by multiple copies of the RUNX1 gene in chromosome 21 and appears to arise through multiple breakage-fusion bridge cycles and chromothripsis. Rob(15;21) or a ring chromosome 21 have been associated with an increased risk for iAMP21-ALL, suggesting that constitutional genetic abnormalities may also drive leukemogenesis. Here we describe homozygous deletion of the SH2B3 gene, chromothripsis of chromosome 21, and a non-Robertsonian somatic t(15;21)(q25.3;q22.1) with NTRK3 gene rearrangement in an adolescent with iAMP21-B-ALL. Molecular cytogenetic studies detected iAMP21 with aCGH analysis revealing further genomic imbalances. The RT-qPCR analysis detected elevated expression levels of RUNX1 (68-fold) and reduced expression of CDK6 (0.057-fold). Studies with constitutive cells collected from mouth swabs showed that SH2B3 biallelic deletion was a somatic alteration occurring during clonal evolution. The identification of novel secondary genetic changes was valuable to discuss sporadic iAMP21 leukemogenic mechanisms. For the first time, we show a t(15;21)(q25.3;q22.1) with NTRK3 rearrangement in an adolescent with iAMP21-ALL.

Tryptanthrin derivatives as efficient singlet oxygen sensitizers.

Halogenated tryptanthrin and aminotryptanthrin were synthesized from indigo or isatin precursors. Dibromo- and tetrabromo-tryptanthrin were obtained from indigo dyes following green chemistry procedures, through microwave-assisted synthesis in mild oxidation conditions. Spectral and photophysical properties of the compounds, including quantitative determination of all the different deactivation pathways of S1 and T1, were obtained in different solvents and temperatures. The triplet state (T1) has a dominant role on the photophysical properties of these compounds, which is further enhanced by the halogens at the fused-phenyl rings. Substitution with an amino group, 2-aminotryptanthrin (TRYP-NH2), leads a dominance of the radiative decay channel. Moreover, with the sole exception of TRYP-NH2, S1 ~ ~ > T1 intersystem crossing constitutes the dominant route, with internal conversion playing a minor role in the deactivation of S1 in all the studied derivatives. In agreement with tryptanthrin, emission of the triplet state of tryptanthrin derivatives (with exception of TRYP-NH2), was observed together with an enhancement of the singlet oxygen sensitization quantum yield: from 70% in tryptanthrin to 92% in the iodine derivative. This strongly contrasts with indigo and its derivatives, where singlet oxygen sensitization is found inefficient.

Aggregation-Induced Emission Leading to White Light Emission in Diphenylbenzofulvene Derivatives.

The search for a unique molecular system able to efficiently emit in the total visible range of the electromagnetic spectra, i. e., white light emission (WLE), is a topic of intense research. We here show that aggregates formed by diphenylbenzofulvene (DPBF) derivatives are from two to four orders of magnitude more emissive than their monomers. From a simple strategy, involving structural modification of a DPBF propelled shape core, a close match with the pure white light emission coordinates is obtained with a combination of two derivatives in films, with featured solid-state emission, without involvement of D-A groups or energy transfer processes.

International Classification of Diseases Codes as screeners for Adverse Drug Events

