Exploring affinity between organic probes and Prussian Blue Analogues via inverse gas chromatography.

Prussian Blue Analogues (PBAs), which are characterized by their open structure, high stability, and non-toxic properties, have recently been the subject of research for various applications, including their use as electrode precursors for capacitive deionization, gas storage, and environmental purification. These materials can be readily tailored to enhance their affinity towards gases for integration with sensing devices. An improved understanding of PBA-gas interactions is expected to enhance material development and existing sensor deposition schemes greatly. The use of inverse gas chromatography (IGC) is a robust approach for examining the relationship between porous materials and gases. In this study, the adsorption properties of (functionalized) hydrocarbons, i.e., probe molecules, on the copper hexacyanoferrate (CuHCF) lattice were studied via IGC, demonstrating that alkylbenzenes have a higher affinity for this material than n-alkanes. This difference was rationalized by steric hindrance, π-π interactions, and vapour pressure effects. Along the same line, the five isomers of hexane showed decreasing selectivity upon increased steric hindrance. Enthalpy values for n-pentane, n-hexane and n-heptane were lower than that of toluene. The introduction of increased probe masses resulted in a surface coverage of 46% for toluene. For all n-alkane probe molecules this percentage was lower. However, the isotherms of these probes did not show saturation points and the observed linear regime proves beneficial for gas sensing. Our work demonstrates the versatility of CuHCF for gas sensing purposes and the potential of IGC to characterize the adsorption characteristics of such a porous nanomaterial.

Chemical Mediation of Oviposition by Anopheles Mosquitoes: a Push-Pull System Driven by Volatiles Associated with Larval Stages.

The oviposition behavior of mosquitoes is mediated by chemical cues. In the malaria mosquito Anopheles gambiae, conspecific larvae produce infochemicals that affect this behavior. Emanations from first instar larvae proved strongly attractive to gravid females, while those from fourth instars caused oviposition deterrence, suggesting that larval developmental stage affected the oviposition choice of the female mosquito.We examined the nature of these chemicals by headspace collection of emanations of water in which larvae of different stages were developing. Four chemicals with putative effects on oviposition behavior were identified: dimethyldisulfide (DMDS) and dimethyltrisulfide (DMTS) were identified in emanations from water containing fourth instars; nonane and 2,4-pentanedione (2,4-PD) were identified in emanations from water containing both first and fourth instars. Dual-choice oviposition studies with these compounds were done in the laboratory and in semi-field experiments in Tanzania.In the laboratory, DMDS and DMTS were associated with oviposition-deterrent effects, while results with nonane and 2,4-PD were inconclusive. In further studies DMDS and DMTS evoked egg retention, while with nonane and 2,4-PD 88% and 100% of female mosquitoes, respectively, laid eggs. In dual-choice semi-field trials DMDS and DMTS caused oviposition deterrence, while nonane and 2,4-PD evoked attraction, inducing females to lay more eggs in bowls containing these compounds compared to the controls. We conclude that oviposition of An. gambiae is mediated by these four infochemicals associated with conspecific larvae, eliciting either attraction or deterrence. High levels of egg retention occurred when females were exposed to chemicals associated with fourth instar larvae.

Relation between HLA genes, human skin volatiles and attractiveness of humans to malaria mosquitoes.

