Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 20 de 42
Filter
3.
Mar Pollut Bull ; 191: 114915, 2023 Jun.
Article in English | MEDLINE | ID: mdl-37084613

ABSTRACT

The COVID-19 pandemic caused that most countries established the closure of many beaches, affecting the scientific monitoring of thousands of coastal sectors. This article shows the status of beach litter in South America before and after COVID-19 closure. The data were obtained during the years 2019, 2020 and 2022 on 25 beaches using a technique BLAT-QQ. The results show that cigarette butts were the most frequent type of litter, meanwhile Brazil should improve cleanliness of general gross litter and gross polystyrene. Colombia gross vegetation litter and small vegetation litter, and Ecuador organic litter from animals. The results shown in qualitative and quantitative manner facilitate their understanding for managers, scholars and activists interested on beach litter monitoring. This baseline is useful to analyse regional and worldwide marine litter trends with the purpose to start or restart monitoring of tourist beaches from a science-based method.


Subject(s)
COVID-19 , Waste Products , Humans , Waste Products/analysis , Environmental Monitoring/methods , Pandemics , Plastics , Bathing Beaches , Brazil
4.
IDCases ; 22: e00992, 2020.
Article in English | MEDLINE | ID: mdl-33194548

ABSTRACT

BACKGROUND: Mycobacterium abscessus is one of the most pathogenic and drug-resistant opportunistic microorganisms among the nontuberculous mycobacteria (NTM) involved in skin and soft tissue infections (SSTI) associated with cosmetic surgical procedures. However, NTM infection is often wrongly diagnosed initially causing prolonged suffering. Here is described the author's experience working with patients who developed M. abscessus SSTI after cosmetic procedures. METHODS: Patients who developed NTM infection after undergoing cosmetic procedures, and who presented at the Hospital Metropolitano and Hospital Vozandes (Quito, Ecuador) between 2013-2016. A review of patient medical records was performed. RESULTS: Five patients with culture proven M. abscessus subspecies abscessus SSTI after cosmetic surgeries were identified. All patients were treated with aggressive surgical debridement and antibiotics. CONCLUSIONS: A rapidly spreading wound infection presenting two or more weeks after a cosmetic procedure that fails to respond to standard antimicrobial therapy should raise suspicion for NTM infection. Samples for acid-fast bacilli smear, cultures, and PCR from infected tissue should be taken. Surgical drainage and debridement are recommended along with a long course of antibiotics. In the absence of clinical trials, a combination of amikacin, imipenem, and clarithromycin may be an adequate initial treatment for M. abscessus subspecies abscessus SSTI in immunocompetent patients.

5.
Clin Transl Radiat Oncol ; 18: 140-145, 2019 Sep.
Article in English | MEDLINE | ID: mdl-31341990

ABSTRACT

The latest development in radiation oncology departments towards high precision and adaptive radiation therapy is the clinical introduction of magnetic resonance image guided radiation therapy (MRgRT). Early 2016, patient treatment using MRgRT was started at Amsterdam UMC, location VU University Medical Center. Introducing this novel technique in clinical practice requires thorough preparation with regard to important topics, such as MR-safety and training, equipping the treatment vault and console room, development of MRgRT workflow and logistical issues. Certainly when MRgRT is combined with daily plan adaptation, this indicates adjusting existing workflows and protocols. The MRgRT workflow requires a multidisciplinary process, and while each discipline has had its own tasks and responsibilities, with growing clinical experience there has been a shift towards RTT responsibilities. In this overview we discuss preclinical training and preparation for the implementation of (adaptive) MRgRT, with a particular focus on the perspective of RTTs. Although the reviewed logistics are partly the result of the decision to perform daily plan re-optimization, our experience can be extrapolated to implementation of alternative approaches for MRgRT.

