Your browser doesn't support javascript.
loading
Show: 20 | 50 | 100
Results 1 - 20 de 43
Filter
1.
Small ; : e2311260, 2024 Apr 18.
Article in English | MEDLINE | ID: mdl-38634299

ABSTRACT

Vapor-based deposition techniques are emerging approaches for the design of carbon-supported metal powder electrocatalysts with tailored catalyst entities, sizes, and dispersions. Herein, a pulsed CVD (Pt-pCVD) approach is employed to deposit different Pt entities on mesoporous N-doped carbon (MPNC) nanospheres to design high-performance hydrogen evolution reaction (HER) electrocatalysts. The influence of consecutive precursor pulse number (50-250) and deposition temperature (225-300 °C) are investigated. The Pt-pCVD process results in highly dispersed ultrasmall Pt clusters (≈1 nm in size) and Pt single atoms, while under certain conditions few larger Pt nanoparticles are formed. The best MPNC-Pt-pCVD electrocatalyst prepared in this work (250 pulses, 250 °C) reveals a Pt HER mass activity of 22.2 ± 1.2 A mg-1 Pt at -50 mV versus the reversible hydrogen electrode (RHE), thereby outperforming a commercially available Pt/C electrocatalyst by 40% as a result of the increased Pt utilization. Remarkably, after optimization of the Pt electrode loading, an ultrahigh Pt mass activity of 56 ± 2 A mg-1 Pt at -50 mV versus RHE is found, which is among the highest Pt mass activities of Pt single atom and cluster-based electrocatalysts reported so far.

2.
Angew Chem Int Ed Engl ; 63(28): e202404360, 2024 Jul 08.
Article in English | MEDLINE | ID: mdl-38676693

ABSTRACT

Despite great progress in the construction of non-equilibrium systems, most approaches do not consider the structure of the fuel as a critical element to control the processes. Herein, we show that the amino acid side chains (A, F, Nal) in the structure of abiotic phosphates can direct assembly and reactivity during transient structure formation. The fuels bind covalently to substrates and subsequently influence the structures in the assembly process. We focus on the ways in which the phosphate esters guide structure formation and how structures and reactivity cross regulate when constructing assemblies. Through the chemical functionalization of energy-rich aminoacyl phosphate esters, we are able to control the yield of esters and thioesters upon adding dipeptides containing tyrosine or cysteine residues. The structural elements around the phosphate esters guide the lifetime of the structures formed and their supramolecular assemblies. These properties can be further influenced by the peptide sequence of substrates, incorporating anionic, aliphatic and aromatic residues. Furthermore, we illustrate that oligomerization of esters can be initiated from a single aminoacyl phosphate ester incorporating a tyrosine residue (Y). These findings suggest that activated amino acids with varying reactivity and energy contents can pave the way for designing and fabricating structured fuels.


Subject(s)
Peptides , Phosphates , Phosphates/chemistry , Peptides/chemistry , Esters/chemistry , Molecular Structure
3.
J Am Chem Soc ; 145(48): 26086-26094, 2023 12 06.
Article in English | MEDLINE | ID: mdl-37992133

ABSTRACT

Nature chose phosphates to activate amino acids, where reactive intermediates and complex machinery drive the construction of polyamides. Outside of biology, the pathways and mechanisms that allow spontaneous and selective peptide elongation in aqueous abiotic systems remain unclear. Herein we work to uncover those pathways by following the systems chemistry of aminoacyl phosphate esters, synthetic counterparts of aminoacyl adenylates. The phosphate esters act as solubility tags, making hydrophobic amino acids and their oligomers soluble in water and enabling selective elongation and different pathways to emerge. Thus, oligomers up to dodecamers were synthesized in one flask and on the minute time scale, where consecutive additions activated autonomous phase changes. Depending on the pathway, the resulting phases initially carry nonpolar peptides and amphiphilic oligomers containing phosphate esters. During elongation and phosphate release, shorter oligomers dominate in solution, while the aggregated phase favors the presence of longer oligomers due to their self-assembly propensity. Furthermore we demonstrated that the solution phases can be isolated and act as a new environment for continuous elongation, by adding various phosphate esters. These findings suggest that the systems chemistry of aminoacyl phosphate esters can activate a selection mechanism for peptide bond formation by merging aqueous synthesis and self-assembly.


