Polymorphism and Structural Variety in Sn(II) Carboxylate Coordination Polymers Revealed from Structure Solution of Microcrystals.

The crystal structures of four coordination polymers constructed from Sn(II) and polydentate carboxylate ligands are reported. All are prepared under hydrothermal conditions in KOH or LiOH solutions (either water or methanol-water) at 130-180 °C and crystallize as small crystals, microns or less in size. Single-crystal structure solution and refinement are performed using synchrotron X-ray diffraction for two materials and using 3D electron diffraction (3DED) for the others. Sn2 (1,3,5-BTC)(OH), where 1,3,5-BTC is benzene-1,3,5-tricarboxylate, is a new polymorph of this composition and has a three-dimensionally connected structure with potential for porosity. Sn(H-1,3,5-BTC) retains a partially protonated ligand and has a 1D chain structure bound by hydrogen bonding via ─COOH groups. Sn(H-1,2,4-BTC) contains an isomeric ligand, benzene-1,2,4-tricarboxylate, and contains inorganic chains in a layered structure held by hydrogen bonding. Sn2 (DOBDC), where DOBDC is 2,5-dioxido-benzene-1,4-dicarboxylate, is a new polymorph for this composition and has a three-dimensionally connected structure where both carboxylate and oxido groups bind to the tin centers to create a dense network with dimers of tin. In all materials, the Sn centers are found in highly asymmetric coordination, as expected for Sn(II). For all materials phase purity of the bulk is confirmed using powder X-ray diffraction, thermogravimetric analysis, and infrared spectroscopy.

Organogold(III)-dithiocarbamate compounds and their coordination analogues as anti-tumor and anti-leishmanial metallodrugs.

The limited chemical stability of gold(III)-based compounds in physiological environment has been a challenge in drug discovery, and organometallic chemistry might provide the solution to overcome this issue. In this work, four novel cationic organogold(III)-dithiocarbamate complexes of general structure [(C^N)AuIIIDTC]PF6 (C1a - C4a, DTC = dithiocarbamate, L1 - L4, C^N = 2-anilinopyridine) are presented, and compared to their coordination gold(III)-dithiocarbamate analogues [AuIIIDTCCl2] (C1b - C4b), as potential anti-cancer and anti-leishmanial drugs. Most of the complexes effectively inhibited cancer cell growth, notably C3a presented anti-proliferative effect in the nanomolar range against breast cancer (MCF-7 and MDA-MB-231 cells with moderate selectivity. Pro-apoptotic studies on treated MCF-7 cells showed a high population of cells in early apoptosis. Reactivity studies of C3a towards model thiols (N-acetyl-L-cysteine) refer to a possible mode of action involving bonding between the organogold(III)-core and the thiolate. In the scope of neglected diseases, gold complexes are emerging as promising therapeutic alternatives against leishmaniasis. In this regard, all gold(III)-dithiocarbamate complexes presented anti-leishmanial activity against at least one Leishmania species. Complexes C1a, C4a, C1b, C4b were active against all tested parasites with IC50 values varying between 0.12 and 42 µM, and, overall, organometallic compounds presented more intriguing inhibition profiles. For C4a selectivity over 500-fold for L. braziliensis; even higher than the reference anti-leishmanial drug amphotericin B. Overall, our findings revealed that the organogold(III) moiety significantly amplified the anti-cancer and anti-leishmanial effects with respect to the coordination analogues; thus, showing the great potential of organometallic chemistry in metallodrug-based chemotherapy for cancer and leishmaniasis.

Towards direct and eco-friendly analysis of plants using portable X-ray fluorescence spectrometry: A methodological approach.