6.
Radiat Oncol ; 14(1): 92, 2019 Jun 03.
Article in English | MEDLINE | ID: mdl-31167658

ABSTRACT

Magnetic Resonance-guided radiotherapy (MRgRT) marks the beginning of a new era. MR is a versatile and suitable imaging modality for radiotherapy, as it enables direct visualization of the tumor and the surrounding organs at risk. Moreover, MRgRT provides real-time imaging to characterize and eventually track anatomical motion. Nevertheless, the successful translation of new technologies into clinical practice remains challenging. To date, the initial availability of next-generation hybrid MR-linac (MRL) systems is still limited and therefore, the focus of the present preview was on the initial applicability in current clinical practice and on future perspectives of this new technology for different treatment sites.MRgRT can be considered a groundbreaking new technology that is capable of creating new perspectives towards an individualized, patient-oriented planning and treatment approach, especially due to the ability to use daily online adaptation strategies. Furthermore, MRL systems overcome the limitations of conventional image-guided radiotherapy, especially in soft tissue, where target and organs at risk need accurate definition. Nevertheless, some concerns remain regarding the additional time needed to re-optimize dose distributions online, the reliability of the gating and tracking procedures and the interpretation of functional MR imaging markers and their potential changes during the course of treatment. Due to its continuous technological improvement and rapid clinical large-scale application in several anatomical settings, further studies may confirm the potential disruptive role of MRgRT in the evolving oncological environment.


Subject(s)
Magnetic Resonance Imaging , Neoplasms/radiotherapy , Radiotherapy, Image-Guided , Humans , Neoplasms/diagnostic imaging , Organs at Risk/diagnostic imaging , Organs at Risk/radiation effects , Precision Medicine , Radiotherapy Dosage , Radiotherapy Planning, Computer-Assisted , Radiotherapy, Image-Guided/trends , Radiotherapy, Intensity-Modulated , Reproducibility of Results
7.
Appl Environ Microbiol ; 84(11)2018 06 01.
Article in English | MEDLINE | ID: mdl-29625974

ABSTRACT

The Cuatro Ciénegas Basin (CCB) is located in the Chihuahuan desert in the Mexican state of Coahuila; it has been characterized as a site with high biological diversity despite its extreme oligotrophic conditions. It has the greatest number of endemic species in North America, containing abundant living microbialites (including stromatolites and microbial mats) and diverse microbial communities. With the hypothesis that this high biodiversity and the geographic structure should be reflected in the virome, the viral communities in 11 different locations of three drainage systems, Churince, La Becerra, and Pozas Rojas, and in the intestinal contents of 3 different fish species, were analyzed for both eukaryotic and prokaryotic RNA and DNA viruses using next-generation sequencing methods. Double-stranded DNA (dsDNA) virus families were the most abundant (72.5% of reads), followed by single-stranded DNA (ssDNA) viruses (2.9%) and ssRNA and dsRNA virus families (0.5%). Thirteen families had dsDNA genomes, five had ssDNA, three had dsRNA, and 16 had ssRNA. A highly diverse viral community was found, with an ample range of hosts and a strong geographical structure, with very even distributions and signals of endemicity in the phylogenetic trees from several different virus families. The majority of viruses found were bacteriophages but eukaryotic viruses were also frequent, and the large diversity of viruses related to algae were a surprise, since algae are not evident in the previously analyzed aquatic systems of this ecosystem. Animal viruses were also frequently found, showing the large diversity of aquatic animals in this oasis, where plants, protozoa, and archaea are rare.IMPORTANCE In this study, we tested whether the high biodiversity and geographic structure of CCB is reflected in its virome. CCB is an extraordinarily biodiverse oasis in the Chihuahuan desert, where a previous virome study suggested that viruses had followed the marine ancestry of the marine bacteria and, as a result of their long isolation, became endemic to the site. In this study, which includes a larger sequencing coverage and water samples from other sites within the valley, we confirmed the high virus biodiversity and uniqueness as well as the strong biogeographical diversification of the CCB. In addition, we also analyzed fish intestinal contents, finding that each fish species eats different prey and, as a result, presents different viral compositions even if they coexist in the same pond. These facts highlight the high and novel virus diversity of CCB and its "lost world" status.


Subject(s)
Bacteriophages/classification , Biodiversity , DNA Viruses/classification , Fishes/virology , Microbiota , RNA Viruses/classification , Animals , Bacteriophages/isolation & purification , DNA Viruses/isolation & purification , DNA, Bacterial/genetics , Genetic Variation , Geography , Intestines/virology , Mexico , Phylogeny , RNA Viruses/isolation & purification , RNA, Ribosomal, 16S/genetics , Water Microbiology
8.
Radiother Oncol ; 125(3): 439-444, 2017 12.
Article in English | MEDLINE | ID: mdl-28811038

