Further evaluation of the shape of atomic Hirshfeld surfaces: M...H contacts and homoatomic bonds.

It is well known that Hirshfeld surfaces provide an easy and straightforward way of analysing intermolecular interactions in the crystal environment. The use of atomic Hirshfeld surfaces has also demonstrated that such surfaces carry information related to chemical bonds which allow a deeper evaluation of the structures. Here we briefly summarize the approach of atomic Hirshfeld surfaces while further evaluating the kind of information that can be retrieved from them. We show that the analysis of the metal-centre Hirshfeld surfaces from structures refined via Hirshfeld Atom Refinement (HAR) allow accurate evaluation of contacts of type M...H, and that such contacts can be related to the overall shape of the surfaces. The compounds analysed were tetraaquabis(3-carboxypropionato)metal(II), [M(C4H3O4)2(H2O)4], for metal(II)/M = manganese/Mn, cobalt/Co, nickel/Ni and zinc/Zn. We also evaluate the sensitivity of the surfaces by an investigation of seemingly flat surfaces through analysis of the curvature functions in the direction of C-C bonds. The obtained values not only demonstrate variations in curvature but also show a correlation with the hybridization of the C atoms involved in the bond.

Social Justice and the Political Organization of Behavior Analysts: Changing the Institutional Practices of a Brazilian Association.

Given the advancement of behavioral research in culture and social behavior, it seems natural for the community of behavior analysts to progress towards increased political engagement and a dedication to social justice. To reach this goal, it is necessary to act inside one's own communities and organizations. The purpose of this article is to report on the efforts of the Brazilian Association for Behavioral Psychology and Medicine (ABPMC) to increase equity and social justice during the 2017-2018 term. First, we present an overview of the ABPMC. Next, we describe the process of identifying, planning, and implementing equity and social justice actions in the association. The problems targeted were the discontinuation of policies from one term to another, elitism and centralization, the lack of topics with social and political relevance in the annual conference's scientific program, and the lack of support for the participation of women (especially mothers) in clinical and academic practice. Supplementary Information: The online version contains supplementary material available at 10.1007/s40617-020-00510-2.

Susceptibility of Leishmania to novel pentavalent organometallics: Investigating impact on DNA and membrane integrity in antimony(III)-sensitive and -resistant strains.

The aim the present study was to investigate the impact of novel pentavalent organobismuth and organoantimony complexes on membrane integrity and their interaction with DNA, activity against Sb(III)-sensitive and -resistant Leishmania strains and toxicity in mammalian peritoneal macrophages. Ph3M(L)2 type complexes were synthesized, where M = Sb(V) or Bi(V) and L = deprotonated 3-(dimethylamino)benzoic acid or 2-acetylbenzoic acid. Both organobismuth(V) and organoantimony(V) complexes exhibited efficacy at micromolar concentrations against Leishmania amazonensis and L. infantum but only the later ones demonstrated biocompatibility. Ph3Sb(L1)2 and Ph3Bi(L1)2 demonstrated distinct susceptibility profiles compared to inorganic Sb(III)-resistant strains of MRPA-overexpressing L. amazonensis and AQP1-mutated L. guyanensis. These complexes were able to permeate the cell membrane and interact with the Leishmania DNA, suggesting that this effect may contribute to the parasite growth inhibition via apoptosis. Taken altogether, our data substantiate the notion of a distinct mechanism of uptake pathway and action in Leishmania for these organometallic complexes, distinguishing them from the conventional inorganic antimonial drugs.

Prevalence of temporomandibular disorders in the Brazilian population: A systematic review and meta-analysis.

This systematic review aimed to assess the prevalence of temporomandibular disorders (TMD) in the Brazilian population, with studies that used the RDC/TMD or DC/TMD as diagnostic tools. A total of 6365 people from 11 studies were included. Sample mean age ranged from 12 to 69.5 years. The pooled prevalence of TMD was 33.6% (95% CI 31.5-35.8; I2 = 37.2). Prevalence of TMD was higher in females (37.0%) than in males (29.3%). Our results indicate that TMD is a prevalent condition across Brazil's territories. The results from this meta-analysis can help calculate more accurate sample sizes for future studies.

