Estimation of parasitaemia in imported falciparum malaria using the results of a combined rapid diagnostic test. No big help from haematological parameters.

BACKGROUND: Microscopy continues to be the mainstay for the evaluation of parasitaemia in malaria but requires laboratory support and microbiological experience. Other fast and simple methods are necessary. METHODS: A retrospective observational study of imported malaria treated from July-2007 to December-2020 was carried out to evaluate the association between the degree of parasitaemia and both rapid diagnostic tests (RDT) reactivity patterns and haematological parameters. Plasmodium falciparum monoinfections diagnosed by peripheral blood smear and/or polymerase chain reaction (PCR),which also had a positive RDT result in the same blood sample, were included in the study. RESULTS: A total of 273 patients were included. Most of them were male (n = 256; 93.8%) and visiting friends and relatives (VFR) travellers (n = 252; 92.3%). Patients with plasmodial lactate dehydrogenase (pLDH) or aldolase and histidine-rich protein 2 (HRP-2) co-reactivity (Pan/Pf pattern) had a parasitaemia range between 0 and 37% while those with just HRP-2 reactivity (P. falciparum pattern) had ranges between 0 and 1%. Not a single case of P. falciparum pattern was found for parasitaemia ranges greater than 1%, showing a negative predictive value of 100% for high parasitaemia. All the correlations between haematological parameters and parasitaemia resulted to be weak, with a maximum rho coefficient of -0.35 for lymphocytes and platelets, and of 0.40 for neutrophils-to-lymphocytes count ratio. Multivariate predictive models were constructed reflecting a poor predictive capacity. CONCLUSIONS: The reactivity pattern of RDT allows a rapid semi-quantitative assessment of P. falciparum parasitaemia in travellers with imported malaria, discriminating patients with lower parasite loads. Haematological parameters were not able to estimate parasitaemia with sufficient precision.

Magnetic Hyperthermia Enhancement in Iron-based Materials Driven by Carbon Support Interactions.

Magnetic hyperthermia (MH) shows great potential in clinical applications because of its very localized action and minimal side effects. Because of their high saturation magnetization values, reduced forms of iron are promising candidates for MH. However, they must be protected in order to overcome their toxicity and instability (i. e., oxidation) under biological conditions. In this work, a novel methodology for the protection of iron nanoparticles through confinement within graphitic carbon layers after thermal treatment of preformed nanoparticles supported on carbon is reported. We demonstrate that the size and composition of the nascent confined iron nanoparticles, as well as the thickness of their protective carbon layer can be controlled by selecting the nature of the carbon support. Our findings reveal that a higher nanoparticle-carbon interaction, mediated by the presence of oxygen-containing groups, induces the formation of small and well-protected α-Fe-based nanoparticles that exhibit promising results towards MH based on their enhanced specific absorption rate values.

A New Type of Supramolecular Fluid Based on H2 O-Alkylammonium/Phosphonium Solutions.

Here we show that by adjusting the concentration of tetrabutyl ammonium and phosphonium salts in water (≈1.5-2.0 m), hydrophobic solvation triggers the formation of a unique, highly incompressible supramolecular liquid, with a dynamic structure similar to clathrates, involving essentially all H2 O molecules of the solvent. Despite the increasing local order, the thermal diffusivity, and compressibility of these supramolecular liquids is strongly decreased with respect to bulk water due to slower relaxation dynamics. The results presented in this paper open an avenue to design a new family of supramolecular fluids, stable under atmospheric conditions, which can find important technological applications in energy storage and conversion.

Low temperature glass/crystal transition in ionic liquids determined by H-bond vs. coulombic strength.

Self-assembled ionic liquid crystals are anisotropic ionic conductors, with potential applications in areas as important as solar cells, battery electrolytes and catalysis. However, many of these applications are still limited by the lack of precise control over the variety of phases that can be formed (nematic, smectic, or semi/fully crystalline), determined by a complex pattern of different intermolecular interactions. Here we report the results of a systematic study of crystallization of several imidazolium salts in which the relative contribution of isotropic coulombic and directional H-bond interactions is carefully tuned. Our results demonstrate that the relative strength of directional H-bonds with respect to the isotropic Coulomb interaction determines the formation of a crystalline, semi-crystalline or glassy phase at low temperature. The possibility of pinpointing H-bonding directionality in ionic liquids make them model systems to study the crystallization of an ionic solid under a perturbed Coulomb potential.

