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1.
Sci Rep ; 14(1): 11904, 2024 May 24.
Article in English | MEDLINE | ID: mdl-38789603

ABSTRACT

Luminophore stained micro- and nanobeads made from organic polymers like polystyrene (PS) are broadly used in the life and material sciences as luminescent reporters, for bead-based assays, sensor arrays, printable barcodes, security inks, and the calibration of fluorescence microscopes and flow cytometers. Initially mostly prepared with organic dyes, meanwhile luminescent core/shell nanoparticles (NPs) like spherical semiconductor quantum dots (QDs) are increasingly employed for bead encoding. This is related to their narrower emission spectra, tuneability of emission color, broad wavelength excitability, and better photostability. However, correlations between particle architecture, morphology, and photoluminescence (PL) of the luminescent nanocrystals used for encoding and the optical properties of the NP-stained beads have been rarely explored. This encouraged us to perform a screening study on the incorporation of different types of luminescent core/shell semiconductor nanocrystals into polymer microparticles (PMPs) by a radical-induced polymerization reaction. Nanocrystals explored include CdSe/CdS QDs of varying CdS shell thickness, a CdSe/ZnS core/shell QD, CdSe/CdS quantum rods (QRs), and CdSe/CdS nanoplatelets (NPLs). Thereby, we focused on the applicability of these NPs for the polymerization synthesis approach used and quantified the preservation of the initial NP luminescence. The spectroscopic characterization of the resulting PMPs revealed the successful staining of the PMPs with luminescent CdSe/CdS QDs and CdSe/CdS NPLs. In contrast, usage of CdSe/CdS QRs and CdSe QDs with a ZnS shell did not yield luminescent PMPs. The results of this study provide new insights into structure-property relationships between NP stained PMPs and the initial luminescent NPs applied for staining and underline the importance of such studies for the performance optimization of NP-stained beads.

2.
Angew Chem Int Ed Engl ; 63(8): e202312473, 2024 Feb 19.
Article in English | MEDLINE | ID: mdl-37987465

ABSTRACT

Ruddlesden-Popper-type oxides exhibit remarkable chemical stability in comparison to perovskite oxides. However, they display lower oxygen permeability. We present an approach to overcome this trade-off by leveraging the anisotropic properties of Nd2 NiO4+δ . Its (a,b)-plane, having oxygen diffusion coefficient and surface exchange coefficient several orders of magnitude higher than its c-axis, can be aligned perpendicular to the gradient of oxygen partial pressure by a magnetic field (0.81 T). A stable and high oxygen flux of 1.40 mL min-1 cm-2 was achieved for at least 120 h at 1223 K by a textured asymmetric disk membrane with 1.0 mm thickness under the pure CO2 sweeping. Its excellent operational stability was also verified even at 1023 K in pure CO2 . These findings highlight the significant enhancement in oxygen permeation membrane performance achievable by adjusting the grain orientation. Consequently, Nd2 NiO4+δ emerges as a promising candidate for industrial applications in air separation, syngas production, and CO2 capture under harsh conditions.

3.
Nanoscale Adv ; 5(18): 5005-5014, 2023 Sep 12.
Article in English | MEDLINE | ID: mdl-37705785

ABSTRACT

The assembly of nanocrystals (NCs) into three-dimensional network structures is a recently established strategy to produce macroscopic materials with nanoscopic properties. These networks can be formed by the controlled destabilization of NC colloids and subsequent supercritical drying to obtain NC-based aerogels. Even though this strategy has been used for many different semiconductor NCs, the emission of NC-based aerogels is limited to the ultraviolet and visible and no near-infrared (NIR) emitting NC-based aerogels have been investigated in literature until now. In the present work we have optimized a gelation route of NIR emitting PbS and PbS/CdS quantum dots (QDs) by means of a recently established gel formation method using trivalent ions to induce the network formation. Thereby, depending on the surface ligands and QDs used the resulting network structure is different. We propose, that the ligand affinity to the nanocrystal surface plays an essential role during network formation, which is supported by theoretical calculations. The optical properties were investigated with a focus on their steady-state and time resolved photoluminescence (PL). Unlike in PbS/CdS aerogels, the absorption of PbS aerogels and their PL shift strongly. For all aerogels the PL lifetimes are reduced in comparison to those of the building blocks with this reduction being especially pronounced in the PbS aerogels.