Communication disorders in the correctional system: a systematic review.

OBTECTIVES: Good communication is essential for resolving social conflicts, especially in closed communities such as prisons. When communication is interrupted by factors such as hearing loss or difficulties in coordination, voice, language, fluency, or disruption of any of the biological systems required to communicate, Human Communication Disorders can appear. This review aimed to identify the most prevalent communication disorders amongst prison inmates. MATERIAL AND METHOD: Systematic review through databases of studies that analyze individual inmates with communication disorders over the last 38 years. After reading the titles and abstracts and applying the eligibility criteria, 25 articles were selected and included in the final review. RESULTS: A sample of 2,188 individuals was evaluated, two studies were conducted with a female population only, while twelve studied exclusively males, and 11 articles had a mixed population. All the studies included evaluated language and communication disorders in general, with language impairment being more prevalent There are no English language studies evaluating language and communication disorders in incarcerated individuals from African countries, Latin America or Asia. DISCUSSION: Inmates have a high prevalence of language and communication disorders, and thus end up being more vulnerable within the prison system. Speech therapists are important members of the legal workforce and improve the health, well-being and participation of people in contact with or at risk of contact with the judicial system through the prevention, early detection, assessment and treatment of communication disorders.

Experimental charge density and topological analysis of tetraaquabis(hydrogenmaleato)nickel(II): a comparison with Hirshfeld atom refinement.

Experimental charge density analysis is conducted on the coordination compound tetraaquabis(hydrogenmaleato)nickel(II), which exhibits a short intramolecular hydrogen bond. Through topological analysis, the nature of Ni-O bonds is concluded to be intermediate between ionic and covalent, but mainly presenting an ionic character, while the short hydrogen bond is classified as covalent in nature. The compound was also analysed after Hirshfeld atom refinement performed using NoSpherA2. A topological analysis was conducted on the molecular wavefunction and the results are compared with those obtained from experiment. In general, there is good agreement between the refinements, and the chemical bonds involving H atoms are in better agreement with what is expected from neutron data after HAR than they are after multipole refinement.

Antitumor copper(II) complexes with hydroxyanthraquinones and N,N-heterocyclic ligands.

Five ternary copper(II) complexes, [Cu2(phen)2(L1)(ClO4)2] (1), [Cu2(phen)2(L1)(DMSO)2](PF6)2 (2), [Cu2(bpy)2(L1)(ClO4)2(H2O)2] (3), [Cu2(dmp)2(L1)(ClO4)2(H2O)2] (4), and [Cu(phen)(L2)]2(ClO4)2 (5), in which phen = 1,10-phenanthroline, bpy = 2,2'-bipyridine, dmp = 2,9-dimethyl-1,10-phenanthroline, H2L1 = 1,4-dihydroxyanthracene-9,10-dione and HL2 = 1-hydroxyanthracene-9,10-dione, DMSO = dimethylsulfoxide, were synthesized and fully characterized. Complex 2 was obtained through the substitution of perchlorate for DMSO. When two hydroxyquinone groups are present, L1 makes a bridge between two Cu(II) ions, which also bind two nitrogens of the respective diimine ligand. The compounds bind to calf thymus DNA and oxidatively cleave pUC19 DNA according to the following order of activity 1 > 4-5 > 3. Furthermore, complexes 1, 3, 4 and 5 inhibit topoisomerase-I activity and the growth of myelogenous leukemia cells with the IC50 values of 1.13, 10.60, 0.078, and 1.84 µmol L-1, respectively. Complexes 1 and 4 are the most active in cancer cells and in DNA cleavage.

On the use of Hirshfeld surfaces for estimating atomic charges in ionic species: crystal structure of the natural ilmenite (Mg0.4168Fe0.5832)TiO3.

We performed an analysis by single-crystal X-ray diffraction and scanning electron microscopy (SEM), aiming to solve and refine the structure of an ilmenite single crystal [(Fe0.5832Mg04168)TiO3] from the city of Ouvidor (Goiás, Brazil). Hirshfeld partition was used to explore the values of w(r), dnorm and curvedness that achieve complementary surfaces for neighbouring atoms in this ionic system, and the subsequent impact on the charge distribution, allowing the ionic radius and the charges of the ilmenite sample to be modelled.

