ClO-driven degradation of graphene oxide: new insights from DFT calculations.

We present an extensive investigation using density functional theory (DFT) calculations on various model graphene oxide (GO) nanostructures interacting with chlorine monoxide ClO, aiming to understand the role of this highly oxidizing species in C-C bond breakage and the formation of significant holes on GO sheets. During its function, the myeloperoxidase (MPO) enzyme abundantly generates chlorine-oxygen-containing species and their presence has been identified as the cause of degradation in carbon nanotubes of diverse sizes, morphologies, and chemical compositions, both in in vivo and in vitro samples. Notably, Kurapati et al. (Small, 2015, 11, 3985-3994) demonstrated efficient degradation of single GO monolayers through MPO catalysis, though the exact degradation mechanism remains unclear. In our study, we discover that breaking C-C bonds in a single graphene oxide sheet is achievable through a simple mechanism involving the dissociation of two ClO molecules that are chemically attached as nearest neighbor species but bonded to opposite sides of the GO layer (up/down configuration). Two new carbonyl oxygens appear on the surface and the Cl atoms can be transferred to the carbon layer or as physisorbed species near the GO surface. Relatively small energy barriers are associated with these molecular events. Continuing this process on neighboring sites leads to the presence of larger holes on the GO surface, accompanied by an increase in carbonyl species on the carbon network, consistent with X-ray photoelectron spectroscopy measurements. Indeed, the distribution of oxygen functionalities is found to be crucial in defining the damage pattern induced in the carbon layer. We emphasize the important role played by the local charge distribution in the stability or instability of chemical bonds, as well as in the energy barriers and reaction pathways. Finally, we explore the possibility of achieving chlorination of GO following MPO exposure. The here-reported predictions could be the root cause of the experimentally observed low stability of individual GO sheets during the MPO catalytic cycle.

Adsorption of nitric oxide on small Rh(n)± clusters: role of the local atomic environment on the dissociation of the N-O bond.

We present extensive pseudopotential density functional theory calculations dedicated to analyze the stability and dissociation behavior of NO molecules adsorbed on small nonmagnetic Rh(n)± clusters. Following the experimental work of Anderson et al. (J. Phys. Chem. A 2006, 110, 10992), we consider rhodium structures of different sizes (n = 3, 4, 6, and 13) and charge states onto which we attach NO species in both molecular and dissociative configurations. The relative stability between different Rh(n)± isomers depends on the ionization state of the clusters as well as on the presence of NO adsorbates on the surface. Various adsorbed configurations for the NO molecules are found when switching from cationic to neutral to anionic rhodium clusters. In particular adsorbed phases in which the NO molecule is attached with its N-O bond parallel to the plane of square or triangular facets are characterized by elongated nitrogen-oxygen interatomic distances, a fact that plays a fundamental role in the dissociation behavior of the adsorbate. We use the nudged elastic band method to analyze possible reaction pathways and transition states that could be present in our (Rh(n) + NO)± systems. We found (as in surface studies) that the dissociation of the N-O bond is more easily obtained on square facets than on triangular atomic environments, a fact that indirectly reveals the structure of Rh(n)± clusters present in the gas phase experiments. The energy barriers that need to be overcome to achieve the breaking of the N-O bond depend on the charge state of the systems, a result that could be used to tune the catalytic activity of these types of materials.

Antigen-specific suppression of cultured lymphocytes from patients with neurocysticercosis.

The biological parasite-host interactions involved in neurocysticercosis (NC) are of a complex nature. A lymphoproliferation assay was performed using mononuclear cells from 11 patients with NC, who were classified according to the alterations obtained by imaging examinations. Antigen extracts from the membrane and/or scolex of Taenia solium and from the vesicular fluid of Taenia crassiceps were used. Mononuclear cells from patients with NC showed antigen-specific suppression when compared with a control group. The patients presenting calcified cysts showed higher suppression when compared with patients in the active phase of disease. The antigen in the vesicular fluid of T. crassiceps seems to play a suppressor role in vitro, completely inhibiting cell proliferation induced by the mitogens phytohaemagglutinin, concanavalin A and pokeweed mitogen.

Measles vaccine coverage and immune response in children of Caiabi and Metuktire Indian tribes living in malarial endemic area: Parque indígena do Xingu, Central Brazil.

Measles vaccination efficiency was evaluated in children from two Indian tribes - Caiabi and Metuktire - living in the Amazon region, in the Parque Indigena do Xingu (PIX). The population sample, selected at random, made up 37 Caiabi and 28 Metuktire children, aged from 20-75 months (40%). For operational and epidemiological reasons, measles vaccine is given from 6 months of age. The average age of children when they received the vaccine was 11.5 months for the first dose and 20 months for the second. The search for IgG antibodies against measles virus and Plasmodium falciparum was made through immunofluorescence assay (IFA). Measles vaccine coverage has reached 60% at 12 months of age and 92% at 18 months, whereas post-vaccine serum conversion was 95% in Caiabi children (geometric mean of titres (GMT) 126) and 89% in Metuktire (GMT 109). The difference in GMT is not statistically significant. Seventy-three per cent of Caiabi children (GMT 101) and 100% of Metuktire children (GMT135) were plasmodium antibody positive, showing they had been exposed to malarial infection. Despite the differences detected, the immune response to measles vaccine was satisfactory in both groups, with a positive percentage consistent with that achieved in non-malarial areas in Americas. The results show the efficiency of a vaccination programme in an indigenous area despite the difficulties in reaching the villages and maintaining the cold chain, and also despite the malaria endemicity.