ABSTRACT

BACKGROUND AND PURPOSE: To implement a robust and fast stereotactic MR-guided adaptive radiation therapy (SMART) online strategy in locally advanced pancreatic cancer (LAPC). MATERIAL AND METHODS: SMART strategy for plan adaptation was implemented with the MRIdian system (ViewRay Inc.). At each fraction, OAR (re-)contouring is done within a distance of 3cm from the PTV surface. Online plan re-optimization is based on robust prediction of OAR dose and optimization objectives, obtained by building an artificial neural network (ANN). Proposed limited re-contouring strategy for plan adaptation (SMART3CM) is evaluated by comparing 50 previously delivered fractions against a standard (re-)planning method using full-scale OAR (re-)contouring (FULLOAR). Plan quality was assessed using PTV coverage (V95%, Dmean, D1cc) and institutional OAR constraints (e.g. V33Gy). RESULTS: SMART3CM required a significant lower number of optimizations than FULLOAR (4 vs 18 on average) to generate a plan meeting all objectives and institutional OAR constraints. PTV coverage with both strategies was identical (mean V95%=89%). Adaptive plans with SMART3CM exhibited significant lower intermediate and high doses to all OARs than FULLOAR, which also failed in 36% of the cases to adhere to the V33Gy dose constraint. CONCLUSIONS: SMART3CM approach for LAPC allows good OAR sparing and adequate target coverage while requiring only limited online (re-)contouring from clinicians.


Subject(s)
Magnetic Resonance Imaging/methods , Pancreatic Neoplasms/radiotherapy , Radiosurgery/methods , Radiotherapy Planning, Computer-Assisted/methods , Radiotherapy, Image-Guided/methods , Humans , Organs at Risk , Radiosurgery/adverse effects , Radiotherapy Dosage
10.
J Water Health ; 12(1): 94-104, 2014 Mar.
Article in English | MEDLINE | ID: mdl-24642436

ABSTRACT

Municipal water disinfection systems in some areas are not always able to meet water consumer needs, such as ensuring distributed water quality, because household water management can be a contributing factor in water re-contamination. This fact is related to the storage options that are common in places where water is scarce or is distributed over limited time periods. The aim of this study is to assess the removal capacity of a multiple-barrier water disinfection device for protozoa, bacteria, and viruses. Water samples were taken from households in Mexico City and spiked with a known amount of protozoa (Giardia cyst, Cryptosporidium oocyst), bacteria (Escherichia coli), and viruses (rotavirus, adenovirus, F-specific ribonucleic acid (FRNA) coliphage). Each inoculated sample was processed through a multiple-barrier device. The efficiency of the multiple-barrier device to remove E. coli was close to 100%, and more than 87% of Cryptosporidium oocysts and more than 98% of Giardia cysts were removed. Close to 100% of coliphages were removed, 99.6% of the adenovirus was removed, and the rotavirus was almost totally removed. An effect of site by zone was detected; this observation is important because the water characteristics could indicate the efficiency of the multiple-barrier disinfection device.


Subject(s)
Drinking Water , Water Microbiology , Water Purification/instrumentation , Adenoviridae/isolation & purification , Coliphages/isolation & purification , Cryptosporidium parvum/isolation & purification , Equipment Design , Escherichia coli/isolation & purification , Giardia lamblia/isolation & purification , Humans , Mexico , Rotavirus/isolation & purification
11.
Int J Syst Evol Microbiol ; 64(Pt 2): 392-399, 2014 Feb.
Article in English | MEDLINE | ID: mdl-24065772

ABSTRACT

Four Gram-staining-negative, catalase- and oxidase-positive, pale-orange pigmented bacterial strains (435-08(T), 47B-3-09, 412R-09(T) and 60B-3-09) were isolated from diseased rainbow trout. Analysis of their 16S rRNA gene sequences suggested their adscription to the genus Flavobacterium. Strains formed two phylogenetic groups represented by strains 435-08(T) and 47B-3-09 (group A), and strains 412R-09(T) and 60B-3-09 (group B) displaying 16S rRNA sequence similarities greater than 99.8-99.9% within their respective groups. Strain 435-08(T) exhibited the highest levels of similarity with Flavobacterium aquidurense WB-1.1.56(T) (98.6% sequence similarity) and strain 412R-09(T) with Flavobacterium frigidimaris KUC-1(T) and Flavobacterium aquidurense WB-1.1.56(T) (98.9% and 98.6% sequence similarity, respectively). DNA-DNA hybridization studies showed low levels of relatedness between strain 435-08(T) and strain 412R-09(T) and between both strains and the most closely related species of the genus Flavobacterium. The genomic DNA G+C contents of strains 435-08(T) and 412R-09(T) were 36.2 and 34.3 mol%, respectively. The predominant respiratory quinone of both strains was MK-6 and the major fatty acids were iso-C(15 : 0), C(16 : 1)ω7c and C(15 : 0). The two groups of strains could be distinguished from each other and from related species of the genus Flavobacterium by a number of phenotypic properties. Phylogenetic, genotypic and phenotypic evidence indicated that strains of groups A and B represent two novel species of the genus Flavobacterium, for which the names Flavobacterium tructae sp. nov. (type strain 435-08(T) = CECT 7791(T) = CCUG 60100(T)) and Flavobacterium piscis sp. nov. (type strain 412R-09(T) = CECT 7911(T) = CCUG 60099(T)) are proposed.