Synthesis, Characterization, and Application of Core-Shell Co0.16Fe2.84O4@NaYF4(Yb, Er) and Fe3O4@NaYF4(Yb, Tm) Nanoparticle as Trimodal (MRI, PET/SPECT, and Optical) Imaging Agents.

Multimodal nanoparticulate materials are described, offering magnetic, radionuclide, and fluorescent imaging capabilities to exploit the complementary advantages of magnetic resonance imaging (MRI), positron emission tomography/single-photon emission commuted tomography (PET/SPECT), and optical imaging. They comprise Fe3O4@NaYF4 core/shell nanoparticles (NPs) with different cation dopants in the shell or core, including Co0.16Fe2.84O4@NaYF4(Yb, Er) and Fe3O4@NaYF4(Yb, Tm). These NPs are stabilized by bisphosphonate polyethylene glycol conjugates (BP-PEG), and then show a high transverse relaxivity (r2) up to 326 mM(-1) s(-1) at 3T, a high affinity to [(18)F]-fluoride or radiometal-bisphosphonate conjugates (e.g., (64)Cu and (99m)Tc), and fluorescent emissions from 500 to 800 nm under excitation at 980 nm. The biodistribution of intravenously administered particles determined by PET/MR imaging suggests that negatively charged Co0.16Fe2.84O4@NaYF4(Yb, Er)-BP-PEG (10K) NPs cleared from the blood pool more slowly than positively charged NPs Fe3O4@NaYF4(Yb, Tm)-BP-PEG (2K). Preliminary results in sentinel lymph node imaging in mice indicate the advantages of multimodal imaging.

Dynamics of Gold Nanoparticles on Carbon Nanostructures Driven by van der Waals and Electrostatic Interactions.

Transmission electron microscopy studies on the assembly and growth of gold nanoparticles on carbon nanotubes supported on few-layer graphene and amorphous carbon reveal a competition between van der Waals forces and electrostatic interactions, enabling controlled positioning and sizing of adsorbed nanoparticles at the nanochannels formed between the carbon nanotube and the few-layer graph-ene surface.

A high saturation factor in Overhauser DNP with nitroxide derivatives: the role of (14)N nuclear spin relaxation.

Overhauser DNP enhancements of toluene were measured at a magnetic field of 0.35 Tesla in a series of chemically functionalized nitroxide radicals. We observe that the enhancements increase systematically with polarizer size and rotational correlation time. Examination of the saturation factor of (14)N nitroxides by pulsed ELDOR spectroscopy led to a quantitative interpretation of the enhancements, for which the saturation factor increases up to almost unity due to enhanced nuclear ((14)N) relaxation in the nitroxide radical. The observation has a direct impact on the choice of optimum DNP polarizers in liquids.

Boosting Oxygen Reduction Reaction Selectivity in Metal Nanoparticles with Polyoxometalates.

The lack of selectivity toward the oxygen reduction reaction (ORR) in metal nanoparticles can be linked to the generation of intermediates. This constitutes a crucial constraint on the performance of specific electrochemical devices, such as fuel cells and metal-air batteries. To boost selectivity of metal nanoparticles, a novel methodology that harnesses the unique electrocatalytic properties of polyoxometalates (POM) to scavenge undesired intermediates of the ORR (such as HO2 -) promoting selectivity is proposed. It involves the covalent functionalization of metal nanoparticle's surface with an electrochemically active capping layer containing a new sulfur-functionalized vanadium-based POM (AuNP@POM). To demonstrate this approach, preformed thiolate Au(111) nanoparticles with a relatively poor ORR selectivity are chosen. The dispersion of AuNP@POM on the surface of carbon nanofibers (CNF) enhances oxygen diffusion, and therefore the ORR activity. The resulting electrocatalyst (AuNP@POM/CNF) exhibits superior stability against impurities like methanol and a higher pH tolerance range compared to the standard commercial Pt/C. The work demonstrates for the first time, the use of a POM-based electrochemically active capping layer to switch on the selectivity of poorly selective gold nanoparticles, offering a promising avenue for the preparation of electrocatalyst materials with improved selectivity, performance, and stability for ORR-based devices.

Electrochemically Versatile Graphite Nanoplatelets Prepared by a Straightforward, Highly Efficient, and Scalable Route.