The assessment of the nutritional status of plants is traditionally performed by wet-digestion methods using oven-dried and ground samples. This process requires sampling, takes time, and it is non-environmentally friendly. Agricultural and environmental science have been greatly benefited by in-field, ecofriendly methods, and real-time element measurements. This work employed the portable X-ray fluorescence spectrometry (pXRF) to analyze intact and fresh leaves of crops aiming to assess the effect of water content and leaf surface (adaxial and abaxial) on pXRF results. Also, pXRF data were used to predict the real concentration of macro- and micronutrients. Eight crops (bean, castor plant, coffee, eucalyptus, guava tree, maize, mango, and soybean) with contrasting water contents were used. Intact leaf fragments (∼2 × 2 cm), fresh or oven-dried (60 °C) were obtained to be analyzed via pXRF on both adaxial and abaxial surface. Conventional wet-digestion method was also performed on powdered material to obtain the concentration of macro- and micronutrients via ICP-OES. The data were subjected to descriptive statistics, principal component analysis (PCA) and random forest (RF) algorithm regression. RF was used to predict the real concentration of macro- and micronutrients based on pXRF measurements obtained directly on intact leaves. Water content had a significant effect on pXRF results. However, a positive correlation between the concentration of macro- and micronutrients obtained via pXRF directly on intact leaves and conventional analysis performed on powdered samples was obtained. PCA analysis allowed a clear differentiation of crops based on elemental composition. The concentrations of macro- and micronutrients were very accurately predicted via RF. Even elements not detected by pXRF (N and B) were satisfactory predicted. From this pilot study, it is possible to concluded that pXRF is feasible for in-field assessment of nutritional status of plants. Further studies are needed to obtain specific and robust calibrations for each crop.

Proximal sensing provides clean, fast, and accurate quality control of organic and mineral fertilizers.

Farms use large quantities of fertilizers from many sources, making quality control a challenging task, as the traditional wet-chemistry analyses are expensive, time consuming and not environmentally-friendly. As an alternative, this work proposes the use of portable X-ray fluorescence (pXRF) spectrometry and machine learning algorithms for rapid and low-cost estimation of macro and micronutrient contents in mineral and organic fertilizers. Four machine learning algorithms were tested. Whole (i.e., as delivered by the manufacturer) (CP) and ground (AQ) samples (429 in total) were analyzed to test the effect of fertilizer granulometry in prediction performance. Model validation indicated highly accurate predictions of macro (N: R2 = 0.92; P: 0.97; K: 0.99; Ca: 0.94, Mg: 0.98; S: 0.96) and micronutrients (B: 0.99; Cu: 0.99; Fe: 0.98; Mn: 0.91; Zn: 0.94) for both organic and mineral fertilizers. RPD values ranged from 2.31 to 9.23 for AQ samples, and Random Forest and Cubist Regression were the algorithms with the best performances. Even samples analyzed as they were received from the manufacturer (i.e., no grinding) provided accurate predictions, which accelerate the confirmation of nutrient contents contained in fertilizers. Results demonstrated the potential of pXRF data coupled with machine learning algorithms to assess nutrient composition in both mineral and organic fertilizers with high accuracy, allowing for clean, fast and accurate quality control. Sensor-driven quality assessment of fertilizers improves soil and plant health, crop management efficiency and food security with a reduced environmental footprint.

Clean quality control of agricultural and non-agricultural lime by rapid and accurate assessment of calcium and magnesium contents via proximal sensors.

Ca and Mg are the most important chemical elements in lime. Properly measuring Ca and Mg contents is essential to assess the quality of lime products. Quality control guarantees the adequate use of lime in industrial processes, in soils, and helps avoiding adulteration. Proximal sensors can aid in this process by determining Ca and Mg contents easily, rapidly and without producing chemical waste. The objective of this study was to evaluate the use an environmentally-friendly method of analyzing the quality of lime. We studied 1) the use of portable X-ray fluorescence (pXRF) to predict concentrations of Ca and Mg in lime, 2) tested if NixPro™ sensor can improve prediction accuracy and 3) tested if sample preparation methods (grinding) affect analyses. 74 samples of lime were analyzed by two different laboratories (lab. 1 = 38, lab. 2 = 36). All samples submitted to pXRF and NixPro™ analyses. Sensor analyses were done in whole (CP) and ground (AQ) samples to test the effect of sample preparation in prediction performance. High correlation was found between Ca and Mg contents measured via pXRF and laboratory analyses. Mg-CP presented the highest correlation coefficient (r = 0.81); Mg-AQ, the lowest (0.57). Predictions presented good performance (R2 > 0.68); Mg had the best results (0.86). Separating models per laboratory showed that some datasets are harder to model, probably due to variability in the source material (limestone). The addition of NixPro™ data contributed to improve prediction accuracy, although slightly. Predictions using CP samples presented the best results, especially for Mg, indicating that grinding is not necessary. This pioneer study demonstrated that fused proximal sensors can be used to rapidly and easily determine contents of Ca and Mg in soil amendments without producing chemical waste.