Subject(s)
Flavobacterium/classification , Oncorhynchus mykiss/microbiology , Phylogeny , Animals , Bacterial Typing Techniques , Base Composition , DNA, Bacterial/genetics , Fatty Acids/chemistry , Flavobacterium/genetics , Flavobacterium/isolation & purification , Molecular Sequence Data , Nucleic Acid Hybridization , RNA, Ribosomal, 16S/genetics , Sequence Analysis, DNA , Spain , Vitamin K 2/analogs & derivatives , Vitamin K 2/chemistry
12.
Syst Appl Microbiol ; 35(5): 315-9, 2012 Jul.
Article in English | MEDLINE | ID: mdl-22795568

ABSTRACT

Three pale-orange bacteria (strains 1083-08, 1084-08(T) and 1095B-08) were isolated from diseased rainbow trout. The isolates were Gram-staining-negative, catalase- and oxidase-positive, rod-shaped cells. Analyses of their 16S rRNA gene sequences confirmed their adscription to the genus Chryseobacterium. The three isolates shared 100% 16S rRNA gene sequence similarity and 98.5% similarity with Chryseobacterium indologenes CCUG 14556(T), being the closest phylogenetically related species. Genomic DNA-DNA hybridization similarity values between the three isolates were 94-100% and 2-39% between strain 1084-08(T) and the type strains of other related Chryseobacterium species, confirming that the isolates represent a novel species within the genus Chryseobacterium. The DNA G+C content of the species was 33.6-36.1mol%. The predominant respiratory quinone of strain 1084-08(T) was MK-6 and the major fatty acids were iso-C(15:0), iso-C(17:1)ω9c, iso-C(17:0) 3-OH and C(16:1)ω6c. The isolates were distinguished from related Chryseobacterium species by a number of phenotypic properties. Based on the phenotypic, genotypic and phylogenetic findings, it is proposed that the new isolates from rainbow trout be classified as a new species of the genus Chryseobacterium, with the name of Chryseobacterium tructae sp. nov. The type strain is 1084-08(T) (=CECT 7798(T)=CCUG 60111(T)).


Subject(s)
Chryseobacterium/classification , Chryseobacterium/isolation & purification , Oncorhynchus mykiss/microbiology , Animals , Chryseobacterium/genetics , Chryseobacterium/physiology , Fish Diseases/microbiology , Gills/microbiology , Liver/microbiology , Phylogeny
13.
Syst Appl Microbiol ; 35(2): 86-91, 2012 Mar.
Article in English | MEDLINE | ID: mdl-22227311

ABSTRACT

Eighteen isolates of a Gram-negative, catalase and oxidase-positive, rod-shaped bacterium, recovered from diseased rainbow trout (Oncorhynchus mykiss), were characterized, using a polyphasic taxonomic approach. Studies based on comparative 16S rRNA gene sequence analysis showed that that the eighteen new isolates shared 99.2-100% sequence similarities. Phylogenetic analysis revealed that isolates from trout belonged to the genus Flavobacterium, showing the highest sequence similarities to F. chungangense (98.6%), F. frigidimaris (98.1%), F. hercynium (97.9%) and F. aquidurense (97.8%). DNA-DNA reassociation values between the trout isolates (exemplified by strain 631-08(T)) and five type strains of the most closely related Flavobacterium species exhibited less than 27% similarity. The G+C content of the genomic DNA was 33.0 mol%. The major respiratory quinone was observed to be menaquinone 6 (MK-6) and iso-C(15:0), C(15:0) and C(16:1) ω7c the predominant fatty acids. The polar lipid profile of strain 631-08(T) consisted of phosphatidylethanolamine, unknown aminolipids AL1 and AL3, lipids L1, L2, L3 and L4 and phospholipid PL1. The novel isolates were differentiated from related Flavobacterium species by physiological and biochemical tests. On the basis of the evidence from this polyphasic study, it is proposed that the isolates from rainbow trout be classified as a new species of the genus Flavobacterium, Flavobacterium oncorhynchi sp. nov. The type strain is 631-08(T) (= CECT 7678(T) = CCUG 59446(T)).