Nanostructured carbon materials with tailor-made structures (e.g., morphology, topological defect, dopant, and surface area) are of significant interest for a variety of applications. However, the preparation method selected for obtaining these tailor-made structures determines the area of application, precluding their use in other technological areas of interest. Currently, there is a lack of simple and low-cost methodologies versatile enough for obtaining freestanding carbon nanostructures that can be used in either energy storage or chemical detection. Here, a novel methodology for the development of a versatile electrochemically active platform based on freestanding graphite nanoplatelets (GNP) has been developed by exploiting the interiors of hollow carbon nanofibers (CNF) comprising nanographene stacks using dry ball-milling. Even though ball-milling could be considered as a universal method for any carbonaceous material, often, it is not as simple (one step, no purification, and no solvents), efficient (just GNP without tubular structures), and quick (just 20 min) as the sustainable method developed in this work, free of surfactants and stabilizer agents. We demonstrate that the freestanding GNP developed in this work (with an average thickness of 3.2 nm), due to the selective edge functionalization with the minimal disruption of the basal plane, can act either as a supercapacitor or as a chemical sensor, showing both a dramatic improvement in the charge storage ability of more than 30 times and an enhanced detection of electrochemically active molecules such as ascorbic acid with a 236 mV potential shift with respect to CNF in both cases. As shown here, GNP stand as an excellent versatile alternative compared to the standard commercially available carbon-based materials. Overall, our approach paves the way for the discovery of new nanocarbon-based electrochemical active platforms with a wide electrochemical applicability.

Light-induced bi-directional switching of thermal conductivity in azobenzene-doped liquid crystal mesophases.

The development of systems that can be switched between states with different thermal conductivities is one of the current challenges in materials science. Despite their enormous diversity and chemical richness, molecular materials have been only scarcely explored in this regard. Here, we report a reversible, light-triggered thermal conductivity switching of ≈30-40% in mesophases of pure 4,4'-dialkyloxy-3-methylazobenzene. By doping a liquid crystal matrix with the azobenzene molecules, reversible and bidirectional switching of the thermal conductivity can be achieved by UV/Vis-light irradiation. Given the enormous variety of photoactive molecules and chemically compatible liquid crystal mesophases, this approach opens unforeseen possibilities for developing effective thermal switches based on molecular materials.

High-nuclearity metal-organic nanospheres: a Cd66 ball.

Reaction of H(3)L with Cd(NO(3))(2)·4H(2)O in DMF at 150 °C for 3 days affords the metal-organic nanosphere [Cd(66)(µ(3)-OH)(28)(µ(3)-O)(16)(µ(5)-NO(3)-O,O,O',O',O″,O″)(12)(L)(20)(µ(2)-DMF)(12)⊂(DMF)(9)]. The cluster is composed of a spherical shell of 66 Cd(II) cations bridged by 28 µ(3)-hydroxide, 16 µ(3)-oxo, and five µ(5)-NO(3)(-) anions surrounded by a shell of 20 tripodal capping ligands (L) and 12 DMF ligands. The 66 Cd(II) cations and 12 NO(3)(-) anions form a polydeltahedron that has 78 vertices [Cd(II) or NO(3)(-)] (V), 228 edges (E), and 152 triangular faces (F), giving it an Euler characteristic (χ) of 2 (χ = V + F - E). Reaction of H(3)L with Cd(NO(3))(2)·4H(2)O at lower temperatures or with CdCl(2) affords coordination polymer frameworks instead of nanospheres.

Interactions of gold nanoparticles with the interior of hollow graphitized carbon nanofibers.

Interactions of free-standing gold nanoparticles and hollow graphitized nanofibers in colloidal suspension are investigated, revealing the first example of the controlled arrangement of nanoparticles inside nano-containers, as directed by their internal structure. The ordering is highly effective for small gold nanoparticles whose sizes are commensurate with the height of graphitic step-edges in the graphitized carbon nanofibers and is less effective for larger gold nanoparticles. Studies aimed at understanding the role of the organic-solvent surface tension, employed for the filling experiments, demonstrate that gold nanoparticles become preferentially anchored into the hollow graphitized carbon nanofibers under a mixture of pentane/CO(2) in supercritical conditions. It is shown that a three-step cleaning procedure enables effective removal of gold nanoparticles adsorbed on the exterior surface of graphitized carbon nanofibers, while ordered arrays of encapsulated nanoparticles are retained.

Ag5 nanoclusters with dual catalytic antiradical activities.