2-1-2 Stroke microsurgical thrombectomy technique as a tertiary/salvage treatment option.

BACKGROUND: Microsurgical thrombectomy (MST) has been used for many years in few stroke cases without any prospective randomized study, nor detailed systemized technique description. As many centers worldwide are recruited for stroke thrombectomy availability, MST might increase in the near future either as a tertiary or salvage treatment option. A straightforward surgical plan is mandatory empowering a safe, efficient, and rapid neurosurgical operation, so our aim is to describe the 2-1-2 microsurgical technique. METHODS: Three patients presented at emergency department with large stroke not suitable to venous thrombolysis and/or mechanical thrombectomy due to late arrival time and endovascular suite technical problems. They were referred to 2-1-2 MST after imaging showed brain collaterals on head angio-CT scan and ASPECTS greater than 6 points. The procedure comprised 2 insulin needle punctures in the target artery, 1mm micro-scissor transverse arteriotomy, milk thrombus removal and 2 simple sutures micro stitches. Sixty days clinical follow-up and brain imaging control provided data results. RESULTS: All patients treated with 2-1-2 MST technique had complete thrombus removal by precise surgical maneuvers avoiding surgeons unplanned and insecure movements to reduced operation time. Head angio-CT scan evidenced complete cerebrovascular circulation re-flow with clinical improvements in 60 days follow-up without complications or hospital readmissions. CONCLUSIONS: 2-1-2 MST technique can be rapidly and efficaciously performed in a systemized manner offering a tertiary or salvage technique for acute stroke treatment. Specific microsurgical training is mandatory to accomplish this treatment and larger studies are necessary to confirm our hypothesis.

Environmental and human-health risks of As in soils with abnormal arsenic levels located in irrigated agricultural areas of Paracatu (MG), Brazil.

The municipality of Paracatu (Brazil) is notorious for its large irrigated agricultural area and by abnormal arsenic (As) levels in selected soils of the region. Concerns regarding As exposure via ingestion of water and food are frequent, yet little is known about the behavior of arsenic in irrigated agricultural soils, as well as on As bioaccessibility/bioavailability in agroecosystems of this region. This work evaluated total and available As in agricultural soils cultivated under irrigation and in soils under native vegetation in Paracatu. We also assessed reactive arsenic fractions and As bioaccessibility in the soil, as well as arsenic levels in plant shoots to estimate As risks in these agroecosystems. Soil (different depths) and plant tissue samples were collected in 6 irrigated agricultural areas (CA1 to CA6) and 4 reference areas (RA1 to RA4). Total soil-As did not differ between soil depths, reinforcing that the source of As in agricultural soils is natural. This was evident when counterpointing arsenic and phosphorus contents at different soil depths, as both accumulate on the surface of oxidic soils when added to agroecosystems by anthropogenic routes (e.g., phosphate fertilization for P and irrigation for As). Available As levels in soils and plants were very small (below detection limit). Furthermore, all soils presented very low oral As bioaccessibility. Our findings revealed that the irrigated soils are not As polluted due to the low enrichment and accumulation of arsenic, as well as the prevalence of low ecological risks. There is no non-carcinogenic risk for the local population, except for children in RA2. The estimated carcinogenic risk for children followed the order RA2 > CA3 > CA4 > RA3 > CA2, and for adults, RA2 > CA3. Ultimately, the strategy of comparing the behavior of P and As in the soils of this study proved to be efficient in showing that there are no major risks to humans and the environment in the investigated area. However, periodic monitoring of As bioavailability in these areas is recommended.