4.
Parasit Vectors ; 16(1): 270, 2023 Aug 09.
Article in English | MEDLINE | ID: mdl-37559080

ABSTRACT

BACKGROUND: Insecticide-based malaria vector control is increasingly undermined due to the development of insecticide resistance in mosquitoes. Insecticide resistance may partially be related to the use of pesticides in agriculture, while the level and mechanisms of resistance might differ between agricultural practices. The current study aimed to assess whether phenotypic insecticide resistance and associated molecular resistance mechanisms in Anopheles gambiae sensu lato differ between agricultural practices. METHODS: We collected An. gambiae s.l. larvae in six sites with three different agricultural practices, including rice, vegetable and cocoa cultivation. We then exposed the emerging adult females to discriminating concentrations of bendiocarb (0.1%), deltamethrin (0.05%), DDT (4%) and malathion (5%) using the standard World Health Organization insecticide susceptibility test. To investigate underlying molecular mechanisms of resistance, we used multiplex TaqMan qPCR assays. We determined the frequency of target-site mutations, including Vgsc-L995F/S and Vgsc-N1570Y, and Ace1-G280S. In addition, we measured the expression levels of genes previously associated with insecticide resistance in An. gambiae s.l., including the cytochrome P450-dependent monooxygenases CYP4G16, CYP6M2, CYP6P1, CYP6P3, CYP6P4, CYP6Z1 and CYP9K1, and the glutathione S-transferase GSTe2. RESULTS: The An. gambiae s.l. populations from all six agricultural sites were resistant to bendiocarb, deltamethrin and DDT, while the populations from the two vegetable cultivation sites were additionally resistant to malathion. Most tested mosquitoes carried at least one mutant Vgsc-L995F allele that is associated with pyrethroid and DDT resistance. In the cocoa cultivation sites, we observed the highest 995F frequencies (80-87%), including a majority of homozygous mutants and several in co-occurrence with the Vgsc-N1570Y mutation. We detected the Ace1 mutation most frequently in vegetable-growing sites (51-60%), at a moderate frequency in rice (20-22%) and rarely in cocoa-growing sites (3-4%). In contrast, CYP6M2, CYP6P3, CYP6P4, CYP6Z1 and CYP9K1, previously associated with metabolic insecticide resistance, showed the highest expression levels in the populations from rice-growing sites compared to the susceptible Kisumu reference strain. CONCLUSION: In our study, we observed intriguing associations between the type of agricultural practices and certain insecticide resistance profiles in the malaria vector An. gambiae s.l. which might arise from the use of pesticides deployed for protecting crops.


Subject(s)
Anopheles , Insecticides , Malaria , Pyrethrins , Animals , Female , Insecticides/pharmacology , Insecticide Resistance/genetics , DDT , Cote d'Ivoire , Malathion , Mosquito Vectors/genetics , Pyrethrins/pharmacology , Agriculture
5.
Front Vet Sci ; 10: 1186650, 2023.
Article in English | MEDLINE | ID: mdl-37520008

ABSTRACT

Oral mucosal melanoma (OMM) is a common neoplasm in canines, although it is rare in humans. Cancer cells present alterations in energetic metabolism, and the Warburg effect states that most cancer cells undergo aerobic glycolysis. This can be reversed by certain drugs, resulting in decreased cell viability and cell death. We sought to evaluate the effects of sodium dichloroacetate (DCA) and omeprazole (OMP) alone or in combination on canine OMM and human melanoma cells. CMGD5 and SK-MEL-28 cell lines were treated with DCA and OMP alone or in combination, and cell viability was assessed using the crystal violet assay. Cell death (apoptosis and necrosis) was assessed by Annexin V and propidium iodide (PI) staining assays using flow cytometry. In addition, the oxygen consumption rate (OCR) was evaluated using a SeaHorse XF assay. Treatment with DCA or OMP alone resulted in a significant, but not dose-dependent, reduction in cell viability in both cell lines; however, the combination of DCA and OMP resulted in a significant and dose-dependent decrease in viability in both cell lines. DCA and OMP, alone or in combination, did not alter OCR at the concentrations tested in either cell line. Since the combination of DCA and OMP potentialized the inhibition of viability and increased cell death in a synergistic manner in melanoma cells, this approach may represent a new repurposing strategy to treat cancer.