Códigos da Classificação Internacional de Doenças como Rastreadores de Eventos Adversos a MedicamentosARTIGO DE REVISÃOJosé Romério Rabelo Melo1,2 , Elisabeth Carmen Duarte,3 Silvia Maria de Freitas4 , Eduardo Gabriel Pinheiro5 , Eudiana Vale Francelino6,7 , Paulo Sergio Dourado Arrais7 Introdução: Os Eventos Adversos a Medicamentos-EAM representam riscos à saúde e sua subnotificação representa um desafio para a saúde pública. A busca ativa de casos suspeitos de EAM nos bancos de dados de saúde utilizando a Classificação Internacional de Doenças-CID é uma das estratégias que pode reduzir as subnotificações desses eventos. Objetivo: O objetivo desse estudo é identificar os códigos da CID mais usados como rastreadores de EAM e avaliar a sua concordância entre os pesquisadores. Métodos: Foi realizada uma revisão sistemática da literatura utilizando as bases de dados PubMed, Scopus, Web of Science, MEDLINE e LILACS com os descritores "Classificação Internacional de Doenças", "CID-10", "Efeitos Colaterais e Reações Adversas Relacionados a Medicamentos", "Envenenamento", "Erros de Medicação". Os artigos incluídos tiveram seus códigos CID identificados, comparados e sua qualidade avaliada. A análise de concordância dos códigos foi feita usando o modelo de ensaios de Bernoulli, testes de proporções binomial exata e a técnica de false discovery rate para analisar as hipóteses postas. A análise estatística foi feita com o software R. O estudo está registrado no PROSPERO sob n.º CRD42019120694. Resultados: Foram identificados 5.167 artigos e após os critérios de seleção, 33 foram incluídos nessa revisão. Foram identificados 1.105 códigos da CID. O coeficiente de prevalência dos EAM variou entre 0,18% e 18,4% em internações hospitalares e a taxa de mortalidade variou entre 0,12 a 45,9 óbitos por 100 mil óbitos. Somente 195 (17,7%) códigos tiveram alta concordância entre os pesquisadores. Muitos códigos CID utilizados para detectar EAM possuem baixa concordância entre os pesquisadores e produziram diferentes taxas do evento. Conclusão: Os códigos rastreadores de EAM identificados representam um método simples e eficiente para captação de eventos adversos em grandes bancos de dados em saúde, contribuindo na redução da subnotificação nos tradicionais sistemas de notificações de EAM.Palavras-chave: Informática médica, Farmacoepidemiologia, Segurança do paciente, Classificação internacional de doenças, Efeitos colaterais e reações adversas relacionadas a medicamentos. (AU)

International Classification of Diseases Codes as screeners for Adverse Drug EventsREVIEW ARTICLEJosé Romério Rabelo Melo1,2 , Elisabeth Carmen Duarte,3 Silvia Maria de Freitas4 , Eduardo Gabriel Pinheiro5 , Eudiana Vale Francelino6,7 , Paulo Sergio Dourado Arrais7 1. Agência Nacional de Vigilância Sanitária/Gerência Geral de Inspeção e Fiscalização, Brasília, (DF), Brasil2. Universidade Federal do Ceará-UFC. Programa de Pós-Graduação de Ciências Farmacêuticas, Fortaleza, (CE), Brasil3. Universidade de Brasília-UnB. Faculdade de Medicina. Núcleo de Medicina Tropical, (DF), Brasil4. Universidade Federal do Ceará-UFC. Departamento de Estatística e Matemática Aplicada. Fortaleza, (CE), Brasil5. Instituto de Matemática, Estatística e Computação Científica (IMECC). Programa de Pós-Graduação em Estatística, UNICAMP. Campinas, (SP), Brasil6. Universidade Federal do Ceará-UFC. Faculdade de Farmácia, Odontologia e Enfermagem. Grupo de Prevenção ao Uso Indevido de Medicamentos-GPUIM. Departamento de Farmácia, Fortaleza, (CE), Brasil7. Universidade Federal do Ceará-UFC. Faculdade de Farmácia, Odontologia e Enfermagem. Departamento de Farmácia, Fortaleza, (CE), Brasilhttps://doi.org/10.11606/issn.2176-7262.rmrp.2021.178993Introduction: Adverse drug events (ADEs) represent health risks and their underreporting represents a challenge to public health. The active search for suspected cases of ADE in health databases using the International Classification of Diseases-CID is one of the strategies that can reduce underreporting of these events. Objective: The aim of this study is to identify the ICD codes most commonly used as tracers of ADE and to assess their concordance among researchers. Methods: A systematic literature review was conducted using the PubMed, Scopus, Web of Science, MEDLINE and LILACS databases with the descriptors "International Classification of Diseases", "ICD-10", "Drug-Related Side Effects and Adverse Reactions", "Poisoning", "Medication Errors". The included articles had their ICD codes identified, compared and their quality assessed. The analysis of concordance of the codes was done using Bernoulli's test model, exact binomial proportions tests and the false discovery rate technique to analyze the hypotheses posed. Statistical analysis was done using R software. The study is registered in PROSPERO under CRD42019120694. Results: A total of 5,167 articles were identified and after the selection criteria, 33 were included in this review. A total of 1,105 ICD codes were identified. The prevalence coefficient of ADEs ranged from 0.18% to 18.4% in hospital admissions and the mortality rate ranged from 0.12 to 45.9 deaths per 100,000 deaths. Only 195 (17.7%) codes had high concordance among researchers. Many ICD codes used to detect ADEs have low inter-rater concordance and produced different event rates. Conclusion: The identified ADE tracking codes represent a simple and efficient method for capturing adverse events in large healthcare databases, contributing to the reduction of underreporting in traditional ADE reporting systems. (AU)