Foliar Elemental Analysis of Brazilian Crops via Portable X-ray Fluorescence Spectrometry.

Foliar analysis is very important for the nutritional management of crops and as a supplemental parameter for soil fertilizer recommendation. The elemental composition of plants is traditionally obtained by laboratory-based methods after acid digestion of ground and sieved leaf samples. This analysis is time-consuming and generates toxic waste. By comparison, portable X-ray fluorescence (pXRF) spectrometry is a promising technology for rapid characterization of plants, eliminating such constraints. This worked aimed to assess the pXRF performance for elemental quantification of leaf samples from important Brazilian crops. For that, 614 samples from 28 plant species were collected across different regions of Brazil. Ground and sieved samples were analyzed after acid digestion (AD), followed by quantification via inductively coupled plasma optical emission spectroscopy (ICP-OES) to determine the concentration of macronutrients (P, K, Ca, Mg, and S) and micronutrients (Fe, Zn, Mn, and Cu). The same plant nutrients were directly analyzed on ground leaf samples via pXRF. Four certified reference materials (CRMs) for plants were used for quality assurance control. Except for Mg, a very strong correlation was observed between pXRF and AD for all plant-nutrients and crops. The relationship between methods was nutrient- and crop-dependent. In particular, eucalyptus displayed optimal correlations for all elements, except for Mg. Opposite to eucalyptus, sugarcane showed the worst correlations for all the evaluated elements, except for S, which had a very strong correlation coefficient. Results demonstrate that for many crops, pXRF can reasonably quantify the concentration of macro- and micronutrients on ground and sieved leaf samples. Undoubtedly, this will contribute to enhance crop management strategies concomitant with increasing food quality and food security.

Pain and Satisfaction Levels upon Removal of External Fixator at an Outpatient Facility.

Objective To quantify the levels of satisfaction and pain of patients submitted to external fixation removal without anesthesia at an outpatient facility. Methods The present was a prospective study involving 28 patients using external fixators who answered 3 questionnaires associated with the Visual Analogue and Numerical Pain Scale during different moments of the removal. Results The average pain prior to fixator removal was of 3.61. Shortly after the procedure, the patients reported that, on average, the most intense pain scored 6.68, and the least intense pain, 2.25 points. The average pain variation was of 4.43 points, and pain after 1 week scored, on average, 2.03 points. The recollection of the pain after fixator removal scored lower than the pain reported immediately after the procedure (mean value: 5.29). Most patients were middle-aged men, and 89.3% used circular external fixators. The main limb segment involved was the leg, and most patients (71.4%) had never used an external fixator before; they preferred the removal at an outpatient facility because it was faster (75%), and to avoid hospitalization (25%). The most intense pain was felt during the removal of Schanz pins (60.7%), being worse in the extremities of the limbs for 75% of the patients. An absolute majority of 85.7% was satisfied with the removal, and 82.1% stated that they would undergo the procedure again. Conclusion External fixator removal at an outpatient facility without anesthesia is a well-tolerated option for patients, with good levels of approval and satisfaction.

Pain and Satisfaction Levels upon Removal of External Fixator at an Outpatient Facility / Nível de satisfação e dor na retirada de fixador externo em um ambulatório

Abstract Objective To quantify the levels of satisfaction and pain of patients submitted to external fixation removal without anesthesia at an outpatient facility. Methods The present was a prospective study involving 28 patients using external fixators who answered 3 questionnaires associated with the Visual Analogue and Numerical Pain Scale during different moments of the removal. Results The average pain prior to fixator removal was of 3.61. Shortly after the procedure, the patients reported that, on average, the most intense pain scored 6.68, and the least intense pain, 2.25 points. The average pain variation was of 4.43 points, and pain after 1 week scored, on average, 2.03 points. The recollection of the pain after fixator removal scored lower than the pain reported immediately after the procedure (mean value: 5.29). Most patients were middle-aged men, and 89.3% used circular external fixators. The main limb segment involved was the leg, and most patients (71.4%) had never used an external fixator before; they preferred the removal at an outpatient facility because it was faster (75%), and to avoid hospitalization (25%). The most intense pain was felt during the removal of Schanz pins (60.7%), being worse in the extremities of the limbs for 75% of the patients. An absolute majority of 85.7% was satisfied with the removal, and 82.1% stated that they would undergo the procedure again. Conclusion External fixator removal at an outpatient facility without anesthesia is a well-tolerated option for patients, with good levels of approval and satisfaction.