6.
Sci Rep ; 13(1): 11957, 2023 Jul 24.
Article in English | MEDLINE | ID: mdl-37488159

ABSTRACT

Surface-functionalized polymer beads encoded with molecular luminophores and nanocrystalline emitters such as semiconductor nanocrystals, often referred to as quantum dots (QDs), or magnetic nanoparticles are broadly used in the life sciences as reporters and carrier beads. Many of these applications require a profound knowledge of the chemical nature and total number of their surface functional groups (FGs), that control bead charge, colloidal stability, hydrophobicity, and the interaction with the environment and biological systems. For bioanalytical applications, also the number of groups accessible for the subsequent functionalization with, e.g., biomolecules or targeting ligands is relevant. In this study, we explore the influence of QD encoding on the amount of carboxylic acid (COOH) surface FGs of 2 µm polystyrene microparticles (PSMPs). This is done for frequently employed oleic acid and oleylamine stabilized, luminescent core/shell CdSe QDs and two commonly used encoding procedures. This included QD addition during bead formation by a thermally induced polymerization reaction and a post synthetic swelling procedure. The accessible number of COOH groups on the surface of QD-encoded and pristine beads was quantified by two colorimetric assays, utilizing differently sized reporters and electrostatic and covalent interactions. The results were compared to the total number of FGs obtained by a conductometric titration and Fourier transform infrared spectroscopy (FTIR). In addition, a comparison of the impact of QD and dye encoding on the bead surface chemistry was performed. Our results demonstrate the influence of QD encoding and the QD-encoding strategy on the number of surface FG that is ascribed to an interaction of the QDs with the carboxylic acid groups on the bead surface. These findings are of considerable relevance for applications of nanoparticle-encoded beads and safe-by-design concepts for nanomaterials.

7.
Malar J ; 22(1): 93, 2023 Mar 13.
Article in English | MEDLINE | ID: mdl-36915098

ABSTRACT

BACKGROUND: Knowing the species composition and insecticide resistance status of the target vector population is important to guide malaria vector control. The aim of this study was to characterize the malaria vector population in terms of species composition, insecticide susceptibility status and potential underlying resistance mechanisms in Ellibou, southern Côte d'Ivoire. METHODS: A 1-year longitudinal entomological survey was conducted using light traps and pyrethroid spray catches to sample adult mosquitoes in combination with larval sampling. The susceptibility status of Anopheles gambiae sensu lato (s.l.) to bendiocarb, deltamethrin, DDT and malathion was assessed using the World Health Organization insecticide susceptibility test. Additionally, An. gambiae specimens were screened for knockdown (kdr) and acetylcholineesterase (ace1) target site resistance alleles, and the expression levels of eight metabolic resistance genes, including seven cytochrome P450 monooxygenases (P450s) and one glutathione S-transferase (GST), measured with reverse transcription quantitative real-time polymerase chain reaction (qPCR). RESULTS: Overall, 2383 adult mosquitoes from 12 different taxa were collected with Culex quinquefasciatus and An. gambiae being the predominant taxa. Molecular identification of An. gambiae s.l. revealed the presence of Anopheles arabiensis, Anopheles coluzzii, An. gambiae sensu stricto (s.s.) and Anopheles coluzzii/An. gambiae s.s. hybrids. Anopheles gambiae mosquitoes were resistant to all insecticides except malathion. PCR diagnostics revealed the presence of ace1-G280S and the kdr L995F, L995S and N1570Y target-site mutations. Additionally, several genes were upregulated, including five P450s (i.e., CYP6P3, CYP6M2, CYP9K1, CYP6Z1, CYP6P1) and GSTE2. CONCLUSION: This is the first documented presence of An. arabiensis in Côte d'Ivoire. Its detection - together with a recent finding further north of the country - confirms its existence in the country, which is an early warning sign, as An. arabiensis shows a different biology than the currently documented malaria vectors. Because the local An. gambiae population was still susceptible to malathion, upregulation of P450s, conferring insecticide resistance to pyrethroids, together with the presence of ace1, suggest negative cross-resistance. Therefore, organophosphates could be an alternative insecticide class for indoor residual spraying in the Ellibou area, while additional tools against the outdoor biting An. arabiensis will have to be considered.