Subject(s)
Peptides , Water , Water/chemistry , Peptides/chemistry , Organophosphates , Amino Acids/chemistry , Phosphates/chemistry , Esters
4.
Macromol Rapid Commun ; 40(11): e1900015, 2019 Jun.
Article in English | MEDLINE | ID: mdl-30892758

ABSTRACT

Ultrathin single crystal γ-Al(OH)3 (Gibbsite) nanoplatelets with average thickness <20 nm and length <800 nm, pretreated with trimethylaluminum (TMA), represent highly efficient activators and supports bis(imino)pyridine iron (II) (FeBIP) complex to produce high density polyethylene (HDPE) as well as gibbsite/HDPE nanocomposites in exceptionally high yields. Opposite to both methylaluminoxane (MAO)-activated homogeneous FeBIP catalyst and heterogenous silica-supported single site catalysts, no addition of MAO is required. At low TMA/Fe = 50 molar ratio, the superior catalyst activity (up to 6500 kg mol-1 h-1 bar-1 ) of FeBIP@TMA@Gibbsite is paralleled by controlled polyethylene particle growth without encountering reactor-fouling problems typical for homogeneous catalysts. TMA@Gibbsite is compared with other AlR3 @Gibbsite activators. The Al/Fe molar ratio governs catalyst activity as well as molar mass, molar mass distribution, and thermal properties of polyethylene. Moreover, hexagonal gibbsite nanoplatelets are uniformly dispersed in polyethylene to yield agglomerate-free polyethylene/gibbsite nanocomposites.


Subject(s)
Ethylenes/chemistry , Iron/chemistry , Nanocomposites/chemistry , Nanotechnology/methods , Polymers/chemistry , Catalysis
5.
Proc Natl Acad Sci U S A ; 110(32): 12887-92, 2013 Aug 06.
Article in English | MEDLINE | ID: mdl-23886665

ABSTRACT

Mechanical aspects of the cellular environment can influence cell function, and in this context hydrogels can serve as an instructive matrix. Here we report that physicochemical properties of hydrogels derived from polysaccharides (agarose, κ-carrageenan) having an α-helical backbone can be tailored by inducing a switch in the secondary structure from α-helix to ß-sheet through carboxylation. This enables the gel modulus to be tuned over four orders of magnitude (G' 6 Pa-3.6 × 10(4) Pa) independently of polymer concentration and molecular weight. Using carboxylated agarose gels as a screening platform, we demonstrate that soft-carboxylated agarose provides a unique environment for the polarization of endothelial cells in the presence of soluble and bound signals, which notably does not occur in fibrin and collagen gels. Furthermore, endothelial cells organize into freestanding lumens over 100 µm in length. The finding that a biomaterial can modulate soluble and bound signals provides impetus for exploring mechanobiology paradigms in regenerative therapies.


Subject(s)
Carbohydrate Conformation , Hydrogels/chemistry , Molecular Structure , Polysaccharides/chemistry , Carrageenan/chemistry , Carrageenan/pharmacology , Carrageenan/ultrastructure , Circular Dichroism , Human Umbilical Vein Endothelial Cells/drug effects , Human Umbilical Vein Endothelial Cells/physiology , Humans , Hydrogels/pharmacology , Hydrogen Bonding , Microscopy, Atomic Force , Microscopy, Electron, Scanning , Models, Molecular , Molecular Dynamics Simulation , Neovascularization, Physiologic/drug effects , Polysaccharides/pharmacology , Polysaccharides/ultrastructure , Rheology/methods , Sepharose/chemistry , Sepharose/pharmacology , Sepharose/ultrastructure , Spectroscopy, Fourier Transform Infrared
6.
J Bacteriol ; 195(7): 1411-20, 2013 Apr.
Article in English | MEDLINE | ID: mdl-23335414

ABSTRACT

Of the various kinds of cell division, the most common mode is binary fission, the division of a cell into two morphologically identical daughter cells. However, in the case of asymmetric cell division, Caulobacter crescentus produces two morphologically and functionally distinct cell types. Here, we have studied cell cycle progression of the human pathogen Helicobacter pylori using a functional green fluorescent protein (GFP) fusion of FtsZ protein and membrane staining. In small cells, representing newly divided cells, FtsZ localizes to a single cell pole. During the cell cycle, spiral intermediates are formed until an FtsZ ring is positioned with very little precision, such that central as well as acentral rings can be observed. Daughter cells showed considerably different sizes, suggesting that H. pylori divides asymmetrically. Fluorescence recovery after photobleaching (FRAP) analyses demonstrate that the H. pylori FtsZ ring is about as dynamic as that of Escherichia coli but that polar assemblies show less turnover. Strikingly, our results demonstrate that H. pylori cell division follows a different route from that in E. coli and Bacillus subtilis. It is also different from that in C. crescentus, where cytokinesis regulation proteins like MipZ play a role. Therefore, this report provides the first cell-biological analysis of FtsZ dynamics in the human pathogen H. pylori and even in epsilonproteobacteria to our knowledge. In addition, analysis of the filament architecture of H. pylori and E. coli FtsZ filaments in the heterologous system of Drosophila melanogaster S2 Schneider cells revealed that both have different filamentation properties in vivo, suggesting a unique intrinsic characteristic of each protein.