Subject(s)
Flavobacteriaceae Infections/microbiology , Flavobacterium/classification , Flavobacterium/genetics , Oncorhynchus mykiss/microbiology , Animals , Bacterial Typing Techniques , Base Composition , Base Sequence , DNA, Bacterial/analysis , DNA, Bacterial/genetics , DNA, Ribosomal/analysis , DNA, Ribosomal/genetics , Flavobacterium/isolation & purification , Molecular Sequence Data , Phylogeny , RNA, Ribosomal, 16S/analysis , RNA, Ribosomal, 16S/genetics , Sequence Alignment , Sequence Analysis, DNA
14.
Int J Syst Evol Microbiol ; 62(Pt 12): 2934-2940, 2012 Dec.
Article in English | MEDLINE | ID: mdl-22268076

ABSTRACT

A taxonomic study was carried out on five Gram-staining-negative, catalase- and oxidase-positive, rod-shaped bacteria isolated from the gills and livers of five diseased rainbow trout. The five novel isolates were designated strains 687B-08(T), 445-08, 452-08, 453B-08 and 967B-08. In phylogenetic analyses based on 16S rRNA gene sequences, the five novel strains appeared almost identical (99.0-100 % sequence similarity) and to belong to the genus Chryseobacterium. Strain 687B-08(T) (the strain selected to represent the five novel isolates) was found to be most closely related to Chryseobacterium oncorhynchi 701B-08(T) (98.9% sequence similarity), Chryseobacterium ureilyticum F-Fue-04IIIaaaa(T) (98.6%), Chryseobacterium indologenes ATCC 29897(T) (98.3%), Chryseobacterium jejuense JS17-8(T) (98.1%) and Chryseobacterium gleum ATCC 35910(T) (98.1%). In DNA-DNA hybridizations, DNA-DNA relatedness values of 99-100% were recorded between the five novel strains. Lower DNA-DNA relatedness values (21-57%) were recorded between strain 687B-08(T) and C. oncorhynchi 701B-08(T), C. ureilyticum F-Fue-04IIIaaaa(T) and the type strains of other closely related, established species of the genus Chryseobacterium. The predominant respiratory quinone of strain 687B-08(T) was MK-6 and the major cellular fatty acids were iso-C(15:0), iso-C(17:1)ω9c, iso-C(17:0) 3-OH and C(16:1)ω6c. The G+C content of the genomic DNA of strain 687B-08(T) was 38.6 mol%. Based on the phenotypic and genotypic evidence, the five novel strains isolated from rainbow trout represent a single, novel species of the genus Chryseobacterium, for which the name Chryseobacterium viscerum sp. nov. is proposed. The type strain is 687B-08(T) ( = CECT 7793(T)  = CCUG 60103(T)).


Subject(s)
Chryseobacterium/classification , Oncorhynchus mykiss/microbiology , Phylogeny , Animals , Bacterial Typing Techniques , Base Composition , Chryseobacterium/genetics , Chryseobacterium/isolation & purification , DNA, Bacterial/genetics , Fatty Acids/analysis , Fish Diseases/microbiology , Gills/microbiology , Liver/microbiology , Molecular Sequence Data , Nucleic Acid Hybridization , RNA, Ribosomal, 16S/genetics , Sequence Analysis, DNA , Vitamin K 2/analogs & derivatives , Vitamin K 2/analysis
15.
Syst Appl Microbiol ; 35(1): 24-9, 2012 Feb.
Article in English | MEDLINE | ID: mdl-22115847

ABSTRACT

Genotypic and phenotypic analyses were performed on five Gram-negative, catalase and oxidase-positive, rod-shaped bacteria isolated from the gill and liver of four rainbow trout. Studies based on comparative 16S rRNA gene sequence analysis showed that the five new isolates shared 99.8-100% sequence similarity and that they belong to the genus Chryseobacterium. The nearest phylogenetic neighbours of the strain 701B-08(T) were Chryseobacterium ureilyticum F-Fue-04IIIaaaa(T) (99.1% 16S rRNA gene sequence similarity) and Chryseobacterium joosteii LMG 18212(T) (98.6%). DNA-DNA hybridization values between the five isolates were 91-99% and ranged from 2 to 53% between strain 701B-08(T) and the type strains of phylogenetically closely related species of Chryseobacterium. Strain 701B-08(T) had a DNA G+C content of 36.3 mol%, the major fatty acids were iso-C(15:0), iso-C(17:1)ω9c, C(16:1)ω6c and iso-C(17:0) 3-OH and the predominant respiratory quinone was MK-6. The novel isolates were distinguished from related Chryseobacterium species by physiological and biochemical tests. The genotypic and phenotypic properties of the isolates from rainbow trout suggest their classification as representatives of a novel species of the genus Chryseobacterium, for which the name Chryseobacterium oncorhynchi sp. nov. is proposed. The type strain is 701B-08(T) (=CECT 7794(T)=CCUG 60105(T)).