Resumo Objetivo Quantificar os níveis de satisfação e dor dos pacientes submetidos a retirada ambulatorial de fixadores externos sem anestesia. Métodos Estudo prospectivo envolvendo 28 pacientes usando fixadores externos submetidos a três questionários associados à Escala Visual Analógica e Numérica da dor durante diferentes etapas da retirada. Resultados A média de dor prévia à retirada foi de 3,61. Logo após o término do procedimento, encontramos média de 6,68 para a dor mais intensa, e de 2,25 para a dor menos intensa. A variação da dor média foi de 4,43, e a dor após uma semana teve média de 2,03. A lembrança dolorosa da retirada foi menor do que a dor referida imediatamente após a retirada (média de 5,29). A predominância no estudo foi de pacientes do sexo masculino de meia-idade, e 89,3% usavam fixador externo do tipo circular. O principal segmento dos membros envolvido foi a perna, e a maior parte dos pacientes não havia feito uso de fixador externo previamente (71,4%); eles optaram pela retirada ambulatorial por se tratar de opção mais rápida (75%), e para evitar internação hospitalar (25%). O momento de dor mais intensa ocorreu durante a retirada dos pinos de Schanz (60,7%), sendo pior nas extremidades dos membros para 75% dos entrevistados. Uma maioria absoluta de 85,7% mostrou-se satisfeita após a retirada, e 82,1% afirmaram que se submeteriam novamente ao procedimento. Conclusão A retirada ambulatorial de fixadores externos sem anestesia é uma opção bem tolerada pelos pacientes, tratando-se de um procedimento com bons níveis de aceitabilidade e satisfação.

Nanocrystalline Transition-Metal Gallium Oxide Spinels from Acetylacetonate Precursors via Solvothermal Synthesis.

The synthesis of mixed-metal spinels based on substituted γ-Ga2O3 is reported using metal acetylacetonate precursors in solvothermal reactions with alcohols as solvents at 240 °C. New oxides of Cr, Mn and Fe have been produced, all of which are formed as nanocrystalline powders, as seen by high-resolution transmission electron microscopy (HR-TEM). The first chromium-gallium mixed oxide is thus formed, with composition 0.33Ga1.87Cr0.8O4 ( = vacant site). X-ray absorption near-edge spectroscopy (XANES) at the chromium K-edge shows the presence of solely octahedral Cr3+, which in turn implies a mixture of tetrahedral and octahedral Ga3+, and the material is stable on annealing to at least 850 °C. An analogous manganese material with average chemical composition close to MnGa2O4 is shown to contain octahedral Mn2+, along with some Mn3+, but a different inversion factor to materials reported by conventional solid-state synthesis in the literature, which are known to have a significant proportion of tetrahedral Mn2+. In the case of iron, higher amounts of the transition metal can be included to give an Fe:Ga ratio of 1:1. Elemental mapping using energy dispersive X-ray spectroscopy on the TEM, however, reveals inhomogeneity in the distribution of the two metals. This is consistent with variable temperature 57Fe Mössbauer spectroscopy that shows the presence of Fe2+ and Fe3+ in more than one phase in the sample. Variable temperature magnetisation and electron paramagnetic resonance (EPR) indicate the presence of superparamagnetism at room temperature in the iron-gallium oxides.

Minilaparoscopy-assisted transumbilical laparoscopic cholecystectomy.