Subject(s)
Bacterial Proteins/analysis , Cell Division , Cytoskeletal Proteins/analysis , Helicobacter pylori/chemistry , Helicobacter pylori/physiology , Bacterial Proteins/genetics , Cytoskeletal Proteins/genetics , Genes, Reporter , Green Fluorescent Proteins/analysis , Green Fluorescent Proteins/genetics , Helicobacter pylori/cytology , Helicobacter pylori/metabolism , Recombinant Fusion Proteins/analysis , Recombinant Fusion Proteins/genetics
7.
Langmuir ; 29(12): 4092-5, 2013 Mar 26.
Article in English | MEDLINE | ID: mdl-23438034

ABSTRACT

When polymeric nanoparticles (NPs) are formed by nanoprecipitation, which is a nucleation-growth process, the control over size requires changing the polymer concentration or solvent composition. Here, we demonstrate that the NP size can be controlled independent of polymer variables by introducing a polyelectrolyte (PE) in the aqueous phase. PEs that exhibit hydrogen bonding (H-bonding) yield a reduction in NP size, whereas PEs that do not possess this characteristic promote the formation of larger NPs. The observed effect can be attributed to the formation of a diffusional barrier around the NP in the form of a dense shell. This principle of controlling NP size is not limited to polymers and can also be employed in the production of lipid NPs.


Subject(s)
Acrylic Resins/chemistry , Lactic Acid/chemistry , Nanoparticles/chemistry , Polyglycolic Acid/chemistry , Polystyrenes/chemistry , Diffusion , Hydrogen Bonding , Microscopy, Electron, Transmission , Nanoparticles/ultrastructure , Particle Size , Polyesters/chemistry , Polylactic Acid-Polyglycolic Acid Copolymer , Solvents/chemistry , Surface Properties , Water/chemistry
8.
Macromol Rapid Commun ; 34(15): 1249-55, 2013 Aug.
Article in English | MEDLINE | ID: mdl-23836705

ABSTRACT

Graphene functionalization by hydroxyalkylation and grafting with polyether polyols enables polyurethane (PU) nanocomposites formation by in situ polymerization with isocyanates combined with effective covalent interfacial coupling. Functionalized graphene (FG) hydroxylation is achieved either by alkylation, transesterification, or grafting of thermally reduced graphite oxide. In the presence of K2 CO3 as catalyst the reaction of FG-OH with ethylene carbonate at 180 °C affords hydroxyethylated FG, whereas transesterification with castor oil produces riconoleiate-modified FG polyols. In the "grafting-from" process, FG-alkoholate macro initiators initiate the graft polymerization of propylene oxide to produce hybrid FG polyols containing 38 and 59 wt% oligopropylene oxide. In the "grafting-to" process 3-ethyl-3-hydroxymethyl-oxetane is cationically polymerized onto FG-OH, producing novel hyperbranched FG-based polyether polyols. Whereas hydroxylation and grafting of FG greatly improve FG dispersion in organic solvents, polyols and even PU, as confirmed by transmission electron microscopy, matrix reinforcement of FG/PU is impaired by increasing alkyl chain length and polyol graft copolymer content.


Subject(s)
Graphite/chemistry , Nanocomposites/chemistry , Polymers/chemical synthesis , Polyurethanes/chemistry , Alkylation , Carbonates/chemistry , Catalysis , Hydroxylation , Polymers/chemistry , Potassium/chemistry
9.
Angew Chem Int Ed Engl ; 52(1): 455-8, 2013 Jan 02.
Article in English | MEDLINE | ID: mdl-23125048

ABSTRACT

A new family of hyperbranched polymeric ionic liquids ("hyperILs") with onion-like topology and facile polarity design were tailored as transporters and compartmentalized systems. Applications include transport and dispersion of water-soluble dyes and functionalized graphene nanosheets from aqueous phase into nonpolar fluids, including polymer melts.