Chemical cues are considered to be the most important cues for mosquitoes to find their hosts and humans can be ranked for attractiveness to mosquitoes based on the chemical cues they emit. Human leukocyte antigen (HLA) genes are considered to be involved in the regulation of human body odor and may therefore affect human attractiveness to mosquitoes, and hence, affect the force of malaria transmission. In the present study the correlations between HLA profiles, human skin volatiles and human attractiveness to the malaria mosquito Anopheles gambiae Giles sensu stricto were examined. Skin emanations of 48 volunteers were collected by rubbing a foot over glass beads. Previously the attractiveness of these emanations to An. gambiae was determined. In this study, the chemical composition of these emanations was determined by gas chromatography-mass spectroscopy (GC-MS) and blood samples of all volunteers were taken for HLA analysis. Hierarchical cluster analysis (HCA), partial least squares discriminant analysis (PLS-DA), Fisher's exact test and random forest regression were used to test for correlations between individuals classified as either highly or poorly attractive to mosquitoes and their HLA profile and volatile composition. HLA profiling suggests that people carrying HLA gene Cw∗07 are more attractive to mosquitoes. GC-MS revealed that limonene, 2-phenylethanol and 2-ethyl-1-hexanol were associated with individuals that were poorly attractive to An.gambiae and lactic acid, 2-methylbutanoic acid, tetradecanoic acid and octanal with individuals that were highly attractive. Such compounds offer potential for disruption of mosquito behavior in malaria intervention programs.

Composition of human skin microbiota affects attractiveness to malaria mosquitoes.

The African malaria mosquito Anopheles gambiae sensu stricto continues to play an important role in malaria transmission, which is aggravated by its high degree of anthropophily, making it among the foremost vectors of this disease. In the current study we set out to unravel the strong association between this mosquito species and human beings, as it is determined by odorant cues derived from the human skin. Microbial communities on the skin play key roles in the production of human body odour. We demonstrate that the composition of the skin microbiota affects the degree of attractiveness of human beings to this mosquito species. Bacterial plate counts and 16S rRNA sequencing revealed that individuals that are highly attractive to An. gambiae s.s. have a significantly higher abundance, but lower diversity of bacteria on their skin than individuals that are poorly attractive. Bacterial genera that are correlated with the relative degree of attractiveness to mosquitoes were identified. The discovery of the connection between skin microbial populations and attractiveness to mosquitoes may lead to the development of new mosquito attractants and personalized methods for protection against vectors of malaria and other infectious diseases.

Cultured skin microbiota attracts malaria mosquitoes.

BACKGROUND: Host-seeking of the African malaria mosquito, Anopheles gambiae sensu stricto, is guided by human odours. The precise nature of the odours, and the composition of attractive blends of volatiles, remains largely unknown. Skin microbiota plays an important role in the production of human body odours. It is hypothesized that host attractiveness and selection of An. gambiae is affected by the species composition, density, and metabolic activity of the skin microbiota. A study is presented in which the production and constituency of volatile organic compounds (VOCs) by human skin microbiota is examined and the behavioural responses of An. gambiae to VOCs from skin microbiota are investigated. METHODS: Blood agar plates incubated with skin microbiota from human feet or with a reference strain of Staphylococcus epidermidis were tested for their attractiveness to An. gambiae in olfactometer bioassays and indoor trapping experiments. Entrained air collected from blood agar plates incubated with natural skin microbiota or with S. epidermidis were analysed using GC-MS. A synthetic blend of the compounds identified was tested for its attractiveness to An. gambiae. Behavioural data were analysed by a chi(2)-test and GLM. GC-MS results were analysed by fitting an exponential regression line to test the effect of the concentration of bacteria. RESULTS: More An. gambiae were caught with blood agar plates incubated with skin bacteria than with sterile blood agar plates, with a significant effect of incubation time and dilution of the skin microbiota. When bacteria from the feet of four other volunteers were tested, similar effects were found. Fourteen putative attractants were found in the headspace of the skin bacteria. A synthetic blend of 10 of these was attractive to An. gambiae. CONCLUSIONS: The discovery that volatiles produced by human skin microorganisms in vitro mediate An. gambiae host-seeking behaviour creates new opportunities for the development of odour-baited trapping systems. Additionally, identification of bacterial volatiles provides a new method to develop synthetic blends, attractive to An. gambiae and possibly other anthropophilic disease vectors.

In the pursuit for better actinide ligands: an efficient strategy for their discovery.