The role of laparoscopy in the modern surgery era is well established. With the prospect of being able to improve the already privileged current situation, new alternatives have been proposed, such as natural orifice endoscopic surgery (NOTES), the method for single transumbilical access (LESS - Laparo-endoscopic single-site surgery) and minilaparoscopy (MINI). The technique proposed by the authors uses a laparoscope with an operative channel like the flexible endoscope used in NOTES. All operative times are carried out through the umbilical trocar as in LESS, and assisted by a minilaparoscopy grasper. This new technic combines, and results from, the rationalization of technical particularities and synergy of these three approaches, seeking to join their advantages and minimize their disadvantages. RESUMO O papel da videolaparoscopia na era moderna da cirurgia encontra-se bem estabelecido. Com a perspectiva de ser possível melhorar a já privilegiada situação atual, novas alternativas têm sido propostas, como a cirurgia por orifícios naturais (NOTES), o método por acesso único transumbilical (LESS - Laparo-endoscopic single-site surgery) e a minilaparoscopia (MINI). A técnica proposta pelos autores utiliza-se de óptica com canal de trabalho como o endoscópio flexível do NOTES, executa-se todos os tempos operatórios pelo trocarte umbilical, como no LESS, e é assistido por pinça de minilaparoscopia. Esta nova técnica combina e resulta da racionalização de particularidades técnicas e do sinergismo destas três abordagens, buscando agregar suas vantagens e minimizar as suas desvantagens.

Papilomatose da vesícula biliar associada à leucodistrofia metacromática, uma causa rara de hemobilia não traumática / Papillomatosis of the gallbrander associated with metachromatic leukodystrophy, a rarre cause of nontraumatic hemobilia

A principal causa de hemobilia é a lesão traumática de ramos intra-hepáticos da artéria hepática. Porém, outras etiologias são descritas. O objetivo deste artigo é apresentar uma rara causa de hemorragia digestiva secundária à hemobilia associada à leucodistrofia metacromática. Revisão bibliográfica evidenciou apenas quatro casos descritos.

The main cause of hemobilia is the traumatic injury of intrahepatic branches of the hepatic artery. However, other etiologies are decribed. The objective of this paper is to present a rare case of gastrointestinal bleeding secondary to hemobilia associated with metachromatic leukodystrophy. Literature review revealed only four cases described.

Bismuth sulphides prepared by thermal and hydrothermal decomposition of a single source precursor: the effect of reaction parameters on morphology, microstructure and catalytic activity.

Bismuth sulphides were prepared by thermal and hydrothermal decomposition of a precursor, bismuth tris-diethyldithiocarbamate, at different temperatures and times. The obtained results showed that the thermal decomposition of the precursor in a tube furnace was not very appropriate to control particle size and morphology. XRD results showed that at 310 °C the precursor was not fully decomposed but at 500 °C besides the orthorhombic bismuth sulphide, the metallic bismuth also started to be formed. At the highest temperature 1D crystals were formed with an apparent mean crystal size of 138 nm. However, hydrothermal decomposition was shown to be a very suitable method to control particle size and morphology just by varying some parameters such as temperature and time. For 6 hours reaction time, as temperature increased, the apparent mean crystal size decreased. The particle morphology was also very affected by this parameter, at 180 °C only 1D particles (nanorods) with lengths varying from 25 to 4700 nm were formed but at 200 °C not only 1D particles but also 2D particles were (nanosheets) obtained. Bismuth sulphide particles obtained at 180 °C and 24 hours reaction time were shown to be formed mostly by 2D particles compared to those obtained at 6 hours. It was clearly seen that the increase in reaction time and temperature led to the formation of bi-dimensional particles. The presence of 1D crystals in the samples obtained by hydrothermal decomposition at 180 °C/6 h and 180 °C/24 h is responsible for their high catalytic efficiency towards methylene blue dye degradation.

Temperature and time dependence on ZnS microstructure and phases obtained through hydrothermal decomposition of diethyldithiocarbamate complexes.

Zinc sulphide was obtained through hydrothermal decomposition of [Zn(S2CNEt2)] under different experimental conditions such as temperatures and reaction times. Hydrothermal reactions were carried out in a stainless steel autoclave at 160, 180 and 200 °C for 3, 6 and 24 hours. The obtained products were characterized using X-ray diffraction, scanning and high resolution transmission electron microscopies. Particle size and microstrain were determined by Rietveld refinement of experimental X-ray diffraction patterns. The obtained crystal size values were in the range of 6.1 to 30 nm and as the temperature and reaction times increase the particle size also increases. Band gap values are in the range of 3.34 to 3.60 eV and are highly dependent on the crystal microstrain. The catalyst activities were studied through the degradation of methylene blue dye solutions under ultraviolet radiation.