Immune responses to multiple antigen peptides containing T and B epitopes from Plasmodium falciparum circumsporozoite protein of Brazilian individuals naturally exposed to malaria.

We have evaluated the immune responses of individuals living in a malaria endemic area of Brazil to the (T1B)4, a multiple antigen peptide (MAP) from Plasmodium falciparum circumsporozoite (CS) protein and the related monoepitope MAPs, B4 and (T1)4, and the linear peptides, T1B and B. The highest antibody frequencies were against MAPs containing the B cell epitope sequence (T1B)4 (42.2%) and B4 (28.8%), while the highest lymphoproliferative response frequencies were against the MAPs containing the T cell epitope sequence (T1)4 (47%) and (T1B)4 (36.4%). We analysed individual responses considering lymphoproliferative response to (T1)4 MAP and IgG antibody titre to (T1B)4 as patterns of ideal cellular and humoral responses, respectively. The frequency of responders, cellular and/or humoral was 66.6%, significantly higher than non responders (P = 0.003). We also determined the HLA class II haplotype of each individual but no association between these and immune response patterns to the MAPs was observed. The results showed that individuals primed against P. falciparum in their natural habitat, present a very diverse array of responses against the same peptide antigens, varying from no response in one-third of the individuals to cognate B and T cell responses. Our study underlines the importance of previous studies of vaccine candidates to guarantee that the immunization will be capable of reverting inefficient or absent responses to malaria epitopes.

Standardization of procedures of Plasmodium falciparum antigen preparation for serologic tests.

The objective of the present study is to standardize the technical variables for preparation and storage of Plasmodium falciparum and of antigen components extracted with the amphoteric detergent Zwittergent. P. falciparum obtained from in vitro culture was stored at different temperatures and for different periods of time. For each variable, antigen components of the parasite were extracted in the presence or absence of protease inhibitors and submitted or not to later dialysis. Products were stored for 15, 30 and 60 days at different temperatures and immunological activity of each extract was determined by SDS-PAGE and ELISA using positive or negative standard sera for the presence of IgG directed to blood stage antigens of P. falciparum. Antigen extracts obtained from parasites stored at -20 degrees C up to 10 days or at -70 degrees C for 2 months presented the best results, showing well-defined bands on SDS-PAGE and Western blots and presenting absorbance values in ELISA that permitted safe differentiation between positive and negative sera.

Malaria diagnosis: a review.

Malaria is the most prevalent endemic disease in large parts of the world and is subject to control by health authorities. Today, the goal of malaria control is to prevent mortality and reduce morbidity and socioeconomic losses through the progressive improvement and strengthening of local and national capabilities. The World Health Organization considers early diagnosis as the first basic element of the strategy to control the disease. Traditionally, laboratory diagnosis has been made using the thick blood film, which continues to be the gold standard test. However, this test has disadvantages such as the manner in which the film is prepared, the level of training of the observer, the adequacy of maintenance of materials and equipment and its only fair sensitivity. Thus, many research laboratories have concentrated their efforts on the development of alternative methods for malaria diagnosis. These include methods for the detection of Plasmodia within erythrocytes (fluorescent microscopy, Quantitative Buffy Coat (QBC), dark field microscopy, nucleic acid probes and immunofluorescence), methods for the detection of plasmodial antigens in body fluids (radioimmunoassay, enzyme immunoassay) and methods for the detection of anti-plasmodial antibodies in serum (indirect immunofluorescence, enzyme immunoassay, Western blotting). Here, we critically review the various methods for malaria diagnosis based on the world's literature and our experience with most of them, with emphasis on recent advances.

Malaria diagnosis: a review

Malaria is the most prevalent endemic disease in large parts of the world and is subject to control by health authorities. Today, the goal of malaria control is to prevent mortality and reduce morbidity and socioeconomic losses through the progressive improvement and strengthening of local and national capabilities. The World Health Organization considers early diagnosis as the first basic element of the strategy to control the disease. Traditionally, laboratory diagnosis has been made using the thick blood film, which continues to be the gold standard test. However, this test has disadvantages such as the manner in which the film is prepared, the level of training of the observer, the adequacy of maintenance of materials and equipment and its only fair sensitivity. Thus, many research laboratories have concentrated their efforts on the development of alternative methods for malaria diagnosis. These include methods for the detection of Plasmodia within erythrocytes (fluorescent microscopy, Quantitative Buffy Coat (QBC(), dark field microscopy, nucleic acid probes and immunofluorescence), methods for the detection of plasmodial antigens in body fluids (radioimmunoassay, enzyme immunoassay) and methods for the detection of anti-plasmodial antibodies in serum (indirect immunofluorescence, enzyme immunoassay, Western blotting). Here, we critically review the various methods for malaria diagnosis based on the world's literature and our experience with most of them, with emphasis on recent advances.

Evaluation of different methods for Plasmodia detection, in well defined population groups in an endemic area of Brazil (1).

In Brazil, more than 500,000 new cases of malaria were notified in 1992. Plasmodium falciparum and P. vivax are the responsible species for 99.3% of the cases. For adequate treatment, precoce diagnosis is necessary. In this work, we present the results of the traditional Plasmodia detection method, thick blood film (TBF), and the results of alternative methods: Immunofluorescence assay (IFA) with polyclonal antibody and Quantitative Buffy Coat method (QBC) in a well defined population groups. The analysis were done in relation to the presence or absence of malaria clinical symptoms. Also different classes of immunoglobulins anti-P.falciparum were quantified for the global analysis of the results, mainly in the discrepant results. We concluded that alternative methods are more sensitive than TBF and that the association of epidemiological, clinical and laboratory findings is necessary to define the presence of malaria.