What the radiologist should know about the role of percutaneous gastrostomy: a pictorial essay.

The image-guided gastrostomy techniques, as transoral and transabdominal, can be performed when there is a failure of the endoscopic procedure or in some specific clinical scenarios. This pictorial essay intends to show the percutaneous gastrostomy techniques, indications, technical approaches, post-procedure care, and complications.

As técnicas de gastrostomia guiadas por imagem, por via transoral e transabdominal podem ser realizadas quando há falha na técnica endoscópica ou em cenários clínicos em que a endoscopia não pode ser realizada. Este ensaio iconográfico pretende mostrar as técnicas de gastrostomia percutânea, suas indicações, aspectos técnicos, cuidados pós-procedimento e complicações.

O que o radiologista deve saber sobre o papel da gastrostomia percutânea: ensaio iconográfico / What the radiologist should know about the role of percutaneous gastrostomy: a pictorial essay

Resumo As técnicas de gastrostomia guiadas por imagem, por via transoral e transabdominal podem ser realizadas quando há falha na técnica endoscópica ou em cenários clínicos em que a endoscopia não pode ser realizada. Este ensaio iconográfico pretende mostrar as técnicas de gastrostomia percutânea, suas indicações, aspectos técnicos, cuidados pós-procedimento e complicações.

Abstract The image-guided gastrostomy techniques, as transoral and transabdominal, can be performed when there is a failure of the endoscopic procedure or in some specific clinical scenarios. This pictorial essay intends to show the percutaneous gastrostomy techniques, indications, technical approaches, post-procedure care, and complications.

Vitamin D status and prevalence of hypovitaminosis D in different genders throughout life stages: A Brazilian cross-sectional study.

OBJECTIVES: To evaluate the mean concentration of 25-hydroxivitamin D [25(OH) D] and prevalence of hypovitaminosis D in individuals residing in Rio de Janeiro, Brazil. METHODS: The data of 80,000 consecutive individuals who had 25(OH) D measurements performed by electrochemiluminescence between 1/2/2018 and 2/5/2018 were selected. Patients who reported the use of therapies/supplements were excluded. Levels of 25(OH) D ≥20 ng/mL (ages <60 years) and ≥30 ng/mL (ages ≥60 years) were considered adequate. RESULTS: We analyzed the data of 24,074 individuals (1-95 years old, 64.7% female). Descriptive curves showed that, in both sexes, the mean values of 25(OH) D decreased from the first years of life until adolescence, then slightly increased, and then tended to stabilize during adulthood. Levels of 25(OH) D <20 ng/mL were observed in 6% of girls versus 3.6% of boys and in 13.6% of adolescent girls versus 12.6% of adolescent boys and 11% of adults. The percentage of seniors with serum levels of 25(OH) D <20 ng/mL was 13.6% in women and 12.7% in men; 53.2% of women and 50.6% of men had levels <30 ng/mL. CONCLUSIONS: Mean 25(OH) D values were higher in children and lower in adolescents and women. Approximately 90% of non-seniors and presumably healthy residents of the urban metropolitan region of Rio de Janeiro presented satisfactory levels of 25(OH) D during the summer months; however, in over half of the elderly, the serum concentrations of 25(OH) D were inadequate. Therefore, strategies for the prevention of hypovitaminosis D should be considered in the senior population.

Vitamin D status and prevalence of hypovitaminosis D in different genders throughout life stages: A Brazilian cross-sectional study