Silver nanoclusters of five atoms (Ag5) display outstanding catalytic activities for the deactivation of radicals. Using 2,2-diphenyl-1­picrylhydrazyl (DPPH) radical as a model system, we observed a fast radical reduction to DPPH anions using only [Ag5] 3 to 4 orders of magnitude less than [DPPH]. Moreover, nanoclusters remain stable at the end of the reaction, and can deactivate again DPPH radicals at the same rate, indicating that they act as anti-radical catalysts. The radical scavenger catalytic activity of Ag5 proceeds selectively through the oxidation of methanol (used to dissolve the radical) to formaldehyde, which is supported by DFT calculations. The obtained catalytic rate constants are almost 2 orders of magnitude higher than oxidases, and more than 4 orders of magnitude larger than graphene quantum dots. We also show that Ag5 not only catalyze the reduction of radicals but also their oxidation, promoting the inhibition of the autoxidation mechanisms of hydrocarbon polymers, which are very sensitive to the presence of radicals. For this purpose, thin films of two industrially relevant polymers (polyisoprene and acrylonitrile-butadienestyrene copolymer), were exposed to standard simulated photo-ageing conditions in the presence of Ag5. Using Attenuated Total Reflection-FTIR and DFT modeling we observed that, although Ag5 nanoclusters, with ≈ 15% surface coverage, do not totally inhibit the oxidation, they favour a decomposition that yields inactive products, in contrast with the more detrimental ketone formation pathway. These results not only open new possibilities for developing a post-process inhibition of polymer degradation, for which nowadays there are no efficient procedures, but also, they could be used as very efficient dual-redox catalytic radical scavengers for different industrial or biomedical purposes.

Mechanical interlocking of SWNTs with N-rich macrocycles for efficient ORR electrocatalysis.

Substitutional N-doping of single-walled carbon nanotubes is a common strategy to enhance their electrocatalytic properties in the oxygen-reduction reaction (ORR). Here, we explore the encapsulation of SWNTs within N-rich macrocycles as an alternative strategy to display electroactive sites on the surface of SWNTs. We design and synthesize four types of mechanically interlocked derivatives of SWNTs (MINTs) by combining two types of macrocycles and two types of SWNT samples. Comprehensive electrochemical characterization of these MINTs and their reference SWNTs allows us to establish structure-activity relationships. First, we show that all MINT samples are superior electrocatalysts compared to pristine SWNTs, which serves as general validation of our strategy. Secondly, we show that macrocycles displaying both N atoms and carbonyl groups perform better than those with N atoms only. Finally, we demonstrate that a tighter fit between macrocycles and SWNTs results in enhanced catalytic activity and stability, most likely due to a more effective charge-transfer between the SWNTs and the macrocycles. These results, focusing on the ORR as a testbed, show the possibility of understanding electrocatalytic performance of SWNTs at the molecular level and thus enable the design of more active and more stable catalysts in the future.

Functionalized fullerenes in self-assembled monolayers.

Anisotropy of intermolecular and molecule-substrate interactions holds the key to controlling the arrangement of fullerenes into 2D self-assembled monolayers (SAMs). The chemical reactivity of fullerenes allows functionalization of the carbon cages with sulfur-containing groups, thiols and thioethers, which facilitates the reliable adsorption of these molecules on gold substrates. A series of structurally related molecules, eight of which are new fullerene compounds, allows systematic investigation of the structural and functional parameters defining the geometry of fullerene SAMs. Scanning tunnelling microscopy (STM) measurements reveal that the chemical nature of the anchoring group appears to be crucial for the long-range order in fullerenes: the assembly of thiol-functionalized fullerenes is governed by strong molecule-surface interactions, which prohibit formation of ordered molecular arrays, while thioether-functionalized fullerenes, which have a weaker interaction with the surface than the thiols, form a variety of ordered 2D molecular arrays owing to noncovalent intermolecular interactions. A linear row of fullerene molecules is a recurring structural feature of the ordered SAMs, but the relative alignment and the spacing between the fullerene rows is strongly dependent on the size and shape of the spacer group linking the fullerene cage and the anchoring group. Careful control of the chemical functionality on the carbon cages enables positioning of fullerenes into at least four different packing arrangements, none of which have been observed before. Our new strategy for the controlled arrangement of fullerenes on surfaces at the molecular level will advance the development of practical applications for these nanomaterials.

Single molecule magnets on a gold surface: in situ electrospray deposition, x-ray absorption and photoemission.

Single molecule magnets based on the dodecamanganese (III, IV) cluster with two different types of ligand (acetate and benzoate) have been studied on the Au(111) surface. Due to the non-volatile and fragile nature of the molecules, we have used ultra-high vacuum electrospray deposition to produce a series of surface coverages from a fraction of a monolayer to multilayer films in both cases. Synchrotron radiation based electron spectroscopy has been used to study the adsorption of the molecules on the Au(111) surface and the effect that this has on the oxidation states of the manganese atoms in the core. In both cases, reduction of the core is observed due to the interaction with the surface, to essentially the same extent despite substantial differences in the size and nature of the ligand shell.