Subject(s)
Anopheles , Insecticides , Malaria , Pyrethrins , Animals , Insecticides/pharmacology , Insecticide Resistance/genetics , Anopheles/genetics , Malathion/pharmacology , Cote d'Ivoire , Mosquito Vectors/genetics , Malaria/epidemiology
8.
Small ; 19(21): e2208108, 2023 May.
Article in English | MEDLINE | ID: mdl-36828791

ABSTRACT

Destabilization of a ligand-stabilized semiconductor nanocrystal solution with an oxidizing agent can lead to a macroscopic highly porous self-supporting nanocrystal network entitled hydrogel, with good accessibility to the surface. The previously reported charge carrier delocalization beyond a single nanocrystal building block in such gels can extend the charge carrier mobility and make a photocatalytic reaction more probable. The synthesis of ligand-stabilized nanocrystals with specific physicochemical properties is possible, thanks to the advances in colloid chemistry made in the last decades. Combining the properties of these nanocrystals with the advantages of nanocrystal-based hydrogels will lead to novel materials with optimized photocatalytic properties. This work demonstrates that CdSe quantum dots, CdS nanorods, and CdSe/CdS dot-in-rod-shaped nanorods as nanocrystal-based hydrogels can exhibit a much higher hydrogen production rate compared to their ligand-stabilized nanocrystal solutions. The gel synthesis through controlled destabilization by ligand oxidation preserves the high surface-to-volume ratio, ensures the accessible surface area even in hole-trapping solutions and facilitates photocatalytic hydrogen production without a co-catalyst. Especially with such self-supporting networks of nanocrystals, the problem of colloidal (in)stability in photocatalysis is circumvented. X-ray photoelectron spectroscopy and photoelectrochemical measurements reveal the advantageous properties of the 3D networks for application in photocatalytic hydrogen production.

9.
Small ; 19(10): e2206818, 2023 Mar.
Article in English | MEDLINE | ID: mdl-36642817

ABSTRACT

In this work, the influence of two different types of cations on the gel formation and structure of mixed gel networks comprised of semiconductor (namely CdSe/CdS nanorods NR) and Au nanoparticles (NP) as well as on the respective monocomponent gels is investigated. Heteroassemblies built from colloidal building blocks are usually prepared by ligand removal or cross-linking, thus, both the surface chemistry and the destabilising agent play an essential role in the gelation process. Due to the diversity of the composition, morphology, and optical properties of the nanoparticles, a versatile route to fabricate functional heteroassemblies is of great demand. In the present work, the optics, morphology, and gelation mechanism of pure semiconductor and noble metal as well as their mixed nanoparticle gel networks are revealed. The influence of the gelation agents (bivalent and trivalent cations) on the structure-property correlation is elucidated by photoluminescence, X-ray photoelectron spectroscopy, and electron microscopy measurements. The selection of cations drastically influences the nano- and microstructure of the prepared gel network structures driven by the affinity of the cations to the ligands and the nanoparticle surface. This gelation technique provides a new platform to control the formation of porous assemblies based on semiconductor and metal nanoparticles.

10.
J Phys Chem A ; 126(51): 9605-9617, 2022 Dec 29.
Article in English | MEDLINE | ID: mdl-36524393

ABSTRACT

The growing interest in multifunctional nano-objects based on polymers and magnetic nanoparticles for biomedical applications motivated us to develop a scale-up protocol to increase the yield of polymeric magnetic nanobeads while aiming at keeping the structural features at optimal conditions. The protocol was applied to two different types of magnetic ferrite nanoparticles: the Mn-ferrite selected for their properties as contrast agents in magnetic resonance imaging and iron oxide nanostar shaped nanoparticles chosen for their heat performance in magnetic hyperthermia. At the same time, some experiments on surface functionalization of nanobeads with amino modified polyethyelene glycol (PEG) molecules have provided further insight into the formation mechanism of magnetic nanobeads and the need to cross-link the polymer shell to improve the stability of the beads, making them more suitable for further manipulation and use. The present work summarizes the most important parameters required to be controlled for the upscaling of nanobead synthesis in a bench protocol and proposes an alternative cross-linking strategy based on prefunctionalization of the polymer prior to the nanobead formation as a key parameter to improve the nanobead structural stability in solutions at different pHs and during surface functionalization.