OBJECTIVES: To evaluate the mean concentration of 25-hydroxivitamin D [25(OH) D] and prevalence of hypovitaminosis D in individuals residing in Rio de Janeiro, Brazil. METHODS: The data of 80,000 consecutive individuals who had 25(OH) D measurements performed by electrochemiluminescence between 1/2/2018 and 2/5/2018 were selected. Patients who reported the use of therapies/supplements were excluded. Levels of 25(OH) D ≥20 ng/mL (ages <60 years) and ≥30 ng/mL (ages ≥60 years) were considered adequate. RESULTS: We analyzed the data of 24,074 individuals (1-95 years old, 64.7% female). Descriptive curves showed that, in both sexes, the mean values of 25(OH) D decreased from the first years of life until adolescence, then slightly increased, and then tended to stabilize during adulthood. Levels of 25(OH) D <20 ng/mL were observed in 6% of girls versus 3.6% of boys and in 13.6% of adolescent girls versus 12.6% of adolescent boys and 11% of adults. The percentage of seniors with serum levels of 25(OH) D <20 ng/mL was 13.6% in women and 12.7% in men; 53.2% of women and 50.6% of men had levels <30 ng/mL. CONCLUSIONS: Mean 25(OH) D values were higher in children and lower in adolescents and women. Approximately 90% of non-seniors and presumably healthy residents of the urban metropolitan region of Rio de Janeiro presented satisfactory levels of 25(OH) D during the summer months; however, in over half of the elderly, the serum concentrations of 25(OH) D were inadequate. Therefore, strategies for the prevention of hypovitaminosis D should be considered in the senior population.

Ellagic Acid Inhibits Neuroinflammation and Cognitive Impairment Induced by Lipopolysaccharides.

Neuroinflammation is a predisposing factor for the development of cognitive impairment and dementia. Among the new molecules that are currently being studied, ellagic acid (EA) has stood out for its neuroprotective properties. The present study investigated the effects of ellagic acid in the object recognition test, oxidative stress, cholinergic neurotransmission, glial cell expression, and phosphorylated Tau protein expression. For this, 32 male Wistar rats received an intraperitoneal (IP) application of lipopolysaccharides (LPS) at a dose of 250 µg/kg or 0.9% saline solution (SAL) for 8 days. Two hours after the IP injections, the animals received 100 mg/kg of EA or SAL via intragastric gavage. Behavioral parameters (open field test and object recognition) were performed on days 5, 6, and 7 of the experimental periods. The results showed that the treatment with EA in the LPS group was able to inhibit cognitive impairment, modulate the immune system response by significantly reducing glial cell expression, attenuating phosphorylated Tau and oxidative damage with consequent improvement in the antioxidant system, as well as preventing the increase of acetylcholinesterase activity. Thus, the neuroprotective effects of EA and its therapeutic potential in cognitive disorders secondary to neuroinflammation were demonstrated.

Synthesis, crystal structure and studies on the interaction with albumin of a new silver(I) complex based on 2-(4-nitrobenzenesulfonamido)benzoic acid.

In the present work, the two-dimensional (2D) polymer poly[[µ4-2-(4-nitrobenzenesulfonamido)benzoato-κ4O1:O1:O1':N6]silver(I)] (AgL), [Ag(C13H9N2O6S)]n, was obtained from 2-(4-nitrobenzenesulfonamido)benzoic acid (HL), C13H10N2O6S. FT-IR, 1H and 13C{1H} NMR spectroscopic analyses were used to characterize both compounds. The crystal structures of HL and AgL were determined by single-crystal X-ray diffraction. In the structure of HL, O-H...O hydrogen bonds between neighbouring molecules result in the formation of dimers, while the silver(I) complex shows polymerization associated with the O atoms of three distinct deprotonated ligands (L-). Thus, the structure of the Ag complex can be considered as a coordination polymer consisting of a one-dimensional linear chain, constructed by carboxylate bridging groups, running parallel to the b axis. Neighbouring polymeric chains are further bridged by Ag-C monohapto contacts, resulting in a 2D framework. Fingerprint analysis of the Hirshfeld surfaces show that O...H/H...O hydrogen bonds are responsible for the most significant contacts in the crystal packing of HL and AgL, followed by the H...H and O...C/C...O interactions. The Ag...Ag, Ag...O/O...Ag and Ag...C/C...Ag interactions in the Hirshfeld surface represent 12.1% of the total interactions in the crystal packing. Studies of the interactions of the compounds with human serum albumin (HSA) indicated that both HL and AgL interact with HSA.

New Heteroleptic Ruthenium(II) Complexes with Sulfamethoxypyridazine and Diimines as Potential Antitumor Agents.