10.
Acta Biomater ; 146: 274-283, 2022 07 01.
Article in English | MEDLINE | ID: mdl-35487427

ABSTRACT

Osteoarthritis (OA) is a joint disease affecting millions of patients worldwide. During OA onset and progression, the articular cartilage is destroyed, but the underlying complex mechanisms remain unclear. Here, we uncover changes in the thickness of collagen fibers and their composition at the onset of OA. For articular cartilage explants from knee joints of OA patients, we find that type I collagen-rich fibrocartilage-like tissue was formed in macroscopically intact cartilage, distant from OA lesions. Importantly, the number of thick fibers (>100 nm) has decreased early in the disease, followed by complete absence of thick fibers in advanced OA. We have obtained these results by a combination of high-resolution atomic force microscopy imaging under near-native conditions, immunofluorescence, scanning electron microscopy and a fluorescence-based classification of the superficial chondrocyte spatial organization. Taken together, our data suggests that the loss of tissue functionality in early OA cartilage is caused by a reduction of thick type II collagen fibers, likely due to the formation of type I collagen-rich fibrocartilage, followed by the development of focal defects in later OA stages. We anticipate that such an integrative characterization will be very beneficial for an in-depth understanding of other native biological tissues and the development of sustainable biomaterials. STATEMENT OF SIGNIFICANCE: In early osteoarthritis (OA) the cartilage appears macroscopically intact. However, this study demonstrates that the collagen network already changes in early OA by collagen fiber thinning and the formation of fibrocartilage-like tissue. Both nanoscopic deficiencies already occur in macroscopically intact regions of the human knee joint and are likely connected to processes that result in a weakened extracellular matrix. This study enhances the understanding of earliest progressive cartilage degeneration in the absence of external damage. The results suggest a determination of the mean collagen fiber thickness as a new target for the detection of early OA and a regulation of type I collagen synthesis as a new path for OA treatment.


Subject(s)
Cartilage, Articular , Osteoarthritis , Cartilage, Articular/pathology , Chondrocytes/physiology , Collagen Type I , Collagen Type II , Humans , Osteoarthritis/pathology
11.
J Funct Biomater ; 13(4)2022 Nov 11.
Article in English | MEDLINE | ID: mdl-36412879

ABSTRACT

In this project, different calcification methods for collagen and collagen coatings were compared in terms of their applicability for 3D printing and production of collagen-coated scaffolds. For this purpose, scaffolds were printed from polycaprolactone PCL using the EnvisionTec 3D Bioplotter and then coated with collagen. Four different coating methods were then applied: hydroxyapatite (HA) powder directly in the collagen coating, incubation in 10× SBF, coating with alkaline phosphatase (ALP), and coating with poly-L-aspartic acid. The results were compared by ESEM, µCT, TEM, and EDX. HA directly in the collagen solution resulted in a pH change and thus an increase in viscosity, leading to clumping on the scaffolds. As a function of incubation time in 10× SBF as well as in ALP, HA layer thickness increased, while no coating on the collagen layer was apparently observed with poly-L-aspartic acid. Only ultrathin sections and TEM with SuperEDX detected nano crystalline HA in the collagen layer. Exclusively the incubation in poly-L-aspartic acid led to HA crystals within the collagen coating compared to all other methods where the HA layers formed in different forms only at the collagen layer.

12.
Materials (Basel) ; 15(16)2022 Aug 09.
Article in English | MEDLINE | ID: mdl-36013620

ABSTRACT

In search of a new way to fabricate graphene-like materials, isostatic graphite targets were ablated using high peak power with a nanosecond-pulsed infrared laser. We conducted dry ablations in an argon atmosphere and liquid-phase ablations in the presence of a liquid medium (water or toluene). After the dry ablation, the SEM images of the target showed carbon in the form of a volcano-like grain structure, which seemed to be the result of liquid carbon ejected from the ablation center. No graphite exfoliation could be achieved using dry ablation. When using liquid phase ablation with water or toluene as a liquid medium, no traces of the formation of liquid carbon were found, but cleaner and deeper craters were observed. In particular, when using toluene as a liquid medium, typical graphite exfoliation was found. We believe that due to the extremely high pressure and high temperature induced by the laser pulses, toluene was able to intercalate into the graphite layers. Between the laser pulses, the intercalated toluene was able to flash evaporate and blow-up the graphite, which resulted in exfoliated graphite. Exfoliated graphite was found on the ablated graphite surface, as well as in the toluene medium. The ablation experiments with toluene undertaken in this study demonstrated an effective method of producing micrometer-sized graphene material. When using water as a liquid medium, no massive graphite exfoliation was observed. This meant that under the used laser conditions, toluene was a better intercalant for graphite exfoliation than water.