Subject(s)
Chryseobacterium/classification , Chryseobacterium/isolation & purification , Oncorhynchus mykiss/microbiology , Animals , Bacterial Typing Techniques , Base Composition , Catalase/metabolism , Chryseobacterium/genetics , Chryseobacterium/physiology , Cluster Analysis , DNA, Bacterial/chemistry , DNA, Bacterial/genetics , DNA, Ribosomal/chemistry , DNA, Ribosomal/genetics , Fatty Acids/analysis , Gills/microbiology , Liver/microbiology , Molecular Sequence Data , Nucleic Acid Hybridization , Oxidoreductases/metabolism , Phylogeny , Quinones/analysis , RNA, Ribosomal, 16S/genetics , Sequence Analysis, DNA
16.
Hum Exp Toxicol ; 30(9): 1150-64, 2011 Sep.
Article in English | MEDLINE | ID: mdl-21088065

ABSTRACT

Among non-cancer effects of arsenic, cardiovascular diseases have been well documented; however, few are known about the arsenic fate in cardiovascular tissues. We studied the analytic bioinorganic arsenic behaviour in cardiovascular tissues from an arsenic exposure coronary heart disease patient group from Antofagasta-Chile against a small unexposed arsenic coronary heart patient group. Total arsenic concentrations were measured in pieces of cardiovascular tissues of the arsenic-exposed and unexposed coronary heart patient groups by hydride generation atomic absorption spectrometry (HG-AAS); speciation analysis was made by high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). Pieces of auricle (AU), mammary artery (MAM), saphenous vein (SAP) and fat residuals (FAT) were considered in this study. The arsenic concentrations in AU and MAM tissues were significantly different between both groups of patients. Also, it was demonstrated that the AU is an 'As(3+) target tissue.' Otherwise, linking of the total concentrations of arsenic with conditional variables and variables related to medical geology factors allowed us to infer that the latter are more important for the cardiovascular risk of arsenic exposure in the Antofagasta region. Knowledge of total arsenic and the prevalence of the trivalent ion (As(3+)) in the AU of patients could contribute to understanding the effect of arsenic on cardiovascular diseases.


Subject(s)
Arsenic/toxicity , Cardiovascular Diseases/chemically induced , Cardiovascular System/metabolism , Environmental Exposure/adverse effects , Water Pollutants, Chemical/toxicity , Adult , Aged , Arsenic/isolation & purification , Arsenic/pharmacokinetics , Cardiovascular Diseases/epidemiology , Cardiovascular Diseases/metabolism , Chile/epidemiology , Chromatography, High Pressure Liquid , Environmental Exposure/analysis , Humans , Middle Aged , Spectrophotometry, Atomic , Water Pollutants, Chemical/isolation & purification , Water Pollutants, Chemical/pharmacokinetics
17.
Inorg Chem ; 49(21): 10156-65, 2010 Nov 01.
Article in English | MEDLINE | ID: mdl-20886810