Two new complexes of Ru(II) with mixed ligands were prepared: [Ru(bpy)2smp](PF6) (1) and [Ru(phen)2smp](PF6) (2), in which smp = sulfamethoxypyridazine; bpy = 2,2'-bipyridine; phen = 1,10-phenanthroline. The complexes have been characterized by elemental and conductivity analyses; infrared, NMR, and electrospray ionization mass spectroscopies; and X-ray diffraction of single crystal. Structural analyses reveal a distorted octahedral geometry around Ru(II) that is bound to two bpy (in 1) or two phen (in 2) via their two heterocyclic nitrogens and to two nitrogen atoms from sulfamethoxypyridazine-one of the methoxypyridazine ring and the sulfonamidic nitrogen, which is deprotonated. Both complexes inhibit the growth of chronic myelogenous leukemia cells. The interaction of the complexes with bovine serum albumin and DNA is described. DNA footprinting using an oligonucleotide as substrate showed the complexes' preference for thymine base rich sites. It is worth notifying that the complexes interact with the Src homology SH3 domain of the Abl tyrosine kinase protein. Abl protein is involved in signal transduction and implicated in the development of chronic myelogenous leukemia. Nuclear magnetic resonance (NMR) studies of the interaction of complex 2 with the Abl-SH3 domain showed that the most affected residues were T79, G97, W99, and Y115.

Understanding metal-ligand interactions in coordination polymers using Hirshfeld surface analysis.

Properties related to the size and shape of Hirshfeld surfaces provide insight into the nature and strength of interactions among the building blocks of molecular crystals. In this work, we demonstrate that functions derived from the curvatures of the surface at a point, namely, shape index (S) and curvedness (C), as well as the distances from the surface to the nearest external (de) and internal (di) nuclei, can be used to help understand metal-ligand interactions in coordination polymers. The crystal structure of catena-poly[[[(1,10-phenanthroline-κ2N,N')copper(II)]-µ-4-nitrophthalato-κ2O1:O2] trihydrate], {[Cu(C8H3NO6)(C12H8N2)]·3H2O}n, described here for the first time, was used as a prototypical system for our analysis. Decomposition of the coordination polymer into its metal centre and ligand molecules followed by joint analysis of the Hirshfeld surfaces generated for each part unveil qualitative and semi-quantitative information that cannot be easily obtained either from conventional crystal packing analysis or from Hirshfeld surface analysis of the entire polymeric units. The shape index function S is particularly sensitive to the coordination details and its mapping on the surface of the metallic centre is highly dependent on the nature of the ligand and the coordination bond distance. Correlations are established between the shape of the Hirshfeld surface of the metal and the geometry of the metal-ligand contacts in the crystals. This could be applied not only to estimate limiting coordination distances in metal-organic compounds, but also to help establish structure-property relationships potentially useful for the crystal engineering of such materials.

Physics, chemistry, and Hirshfeld surface analyses of gamma-irradiated thalidomide to evaluate behavior under sterilization doses.

Thalidomide was indicated as a sedative and antiemetic and prescribed for pregnant women. Its tragic teratogenic effects culminated in withdrawal from the market. Since the discovery of its anti-angiogenic and anti-inflammatory actions, thalidomide has been used in the treatment of leprosy and multiple myeloma, which justify studies of its stability. We investigated the effects of irradiation of thalidomide up to 100 kGy (fourfold the usual sterilizing dose for pharmaceutics). The ß polymorph of thalidomide was obtained in an isothermal experiment at 270 °C. All samples underwent gamma irradiation for specific times. At different doses, decomposition of the pharmaceutical was not observed up to 100 kGy. The observed effect was angle turning between the phthalimide and glutarimide rings modulated by repulsion towards the carbonyl group, leading to a stable energetic configuration, as measured by the equilibrium in the torsion angle after irradiation. The thalidomide molecule has a center of symmetry, so a full turn starting from 57.3° will lead to an identical molecule. Further irradiation will start the process again. Samples irradiated at 30 and 100 kGy have more compact unit cells and a lower volume, which leads to an increase in the intermolecular hydrogen interaction within the unit cell, resulting in higher thermal stability for polymorph α.

DEB TACE for Intermediate and advanced HCC - Initial Experience in a Brazilian Cancer Center.