Design, structural and spectroscopic elucidation, and the in vitro biological activities of new diorganotin dithiocarbamates.

The reaction of 2,2-dimethoxy-N-methylethyllamine or 2-methyl-1,3-dioxolane with CS(2) in alkaline media produced two novel dithiocarbamate salts. Subsequent reactions with organotin halides yielded six new complexes: [SnMe(2){S(2)CNR(R(1))(2)}(2)] (1), [Sn(n-Bu)(2){S(2)CNR(R(1))(2)}(2)] (2), [SnPh(2){S(2)CNR(R(1))(2)}(2)] (3), [SnMe(2){S(2)CNR(R(2))(2)}(2)] (4), [Sn(n-Bu)(2){S(2)CNR(R(2))(2)}(2)] (5), [SnPh(2){S(2)CNR(R(2))(2)}(2)] (6), where R = methyl, R(1) = CH(2)CH(OMe)(2), and R(2) = 2-methyl-1,3-dioxolane. All compounds were identified in terms of infrared, (1)H and (13)C NMR, and the complexes were also characterized using (119)Sn NMR, (119)Sn Mössbauer and X-ray crystallography. The biological activity of all derivatives has been screened in terms of IC(90) and IC(50) against Aspergillus flavus, Aspergillus niger, Aspergillus parasiticus, Penicillium citrinum, Curvularia senegalensis, Staphylococcus aureus, Listeria monocytogenes, Bacillus cereus, Streptococcus sanguinis, Escherichia coli, Citrobacter freundii, Salmonella typhimurium, and Pseudomonas aeruginosa and the results correlated well with a performed study of structure-activity relationship (SAR). Complexes (3), (5) and (6) displayed the best IC(90) and IC(50) in the presence of the fungi, greater than that of miconazole, used as control drug.

Transumbilical laparoscopic assisted appendectomy compared with laparoscopic and laparotomic approaches in acute appendicitis.

BACKGROUND: Acute appendicitis is the most common cause of acute abdominal surgery. Despite nearly three decades comparing laparoscopic with laparotomic appendectomy, the available scientific evidence does not show consensus of opinion about the best access for the treatment of acute appendicitis. The transumbilical laparoscopic assisted appendectomy combines the advantages of laparoscopic access to the simplicity of the laparotomic technique. AIM: To compare the three technical advantages showing possible tendency to transumbilical laparoscopic assisted appendectomy. METHODS: This is a retrospective study comparing three series with 1232 patients. Variables were: operative time, hospital stay, early and late postoperative complications, postoperative pain and earlier return to daily activities. RESULTS: The averaged surgical time was 59.8 min in laparotomic appendectomy, 75.5 min in laparoscopic appendectomy and 51,7 min in transumbilical laparoscopic assisted appendectomy with significant difference. The incidence of postoperative pain, general complications and wound infection were greater in the group submitted to laparotomic appendectomy. The earlier return to daily activities and short hospital stay were observed in groups laparoscopic appendectomy and transumbilical laparoscopic assisted appendectomy. CONCLUSION: The effectiveness and safety of transumbilical laparoscopic assisted appendectomy can make this technique the preferred choice in the initial management of patients with acute appendicitis.

Apendicectomia videoassistida por acesso único transumbilical comparada à via laparoscópica e laparotômica na apendicite aguda / Transumbilical laparoscopic assisted appendectomy compared with laparoscopic and laparotomic approaches in acute appendicitis