ABSTRACT

The syntheses, crystal structures, and the experimental and theoretical magnetochemical characterization for three tetrametallic Ni(II) clusters, namely, [Ni(4)(L)(4)(Cl)(2)(MeOH)(2)](ClO(4))(2)·4MeOH (1), [Ni(4)(L)(4)(N(3))(2)(MeOH)(2)](ClO(4))(2)·2MeOH (2), and [Ni(4)(L1)(4)(pyz)(2)(PhCOO)(2)(MeOH)(2)](ClO(4))(2)·7MeOH (3) (where HL and HL1 represent bipyridine-2-carboxamideoxime and pyrimidine-2-carboxamideoxime, respectively) are reported. Within the Ni(4)(2+) units of these compounds, distorted octahedral Ni(II) ions are bridged by carboxamideoximato ligands to adopt a distorted tetrahedral disposition. The Ni(4)(2+) unit, of C(2) symmetry, can also be viewed as a cube with single [O-atom] and double [NO oxime] bridging groups as atom edges, which define two almost square-planar Ni(O)(2)Ni rings and four irregular hexagonal Ni(NO)(2)Ni rings. To analyze the magnetic properties of 1-3, we have considered the simplest two-J model, where J(1) = J(2) (exchange interactions between the Ni(II) ions belonging to the Ni(O)(2)Ni square rings) and J(a) = J(b) = J(c) = J(d) (exchange interactions between the Ni(II) ions belonging to the Ni-(NO)(2)Ni hexagonal rings) with the Hamiltonian H = -J(1)(S(1)S(2) + S(3)S(4)) - J(a)(S(1)S(3) + S(1)S(4) + S(2)S(3) + S(2)S(4)). The J(1) and J(a) values derived from the fitting of the experimental susceptibility data are -5.8 cm(-1) and -22.1 cm(-1) for 1; -2.4 cm(-1) and -22.8 cm(-1) for 2, and +15.6 cm(-1) and -10.8 cm(-1) for 3. The magneto-structural results and density-functional theory (DFT) calculations demonstrate that the exchange interactions inside the Ni(µ-O)(2)Ni square rings depend on the Ni-O-Ni bridging angle (θ) and the out-of-plane angle of the NO oximate bridging group with respect to the Ni(O)(2)Ni plane (τ), whereas the interactions propagated through the Ni-N-O(Ni)-Ni exchange pathways defining the side of the hexagonal rings depend on the Ni-N-O-Ni torsion angle (α). In both cases, theoretical magneto-structural correlations were obtained, which allow the prediction of the angle for which ferromagnetic interactions are expected. For compound 3, the existence of the axial magnetic exchange pathway through the syn-syn benzoate bridge may also contribute (in addition to the θ and τ angles) to the observed F interaction in this compound through orbital countercomplementarity, which has been supported by DFT calculations. Finally, DFT calculations clearly show that the antiferromagnetic exchange increases when the dihedral angle between the O-Ni-O planes of the Ni(µ-O)(2)Ni square ring, ß, increases.


Subject(s)
Magnetics , Nickel/chemistry , Organometallic Compounds/chemistry , Oximes/chemistry , Crystallography, X-Ray , Models, Molecular , Molecular Structure , Organometallic Compounds/chemical synthesis , Stereoisomerism
18.
Inorg Chem ; 49(19): 8986-96, 2010 Oct 04.
Article in English | MEDLINE | ID: mdl-20806958

ABSTRACT

The 5-pyrimidyl-tetrazolate anion (pmtz) has six basic nitrogen atoms and, consequently, can exhibit a variety of bridging coordination modes. This ligand reacts with either copper(II) and nickel(II) ions in the presence of bi- and tridentate amines to afford the following pmtz-bridged complexes: [Cu(4)(µ-pmtz)(4)(tmda)(4)](ClO(4))(4) (1) (tmda = N,N,N',N'-tetramethylethylenediamine), [Cu(2)(µ-pmtz)(tren)(2)](ClO(4))(3) (2) (tren = tris(2-aminoethyl)amine), [Ni(2)(µ-pmtz)(tren)(2)](ClO(4))(3) (3), and [Ni(2)(µ-pmtz)(2)(ampa)(2)](n)(SCN)(2n) (ampa = bis(3-aminopropyl)amine) (4). The structure and bridging coordination mode of these complexes depend on the stereoelectronic preferences of the metal ion and the coordination properties of the polyamine (denticity and relative disposition of the donor atoms). Thus, complex 1 is a square tetranuclear compound where the ligand adopts an asymmetric k(2)N(1),N(7):k(2)N(4),N(11) bis(chelating)/bridging mode. Complexes 2 and 3 are dinuclear species. In the former the pmtz exhibits a novel k-N(1):k-N(4) imidazolyl/bridging mode whereas the latter shows a symmetric k(2)N(1),N(7):k(2)N(4),N(11) bis(chelating)/bridging mode. Complex 4 exhibits, however, a linear chain structure where the pmtz ligand connects neighboring nickel(II) atoms by using a tridentate k(2)N(1),N(7):kN(3) chelating/bridging mode. Variable-temperature magnetic susceptibility studies reveal that complexes 1-4 show weak to moderate antiferromagnetic (AF) coupling between the metal ions through the pmtz ligand with J = -14.1 cm(-1) for 1, J = -31.1 cm(-1) for 2, J = -4.09 cm(-1) for 3, and J = -8.7 cm(-1) for 4. The magneto-structural results, as well as DFT theoretical calculations carried out on the experimental geometries and model complexes, demonstrate, first, that the magnitude of the AF interaction observed for imidazolyl pmtz-bridged complexes mainly depends on the Cu-N-C angle (the greater the Cu-N-C angle, the stronger is the AF interaction) and, second, that the tridentate chelating/bridging mode is more effective in mediating AF exchange interactions than the bis(chelating)/bridging or imidazolyl/bridging modes in pmtz-bridged complexes.