Subject(s)
Nanoparticles , Polymers , Polymers/chemistry , Ferric Compounds/chemistry , Nanoparticles/chemistry , Magnetic Resonance Imaging/methods
11.
Langmuir ; 38(37): 11149-11159, 2022 Sep 20.
Article in English | MEDLINE | ID: mdl-36067458

ABSTRACT

Two-dimensional (2D) semiconductor nanoplatelets (NPLs) are strongly photoluminescent materials with interesting properties for optoelectronics. Especially their narrow photoluminescence paired with a high quantum yield is promising for light emission applications with high color purity. However, retaining these features in solid-state thin films together with an efficient encapsulation of the NPLs is a challenge, especially when trying to achieve high-quality films with a defined optical density and low surface roughness. Here, we show photoluminescent polymer-encapsulated inorganic-organic nanocomposite coatings of 2D CdSe/CdS NPLs in poly(diallyldimethylammonium chloride) (PDDA) and poly(ethylenimine) (PEI), which are prepared by sequential layer-by-layer (LbL) deposition. The electrostatic interaction between the positively charged polyelectrolytes and aqueous phase-transferred NPLs with negatively charged surface ligands is used as a driving force to achieve self-assembled nanocomposite coatings with a well-controlled layer thickness and surface roughness. Increasing the repulsive forces between the NPLs by increasing the pH value of the dispersion leads to the formation of nanocomposites with all NPLs arranging flat on the substrate, while the surface roughness of the 165 nm (50 bilayers) thick coating decreases to Ra = 14 nm. The photoluminescence properties of the nanocomposites are determined by the atomic layer thickness of the NPLs and the 11-mercaptoundecanoic acid ligand used for their phase transfer. Both the full width at half-maximum (20.5 nm) and the position (548 nm) of the nanocomposite photoluminescence are retained in comparison to the colloidal CdSe/CdS NPLs in aqueous dispersion, while the measured photoluminescence quantum yield of 5% is competitive to state-of-the-art nanomaterial coatings. Our approach yields stable polymer-encapsulated CdSe/CdS NPLs in smooth coatings with controllable film thickness, rendering the LbL deposition technique a powerful tool for the fabrication of solid-state photoluminescent nanocomposites.

12.
Sci Rep ; 12(1): 12061, 2022 07 14.
Article in English | MEDLINE | ID: mdl-35835808

ABSTRACT

Luminescence-encoded microbeads are important tools for many applications in the life and material sciences that utilize luminescence detection as well as multiplexing and barcoding strategies. The preparation of such beads often involves the staining of premanufactured beads with molecular luminophores using simple swelling procedures or surface functionalization with layer-by-layer (LbL) techniques. Alternatively, these luminophores are sterically incorporated during the polymerization reaction yielding the polymer beads. The favorable optical properties of semiconductor quantum dots (QDs), which present broadly excitable, size-tunable, narrow emission bands and low photobleaching sensitivity, triggered the preparation of beads stained with QDs. However, the colloidal nature and the surface chemistry of these QDs, which largely controls their luminescence properties, introduce new challenges to bead encoding that have been barely systematically assessed. To establish a straightforward approach for the bead encoding with QDs with minimized loss in luminescence, we systematically assessed the incorporation of oleic acid/oleylamine-stabilized CdSe/CdS-core/shell-QDs into 0.5-2.5 µm-sized polystyrene (PS) microspheres by a simple dispersion polymerization synthesis that was first optimized with the organic dye Nile Red. Parameters addressed for the preparation of luminophore-encoded beads include the use of a polymer-compatible ligand such as benzyldimethyloctadecylammonium chloride (OBDAC) for the QDs, and crosslinking to prevent luminophore leakage. The physico-chemical and optical properties of the resulting beads were investigated with electron microscopy, dynamic light scattering, optical spectroscopy, and fluorescence microscopy. Particle size distribution, fluorescence quantum yield of the encapsulated QDs, and QD leaking stability were used as measures for bead quality. The derived optimized bead encoding procedure enables the reproducible preparation of bright PS microbeads encoded with organic dyes as well as with CdSe/CdS-QDs. Although these beads show a reduced photoluminescence quantum yield compared to the initially very strongly luminescent QDs, with values of about 35%, their photoluminescence quantum yield is nevertheless still moderate.