RACIONAL: A apendicite aguda é a causa mais comum de abdome agudo cirúrgico. Apesar de quase três décadas de pesquisa, comparando a apendicectomia laparoscópica com a apendicectomia laparotômica, as evidências científicas disponíveis não mostram consenso de opinião a respeito da melhor via de acesso para o tratamento da apendicite aguda. A apendicectomia videoassistida por acesso único transumbilical visa combinar as vantagens do acesso laparoscópico com a simplicidade da técnica laparotômica. OBJETIVO: Comparar as três técnicas sinalisando as vantagens existentes no acesso único transumbilical. MÉTODOS: Estudo retrospectivo, comparativo de três séries englobando 1232 pacientes. As variáveis analisadas foram: tempo operatório, permanência hospitalar, complicações pós-operatórias precoces e tardias, dor pós-operatória e retorno às atividades habituais. RESULTADOS: Observou-se que os procedimentos acesso único transumbilical, apendicectomia laparoscópica e apendicectomia laparotômica apresentaram tempo de operação, em média, de 51,7 minutos, 75,5 minutos e 59,8 minutos, respectivamente, com diferença estatisticamente significativa. A incidência de dor pós-operatória, complicações gerais e infecção de ferida foram maiores no grupo apendicectomia laparotômica. Os grupos apendicectomia laparoscópica e acesso único transumbilical apresentaram retorno mais precoce às atividades habituais e menor permanência hospitalar. CONCLUSÃO: Atualmente não há condições de estabelecer-se entre as três técnicas a de padrão-ouro para o tratamento da apendicite aguda. A efetividade e a segurança da apendicectomia videoassistida por acesso único transumbilical, associadas aos atrativos da técnica, podem fazer dela a escolha preferencial na abordagem inicial dos pacientes com diagnóstico de apendicite aguda.

BACKGROUND: Acute appendicitis is the most common cause of acute abdominal surgery. Despite nearly three decades comparing laparoscopic with laparotomic appendectomy, the available scientific evidence does not show consensus of opinion about the best access for the treatment of acute appendicitis. The transumbilical laparoscopic assisted appendectomy combines the advantages of laparoscopic access to the simplicity of the laparotomic technique. AIM: To compare the three technical advantages showing possible tendency to transumbilical laparoscopic assisted appendectomy. METHODS: This is a retrospective study comparing three series with 1232 patients. Variables were: operative time, hospital stay, early and late postoperative complications, postoperative pain and earlier return to daily activities. RESULTS: The averaged surgical time was 59.8 min in laparotomic appendectomy, 75.5 min in laparoscopic appendectomy and 51,7 min in transumbilical laparoscopic assisted appendectomy with significant difference. The incidence of postoperative pain, general complications and wound infection were greater in the group submitted to laparotomic appendectomy. The earlier return to daily activities and short hospital stay were observed in groups laparoscopic appendectomy and transumbilical laparoscopic assisted appendectomy. CONCLUSION: The effectiveness and safety of transumbilical laparoscopic assisted appendectomy can make this technique the preferred choice in the initial management of patients with acute appendicitis.

fac-(2-Amido-ethyl-κC,O)trichlorido(urea-κO)tin(IV).

The Sn atom in the title compound, [Sn(C(3)H(6)NO)Cl(3)(CH(4)N(2)O)], is octa-hedrally coordinated within a CCl(3)NO donor set provided by a chelating amido-ethyl ligand (C and O), a urea-O atom and three facially arranged Cl atoms. Systematic variations in the Sn-Cl bond distances are correlated with the relative trans influence exerted by the C and carbonyl-O atoms. The three-dimensional crystal packing is stabilized by N-H⋯O and N-H⋯Cl hydrogen bonds.

(2-Carbamoylethyl-κC,O)triiodidotin(IV).

Two independent but virtually identical mol-ecules comprise the asymmetric unit of the title compound, [Sn(C(3)H(6)NO)I(3)]. The CI(3)O coordination geometry around the Sn(IV) atom is defined by a chelating carbamoylethyl ligand (C(1),O-bidentate) and three I atoms, and is based on a distorted trigonal bipyramid with the carbonyl O atom occupying a position trans to one of the I atoms which forms the longer of the Sn-I bonds. The independent mol-ecules are linked via N-H⋯O hydrogen bonds, which leads to the formation on an eight-membered amide {⋯HNCO}(2) synthon. N-H⋯I hydrogen-bonding inter-actions are also present between neighbouring mol-ecules.