Subject(s)
Magnetics , Molecular Dynamics Simulation , Organometallic Compounds/chemistry , Pyrimidines/chemistry , Tetrazoles/chemistry , Copper/chemistry , Crystallography, X-Ray , Ligands , Models, Molecular , Molecular Structure , Nickel/chemistry , Organometallic Compounds/chemical synthesis
19.
Dalton Trans ; (21): 2887-93, 2008 Jun 07.
Article in English | MEDLINE | ID: mdl-18478153

ABSTRACT

The bimetallic complex [CoNi(pmzt)4] (pmtz- = 5-(pyrimidyl)tetrazolate ligand) has been prepared by hydrothermal treatment of an equimolecular mixture of the mononuclear complexes[Co(pmtz)2(H2O)2] and [Ni(pmtz)2(H2O)2]. The structure of [CoNi(pmzt)4] consists of (4,4) square-grid-like sheets, in which Co(II) and Ni(II) metal ions are connected by pmtz(-) bridging ligands. This compound is a spin-canted antiferromagnet (weak ferromagnet) with Tc = 18 K. Although Co(II) and Ni(II) ions have different spin values, the spin-canted structure can be formed because of the accidental compensation of their magnetic moments. Both magnetic anisotropy and antisymmetric exchange interaction promote the spin canting of the compensated magnetic moments in the 3D antiferromagnetic phase. On passing from the homometallic complex, [Co2(pmzt)4], which is also a spin-canted antiferromagnet with Tc = 15 K, to the bimetallic complex, [CoNi(pmzt)4], Tc increases and the hysteresis parameters, remnant magnetization (Mr) and critical field (Hc), decrease. The increase in Tc may be a consequence of the increase of the JCoNi, whereas the decrease in Mr and Hc is probably due to the presence in [CoNi(pmzt)4] of a lower content of the highly anisotropic Co(II) ion.

20.
J Anal Toxicol ; 32(2): 140-6, 2008 Mar.
Article in English | MEDLINE | ID: mdl-18334097

ABSTRACT

Antitumoral Pt-containing drugs present side effects like nephrotoxicity and ototoxicity. Several systematic experiments have been carried out with Wistar rats treated with cisplatin, carboplatin, and oxaliplatin to study Pt-drugs accumulation and elimination, and Pt-biomolecule distribution in the cells and cytosols of ear, kidney, and liver. Inductively coupled plasma-mass spectrometry (ICP-MS) analysis shows a cisplatin accumulation capability between oxaliplatin (the highest) and carboplatin (the lowest). The maximum concentration of Pt in all the organs studied was achieved around the first week after cisplatin treatment. During the first 30 days, the elimination was very fast, decreasing in the subsequent 60 days in all the organs. Analysis of cytosols by liquid chromatography (LC)-ICP-MS showed an analogous behavior. In most samples, the distribution of the three drugs in the cellular and cytosolic fractions was similar for all the tissues. For kidney and ear, approximately 60% and 30%, respectively, of the metal accumulated was present in the cytosol, the cytosolic fractions smaller than 50 KDa being especially important. Cisplatin-biomolecule interaction strength under denaturing conditions was evaluated by LC-ICP-MS and showed a quite strong bond.


Subject(s)
Antineoplastic Agents/pharmacokinetics , Organoplatinum Compounds/pharmacokinetics , Platinum/metabolism , Animals , Antineoplastic Agents/analysis , Carboplatin/analysis , Carboplatin/pharmacokinetics , Cell Fractionation , Cisplatin/analysis , Cisplatin/pharmacokinetics , Cytosol/chemistry , Cytosol/metabolism , Ear, Inner/chemistry , Ear, Inner/metabolism , Kidney/chemistry , Kidney/metabolism , Liver/chemistry , Liver/metabolism , Mass Spectrometry , Organoplatinum Compounds/analysis , Oxaliplatin , Platinum/analysis , Rats , Tissue Distribution
SELECTION OF CITATIONS
SEARCH DETAIL
...