Subject(s)
Quantum Dots , Coloring Agents , Luminescence , Microspheres , Polymerization , Polystyrenes/chemistry , Quantum Dots/chemistry , Semiconductors
13.
J Chem Phys ; 156(23): 234701, 2022 Jun 21.
Article in English | MEDLINE | ID: mdl-35732518

ABSTRACT

The assembly of CdSe/CdS dot/rod nanocrystals (NCs) with variable length of ZnS tips into aerogel networks is presented. To this end, a partial region selective cation exchange procedure is performed replacing Cd by Zn starting at the NC tip. The produced aerogel networks are investigated structurally and optically. The networks of tip-to-tip connected NCs have an intricate band structure with holes confined to the CdSe cores while electrons are delocalized within the CdS also within connected building blocks. However, the ZnS tips act as a barrier of variable length and strength between the NC building blocks partly confining the electrons. This results in NC based aerogel networks with tunable strength of coupling between building blocks.

14.
Endocr Pract ; 28(5): 509-514, 2022 May.
Article in English | MEDLINE | ID: mdl-35247589

ABSTRACT

OBJECTIVE: Multiple endocrine neoplasia type 1 (MEN1) is a rare genetic syndrome characterized by parathyroid, anterior pituitary, and/or duodenopancreatic neuroendocrine tumors. Studies have indicated that investigating primary hyperparathyroidism (pHPT) with subsequent genetic screening may be an essential tool for the early diagnosis of MEN1 in patients with pituitary tumors (PTs). This study aimed to investigate the presence of pHPT in patients with PTs and, subsequently, to screen for genetic mutations and related tumors in patients with MEN1 syndrome. METHODS: This study included 255 patients with PTs who were assessed for the presence of MEN1 by serum calcium and parathyroid hormone measurements. Mutation screening of the MEN1, CDKN1B, and AIP genes was performed in the index cases showing the MEN1 phenotype. RESULTS: Five patients with PTs presented a clinical condition compatible with MEN1. These patients had a younger age of onset and a more severe clinical condition. Genetic analysis identified a frameshift mutation in the MEN1 gene in one of the cases with the MEN1 phenotype, but point mutations in CDKN1B and AIP were not detected in any of these patients. CONCLUSION: Our results show that periodic screening for pHPT in patients with PTs may be useful to detect MEN1 syndrome; thus, it is recommended in those patients with both findings a genetic analysis of MEN1 gene and an additional search of related tumors. By contrast, our data suggest that CDKN1B and AIP mutations do not seem to play a relevant role in the pathogenesis of MEN1.


Subject(s)
Hyperparathyroidism, Primary , Multiple Endocrine Neoplasia Type 1 , Pituitary Neoplasms , Genetic Profile , Humans , Hyperparathyroidism, Primary/diagnosis , Hyperparathyroidism, Primary/genetics , Hyperparathyroidism, Primary/pathology , Multiple Endocrine Neoplasia Type 1/complications , Multiple Endocrine Neoplasia Type 1/genetics , Mutation , Pituitary Neoplasms/complications , Pituitary Neoplasms/genetics
15.
Phys Chem Chem Phys ; 24(14): 8519-8528, 2022 Apr 06.
Article in English | MEDLINE | ID: mdl-35348140

ABSTRACT

Semiconductor nanoheterostructures (NHSs) are being increasingly used for the photocatalytic conversion of solar energy in which photo-induced charge separation is an essential step and hence it is necessary to understand the effect of various factors such as size, shape, and composition on the charge transfer dynamics. Ultrafast transient absorption spectroscopy is used to investigate the nature and dynamics of photo-induced charge transfer processes in ZnSe-CdS NHSs of different morphologies such as nanospheres (NSs), nanorods (NRs), and nanoplates (NPs). It demonstrates the fast separation of charge carriers and localization of both charges in adjacent semiconductors, resulting in the formation of a charge-separated (CS) state. The lifetime of the charge-separated state follows the order of NSs < NPs < NRs, emphasizing the effect of morphology on the enhancement of photo-induced charge separation and suppression of backward recombination. The separated charge carriers have been utilized in visible light driven hydrogen production and the hydrogen generation activity follows the same order as that for the lifetime of the CS state, underlining the role of charge separation efficiency. Therefore, the variation of the morphology of NHSs plays a significant role in their charge carrier dynamics and hence the photocatalytic hydrogen production activity.