Palladium Nanoparticles Hardwired in Carbon Nanoreactors Enable Continually Increasing Electrocatalytic Activity During the Hydrogen Evolution Reaction.

Invited for this month's cover is the group of Maria Gimenez-Lopez at the University of Santiago de Compostela. The image shows the self-improving electrochemical activity of palladium nanoparticles hardwired into a graphitic step-edge for hydrogen production. The Full Paper itself is available at 10.1002/cssc.202101236.

Palladium Nanoparticles Hardwired in Carbon Nanoreactors Enable Continually Increasing Electrocatalytic Activity During the Hydrogen Evolution Reaction.

Catalysts typically lose effectiveness during operation, with much effort invested in stabilising active metal centres to prolong their functional lifetime for as long as possible. In this study palladium nanoparticles (PdNP) supported inside hollow graphitised carbon nanofibers (GNF), designated as PdNP@GNF, opposed this trend. PdNP@GNF exhibited continuously increasing activity over 30000 reaction cycles when used as an electrocatalyst in the hydrogen evolution reaction (HER). The activity of PdNP@GNF, expressed as the exchange current density, was always higher than activated carbon (Pd/C), and after 10000 cycles PdNP@GNF surpassed the activity of platinum on carbon (Pt/C). The extraordinary durability and self-improving behaviour of PdNP@GNF was solely related the unique nature of the location of the palladium nanoparticles, that is, at the graphitic step-edges within the GNF. Transmission electron microscopy imaging combined with spectroscopic analysis revealed an orchestrated series of reactions occurring at the graphitic step-edges during electrocatalytic cycling, in which some of the curved graphitic surfaces opened up to form a stack of graphene layers bonding directly with Pd atoms through Pd-C bonds. This resulted in the active metal centres becoming effectively hardwired into the electrically conducting nanoreactors (GNF), enabling facile charge transport to/from the catalytic centres resulting in the dramatic self-improving characteristics of the electrocatalyst.

Molecular dopant determines the structure of a physisorbed self-assembled molecular network.

A small percentage of an impurity was shown, via scanning tunneling microscopy, to drastically change the on-surface self-assembly behavior of an aromatic tetracarboxylic acid, by initiating the nucleation and growth of a different polymorph. Molecular modelling simulations were used to shed further light onto the dopant-controlled assembly behaviour.

Migration-associated malaria from Africa in southern Spain.

BACKGROUND: The western area of the province of Almeria, sited in southern Spain, has one of the highest immigrant population rates in Spain, mainly dedicated to agricultural work. In recent years, there has been a significant increase in the number of cases of imported malaria associated with migrants from countries belonging to sub-Saharan Africa. The objective of our study is to describe the epidemiological, clinical and analytical characteristics of malaria patients treated in a specialized tropical unit, paying special attention to the differences between VFR and non-VFR migrants and also to the peculiarities of microscopic malaria cases compared to submicroscopic ones. METHODS: Retrospective observational study of migrants over 14 years of age with imported malaria treated from October 2004 to May 2019. Characteristics of VFR and non-VFR migrants were compared. Malaria cases were divided into microscopic malaria (MM) and submicroscopic malaria (SMM). SMM was defined as the presence of a positive malaria PCR test together with a negative direct microscopic examination and a negative rapid diagnostic test (RDT). Microscopic malaria was defined as the presence of a positive RDT and/or a positive smear examination. RESULTS: Three hundred thirty-six cases of malaria were diagnosed, 329 in sub-Saharan immigrants. Of these, 78.1% were VFR migrants, in whom MM predominated (85.2% of cases). In non-VFR migrants, SMM represented 72.2% of the cases. Overall, 239 (72.6%) patients presented MM and 90 (27.4%) SMM. Fever was the most frequent clinical manifestation (64.4%), mainly in the MM group (MM: 81.1% vs SMM: 20.0%; p < 0.01). The most frequent species was P. falciparum. Patients with SMM presented fewer cytopenias and a greater number of coinfections due to soil-transmitted helminths, filarial and intestinal protozoa compared to patients with MM. CONCLUSIONS: Imported malaria in our area is closely related to sub-Saharan migration. VFR migrants are the main risk group, highlighting the need for actions aimed at improving disease prevention measures. On the other hand, almost a third of the cases are due to SMM. This fact could justify its systematic screening, at least for those travelers at greater risk.