BACKGROUND: According to Barcelona Clinic Liver Cancer classification transarterial chemoembolization is indicated in patients with Hepatocellular Carcinoma in the intermediate stage. Drug-eluting microspheres can absorb and release the chemotherapeutic agent slowly for 14 days after its intra-arterial administration. This type of transarterial chemoembolization approach appears to provide at least equivalent effectiveness with less toxicity. METHODS: This is a prospective, single-center study, which evaluated 21 patients with intermediate and advanced hepatocellular carcinoma who underwent transarterial chemoembolization with drug-eluting microspheres. The follow up period was 2 years. Inclusion criteria was Child-Pugh A or B liver disease patients, intermediate or advanced hepatocellular carcinoma and performance status equal or below 2. Transarterial chemoembolization with drug-eluting microspheres was performed at 2-month intervals during the first two sessions. The third and subsequent sessions were performed according to the image findings on follow-up, on a "demand schedule". Tumor response and time to progression were evaluated along the two-year follow up period. RESULTS: Of the 21 patients 90% presented with liver cirrhosis, 62% had Barcelona Clinic Liver Cancer stage B and 38% had Barcelona Clinic Liver Cancer stage C hepatocellular carcinoma. Average tumor size was 6.9 cm. The average number of Transarterial chemoembolization with drug-eluting microspheres procedures was 3 with a total of 64 sessions. The predominant toxicity was mild. Liver function was not significantly affected in most patients. Two deaths occurred within 90 days after Transarterial chemoembolization with drug-eluting microspheres (ischemic hepatitis and hydropic decompensation). Technical success was achieved in 63 of 64 procedures. The mean hospital stay was 1.5 days. The progression free and overall survival at 1 and 2 years were 73.0% and 37.1%, 73.7% and 41.6%, respectively. CONCLUSION: Transarterial chemoembolization with drug-eluting microspheres is able to deliver significant tumor response and progression free survival rate with acceptable toxicity. Larger studies are needed to identify exactly which subset of advanced hepatocellular patients may benefit from this treatment. TRIAL REGISTRATION: study ID ISRCTN16295622. Registered October 14th 2016. Retrospectively registered. Website registration: http://www.isrctn.com/ISRCTN16295622.

Synthesis and Characterization of Cobalt(III), Nickel(II) and Copper(II) Mononuclear Complexes with the Ligand 1,3-bis[(2-aminoethyl)amino]-2-propanol and Their Catalase-Like Activity.

In this work, we present the synthesis and characterization of two new mononuclear complexes with the ligand 1,3-bis[(2-aminoethyl)amino]-2-propanol (HL), [Co(L)(H2O)](ClO4)2 (1), [Ni(HL)](ClO4)2 (2), as well as the known complex [Cu(HL)](ClO4)2 (3) for comparison. Their abilities to catalyze the dismutation of H2O2 and the oxidation of cyclohexane were investigated. The complexes were characterized by X-ray diffraction, elemental analysis, electronic and infrared spectroscopy, cyclic voltammetry, electrospray ionization mass spectrometry (ESI-MS) and conductivity measurements. The X-ray structures showed that the nickel (2) and copper (3) complexes are tetracoordinated, with the metal ion bound to the nitrogen atoms of the ligand. On the other hand, the cobalt complex (1) is hexacoordinated, possessing additional bonds to the alkoxo group of the ligand and to a water molecule. Neither of the complexes was able to catalyze the oxidation of cyclohexane, but all of them exhibited catalase-like activity, following Michaelis-Menten kinetics, which suggest resemblance with the catalase natural enzymes. The catalytic activity followed the order: [Ni(HL)](ClO4)2 (2) > [Cu(HL)](ClO4)2 (3) > [Co(L)(H2O)](ClO4)2 (1). As far as we know, this is the first description of a nickel complex presenting a significant catalase-like activity.

Selective endocytic trafficking in live cells with fluorescent naphthoxazoles and their boron complexes.

Fluorescent naphthoxazoles and their boron derivatives have been synthesized and applied as superior and selective probes for endocytic pathway tracking in live cancer cells. The best fluorophores were compared with the commercially available acridine orange (co-staining experiments), showing far better selectivity.