A novel method for the efficient discovery of new types of minor actinide (MA) ligands is based on the unique combination of "tea bag" split pool combinatorial chemistry and screening based on the inherent radioactivity of the complexed cations. Four multicoordinating Am(3+) chelating groups, such as CMPO (diphenylcarbamoylmethyl)phosphine oxide), PICO (picolinamide), DGA (N,N'-dimethyldiglycoldiamide), and MPMA (N-methyl-N-phenylmalonamide), on a trityl platform immobilized on TentaGelS served as a model library for the development of the screening method. This model library was screened under various conditions (i.e., 0.001 M < or = [HNO3] < or = 3 M, NaNO3 < or = 4 M, and [Eu] < or = 10 x [ligand]) showing competitive extraction of the four ligands. Other libraries of 9 and 72 members were synthesized by functionalization of the trityl platform with ligating groups that are composed of four building blocks (including at least one amide and one (phosphoric) hydrazone moiety). The screening of these two libraries resulted in the discovery of two multicoordinate ligands that contain ligating groups previously not known to complex Am(3+). Both are N-isopropyl amides terminated with a p-methoxyphenyl hydrazide (A2B1C1D10 K(D(Am)) = 2197) or a p-nitrophenyl hydrazide (A2B1C1D11 K(D(Am)) =1989) moiety, respectively. They are more efficient than the immobilized tritylCMPO ligand (K(D(Am)) = 1280) at 3 M HNO3. This method has the advantages of a high analytical sensitivity and the direct comparison of the extraction results. The method also allows the competitive screening of multiple nuclides which can be quantified by their radioactive emission spectrum.

Selective removal of 226Ra2+ from gas-field-produced waters.

The 226Ra2+ selectivity of both the self-assembled (iso)-guanosine-based systems and ionizable thiacalix[4]crown dicarboxylic acids was determined in gas-field-produced water and a metal ion-containing model solution (simulant). Seven gas-field-produced water samples have been analyzed. From a sample (K5D) with average metal ion concentrations ([metal(tot)] = 0.14 M), thiacalix[4]crown-5 dicarboxylic acid (10(-4) M) extracts 60% of the 226Ra2+ content. Extractions performed with the model solution ((M)K5D) indicate that in K5D there is significant competition in 226Ra2+ extraction due to the organic constituents of K5D, in particular with self-assembled extractants guanosine and isoguanosine. Nevertheless, all four extractants extract 226Ra2+ both from the produced water K5D and the model solution (M)K5D, even with a 100-fold excess of [metal(tot)] to [extractant]. The extracted 226Ra2+ cations could effectively be stripped from the extractants bywashing with pH 2 water. The results obtained with the extractants used, especially thiacalix[4]crown-5 dicarboxylic acid 3, clearly demonstrate the way to selectively remove Ra2+ from gas-field-produced waters.

Ionizable (Thia)calix[4]crowns as highly selective 226Ra2+ ionophores.

The 226Ra2+ selectivity of the ionizable (thia)calix[4]crowns 1-4 was determined in the presence of a large excess of the most common alkali and alkaline earth cations. Selective 226Ra2+ (2.9 x 10(-)(8) M) extraction occurs even at extremely high M(n+)/226Ra2+ ratios of 3.5 x 10(7) [M(n+) = Na+, K+, Rb+, Cs+, Mg2+, Ca2+, and Sr2+ (1M)] and an ionophore concentration of 10(-4) M. The selectivity coefficients log(K(Ra)(ex)/K(M)(ex)) are approximately 3.5 for Mg2+, Ca2+, and Sr2+. In the presence of Ba2+, which has very similar chemical properties, only the thiacalix[4]crown-6 derivative 4 showed a selectivity for 226Ra2+. In addition to the remarkable 226Ra2+ selectivities, the effective pH range (pH 8-13) of the thiacalix[4]crown dicarboxylic acids (3 and 4) allows for full regeneration of the ionophores at lower pH values (pH <6).