16.
J Phys Chem C Nanomater Interfaces ; 126(9): 4563-4576, 2022 Mar 10.
Article in English | MEDLINE | ID: mdl-35299818

ABSTRACT

Boron-nitrogen substitutions in polycyclic aromatic hydrocarbons (PAHs) have a strong impact on the optical properties of the molecules due to a significantly more heterogeneous electron distribution. However, besides these single-molecule properties, the observed optical properties of PAHs critically depend on the degree of intermolecular interactions such as π-π-stacking, dipolar interactions, or the formation of dimers in the excited state. Pyrene is the most prominent example showing the latter as it exhibits a broadened and strongly bathochromically shifted emission band at high concentrations in solution compared to the respective monomers. In the solid state, the impact of intermolecular interactions is even higher as it determines the crystal packing crucially. In this work, a thiophene-flanked BN-pyrene (BNP) was synthesized and compared with its all-carbon analogue (CCP) in solution and in the solid state by means of crystallography, NMR spectroscopy, UV-vis spectroscopy, and photoluminescence (PL) spectroscopy. In solution, PL spectroscopy revealed the solvent-dependent presence of excimers of CCP at high concentrations. In contrast, no excimers were found in BNP. Clear differences were also observed in the single-crystal packing motifs. While CCP revealed overlapped pyrene planes with centroid distances in the range of classical π-stacking interactions, the BNP scaffolds were displaced and significantly more spatially separated.

17.
PLoS Genet ; 18(2): e1009963, 2022 02.
Article in English | MEDLINE | ID: mdl-35143477

ABSTRACT

Insecticide resistance in Anopheles mosquitoes is seriously threatening the success of insecticide-based malaria vector control. Surveillance of insecticide resistance in mosquito populations and identifying the underlying mechanisms enables optimisation of vector control strategies. Here, we investigated the molecular mechanisms of insecticide resistance in three Anopheles coluzzii field populations from southern Côte d'Ivoire, including Agboville, Dabou and Tiassalé. All three populations were resistant to bendiocarb, deltamethrin and DDT, but not or only very weakly resistant to malathion. The absence of malathion resistance is an unexpected result because we found the acetylcholinesterase mutation Ace1-G280S at high frequencies, which would typically confer cross-resistance to carbamates and organophosphates, including malathion. Notably, Tiassalé was the most susceptible population to malathion while being the most resistant one to the pyrethroid deltamethrin. The resistance ratio to deltamethrin between Tiassalé and the laboratory reference colony was 1,800 fold. By sequencing the transcriptome of individual mosquitoes, we found numerous cytochrome P450-dependent monooxygenases - including CYP6M2, CYP6P2, CYP6P3, CYP6P4 and CYP6P5 - overexpressed in all three field populations. This could be an indication for negative cross-resistance caused by overexpression of pyrethroid-detoxifying cytochrome P450s that may activate pro-insecticides, thereby increasing malathion susceptibility. In addition to the P450s, we found several overexpressed carboxylesterases, glutathione S-transferases and other candidates putatively involved in insecticide resistance.


Subject(s)
Anopheles/genetics , Insecticide Resistance/genetics , Malathion/pharmacology , Acetylcholinesterase/genetics , Animals , Anopheles/drug effects , Cote d'Ivoire/epidemiology , Cytochrome P-450 Enzyme System/genetics , Cytochrome P-450 Enzyme System/metabolism , Gene Expression/genetics , Insecticides/pharmacology , Malaria/prevention & control , Malaria/transmission , Malathion/metabolism , Mixed Function Oxygenases/genetics , Mosquito Control , Mosquito Vectors/genetics , Point Mutation , Transcriptome/genetics
18.
Adv Sci (Weinh) ; 9(11): e2105544, 2022 Apr.
Article in English | MEDLINE | ID: mdl-35132807