Thiacalix[4]arene derivatives as radium ionophores: a study on the requirements for Ra2+ extraction.

The synthesis and NOE-based structural characterization is described of thiacalix[4]arene tricarboxylic acid (7), thiacalix[4]crown-5 and -6 monocarboxylic acids (2 and 5), and the bis(N-methylsulfonyl)thiacalix[4]crowns-5 and -6 (4a,b). The 226Ra2+ selectivity coefficients, log(K(Ra)ex/K(M)ex), of the new thiacalix[4]arene derivatives are compared directly with those of thiacalix[4]crown-5 and -6 (1a,b), thiacalix[4]crown-5 and -6 dicarboxylic acids (3a,b), and thiacalix[4]arene di- and tetracarboxylic acids (6 and 8). Thiacalix[4]arene dicarboxylic acid (6) already exhibits a high 226Ra2+ selectivity, but this is significantly improved in the case of 3b, having an additional crown-(6-)ether bridge. The covalent combination of a crown ether and carboxylic acid substituents as in the thiacalix[4]arenes 2,3a,b,4a,b, and 5 gives a better 226Ra2+ selectivity in the presence of Sr2+ or Ba2+ than mixtures of dibenzo-21-crown-7 and thiacalix[4]arene dicarboxylic acid (6) or of pentadecanoic acid and thiacalix[4]crown-6 (1b).

Molecular printboards on silicon oxide: lithographic patterning of cyclodextrin monolayers with multivalent, fluorescent guest molecules.

Three compounds bearing multiple adamantyl guest moieties and a fluorescent dye have been synthesized for the supramolecular patterning of beta-cyclodextrin (CD) host monolayers on silicon oxide using microcontact printing and dip-pen nanolithography. Patterns created on monolayers on glass were viewed by laser scanning confocal microscopy. Semi-quantitative analysis of the patterns showed that with microcontact printing approximately a single monolayer of guest molecules is transferred. Exposure to different rinsing procedures showed the stability of the patterns to be governed by specific supramolecular multivalent interactions. Patterns of the guest molecules created at CD monolayers were stable towards thorough rinsing with water, whereas similar patterns created on poly(ethylene glycol) (PEG) reference monolayers were instantly removed. The patterns on CD monolayers displayed long-term stability when stored under N(2), whereas patterns at PEG monolayers faded within a few weeks due to the diffusion of fluorescent molecules across the surface. Assemblies at CD monolayers could be mostly removed by rinsing with a concentrated CD solution, demonstrating the reversibility of the methodology. Patterns consisting of different guest molecules were produced by microcontact printing of one guest molecule and specific adsorption of a second guest molecule from solution to non-contacted areas, giving well-defined alternating assemblies. Fluorescent features of sub-micrometer dimensions were written using supramolecular dip-pen nanolithography.

Synthesis and conformational evaluation of p-tert-butylthiacalix[4]arene-crowns.

Bridging of p-tert-butylthiacalix[4]arene afforded 1,3-dihydroxythiacalix[4]arene-monocrown-5 (3b), 1,2-alternate thiacalix[4]arene-biscrown-4 and -5 (4a,b), and 1,3-alternate thiacalix[4]arene-biscrown-5 and -6 (5a,b), depending on the metal carbonates and oligoethylene glycol ditosylates used. Starting from 1,3-dialkylated thiacalix[4]arenes, the corresponding bridging reaction gave 1,3-alternate, partial-cone, and cone conformers 10-19, depending on the substituents present. Temperature-dependent studies revealed that the conformationally flexible 1,3-dimethoxythiacalix[4]arene-crowns 10a-c exclusively occupy the 1,3-alternate conformation. Demethylation exclusively gave the cone 1,3-dihydroxythiacalix[4]arene-crowns (3a,c), which could not be obtained by direct bridging of thiacalix[4]arene. The different structures were assigned on the basis of several X-ray crystal structures and extensive 2-D (1)H NMR studies.