ABSTRACT

Room-temperature sodium-sulfur (RT Na-S) batteries are arousing great interest in recent years. Their practical applications, however, are hindered by several intrinsic problems, such as the sluggish kinetic, shuttle effect, and the incomplete conversion of sodium polysulfides (NaPSs). Here a sulfur host material that is based on tungsten nanoparticles embedded in nitrogen-doped graphene is reported. The incorporation of tungsten nanoparticles significantly accelerates the polysulfides conversion (especially the reduction of Na2 S4 to Na2 S, which contributes to 75% of the full capacity) and completely suppresses the shuttle effect, en route to a fully reversible reaction of NaPSs. With a host weight ratio of only 9.1% (about 3-6 times lower than that in recent reports), the cathode shows unprecedented electrochemical performances even at high sulfur mass loadings. The experimental findings, which are corroborated by the first-principles calculations, highlight the so far unexplored role of tungsten nanoparticles in sulfur hosts, thus pointing to a viable route toward stable Na-S batteries at room temperatures.

19.
Langenbecks Arch Surg ; 407(5): 2075-2083, 2022 Aug.
Article in English | MEDLINE | ID: mdl-35147749

ABSTRACT

PURPOSE: One of the major challenges in the management of patients with septic and non-septic open abdomen (OA) is to control abdominal wall retraction. The aim of this study was to evaluate the impact of a novel vertical traction device (VTD) on primary fascial closure (PFC) and prevention of fascial retraction. METHODS: Twenty patients treated with OA were included in this retrospective multicenter study. All patients were initially stabilized with laparostomy and the abdomen temporarily sealed either with a Bogotá bag or a negative pressure wound therapy system (NPWT). RESULTS: The mean duration of OA and fascia-to-fascia distance (FTF) prior to the VTD application were 3 days and 15 cm, respectively. At relook laparotomy 48 h after VTD implementation, the mean FTF distance significantly decreased to 10 cm (p = 0.0081). In all cases, PFC was achieved after a mean period of 7 days. Twelve patients received the VTD in combination with a NPWT, whereas in eight patients, the device was combined with an alternative temporary abdominal closure system (TAC). Although not statistically significant, the FTF distance remarkably decreased in both groups at relook laparotomy 48 h following the device implementation. The mean periods of PFC for patients with septic and non-septic OA were comparable (7.5 vs. 7 days). During follow-up, two patients developed an incisional hernia. CONCLUSION: Vertical traction device prevents fascial retraction and facilitates early PFC in OA. In combination with NPWT, rapid fascial closure of large abdominal defects can be achieved.


Subject(s)
Abdominal Wall , Abdominal Wound Closure Techniques , Negative-Pressure Wound Therapy , Abdomen , Abdominal Wall/surgery , Fascia , Fasciotomy , Humans , Surgical Mesh , Traction
20.
Macromol Rapid Commun ; 43(7): e2100794, 2022 Apr.
Article in English | MEDLINE | ID: mdl-35085414

ABSTRACT

Preparation of low density monolithic and free-standing organic-inorganic hybrid aerogels of various properties is demonstrated using green chemistry from a biosafe natural source (flaxseed mucilage) and freeze-casting and subsequent freeze drying. Bio-aerogels, luminescent aerogels, and magneto-responsive aerogels are obtained by combination of the flaxseed mucilage with different types of nanoparticles. Moreover, the aerogels are investigated as possible drug release systems using curcumin as a model. Various characterization techniques like thermogravimetric analysis, nitrogen physisorption, electron microscopy, UV/Vis absorption, and emission spectroscopy, bulk density, and mechanical measurements, as well as in vitro release profile measurements, are employed to investigate the obtained materials. The flaxseed-inspired organic-inorganic hybrid aerogels exhibit ultra-low densities as low as 5.6 mg cm-3 for 0.5% (w/v) the mucilage polymer, a specific surface area of 4 to 20 m2 g-1 , high oil absorption capacity (23 g g-1 ), and prominent compressibility. The natural biopolymer technique leads to low cost and biocompatible functional lightweight materials with tunable properties (physicochemical and mechanical) and significant potential for applications as supporting or stimuli responsive materials, carriers, reactors, microwave- and electromagnetic radiation protective (absorbing)-materials, as well as in drug delivery and oil absorption.


Subject(s)
Flax , Nanoparticles , Drug Liberation , Gels/chemistry , Porosity
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