13.
Int J Nanomedicine ; 17: 5081-5097, 2022.
Article in English | MEDLINE | ID: mdl-36340183

ABSTRACT

Purpose: The conventional techniques for the preparation of reconstituted high-density lipoprotein (rHDL) are hampered by long process times, the need for large amounts of starting material, and harsh preparation conditions. Here, we present a novel rHDL preparation method to overcome these challenges. Furthermore, we propose a dual mode of action for rHDL loaded with the immunosuppressant drug everolimus (Eve-rHDL) in the context of atherosclerosis and cardiovascular disease. Methods: We use dual centrifugation for rHDL nanoparticle preparation and characterize the physicochemical properties by NS-TEM, N-PAGE, DLS, AF4, and HPLC. In addition, we determine the biological efficacy in human and murine cell culture with regard to cellular uptake, cholesterol efflux, and proliferation. Results: We confirm the characteristic particle size of 10 nm, discoidal morphology, and chemical composition of the rHDL preparations and identify dual centrifugation as an ideal method for cost-effective aseptic rHDL manufacturing. rHDL can be prepared in approx. 1.5 h with batch sizes as little as 89 µL. Moreover, we demonstrate the cholesterol efflux capacity and anti-proliferative activity of Eve-rHDL in vitro. The anti-proliferative effects were comparable to free Eve, thus confirming the suitability of rHDL as a capable drug delivery vehicle. Conclusion: Eve-rHDL shows great efficacy in vitro and may further be employed to target atherosclerotic plaques in vivo. Highly effective anti-atherosclerotic therapy might be feasible by reducing both inflammatory- and lipid burden of the plaques. Dual centrifugation is an ideal technique for the efficient application of the rHDL platform in cardiovascular disease and beyond.


Subject(s)
Atherosclerosis , Cardiovascular Diseases , Plaque, Atherosclerotic , Mice , Humans , Animals , Lipoproteins, HDL/chemistry , Everolimus/pharmacology , Cardiovascular Diseases/drug therapy , Atherosclerosis/drug therapy , Plaque, Atherosclerotic/drug therapy , Cholesterol , Centrifugation
14.
Chemistry ; 16(12): 3849-58, 2010 Mar 22.
Article in English | MEDLINE | ID: mdl-20187043

ABSTRACT

Stable chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, and iridium metal nanoparticles (M-NPs) have been reproducibly obtained by facile, rapid (3 min), and energy-saving 10 W microwave irradiation (MWI) under an argon atmosphere from their metal-carbonyl precursors [M(x)(CO)(y)] in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF(4)]). This MWI synthesis is compared to UV-photolytic (1000 W, 15 min) or conventional thermal decomposition (180-250 degrees C, 6-12 h) of [M(x)(CO)(y)] in ILs. The MWI-obtained nanoparticles have a very small (<5 nm) and uniform size and are prepared without any additional stabilizers or capping molecules as long-term stable M-NP/IL dispersions (characterization by transmission electron microscopy (TEM), transmission electron diffraction (TED), and dynamic light scattering (DLS)). The ruthenium, rhodium, or iridium nanoparticle/IL dispersions are highly active and easily recyclable catalysts for the biphasic liquid-liquid hydrogenation of cyclohexene to cyclohexane with activities of up to 522 (mol product) (mol Ru)(-1) h(-1) and 884 (mol product) (mol Rh)(-1) h(-1) and give almost quantitative conversion within 2 h at 10 bar H(2) and 90 degrees C. Catalyst poisoning experiments with CS(2) (0.05 equiv per Ru) suggest a heterogeneous surface catalysis of Ru-NPs.

15.
J Nanosci Nanotechnol ; 10(9): 6041-5, 2010 Sep.
Article in English | MEDLINE | ID: mdl-21133145

ABSTRACT

The optical properties of quantum dots strongly depend on the synthesis conditions including the reagent grade of the chemicals. We developed a synthesis set-up allowing the reproducible preparation of quantum dots with a high control over chemical and physical parameters. Here, we report on the effects of the injection speed, the stirring velocity and the reagent grade of the chemicals on the photoluminescence behaviour of CdSe quantum dots. Additionally we compared the commonly used hot-injection method with a novel one-pot approach leading to a slightly larger particle size distribution of the resulting high quality quantum dots in the latter case.

16.
Materials (Basel) ; 13(21)2020 Oct 28.
Article in English | MEDLINE | ID: mdl-33126719

ABSTRACT

The glass transition temperature (Tg) is one of the most important properties of polymeric materials. In order to reveal whether the scissors effect, i.e., the Fox-Flory relationship between Tg and the average molecular weight between crosslinking points (Mc), reported only in one case for polymer conetworks so far, is more generally effective or valid only for a single case, a series of poly(methyl methacrylate)-l-polyisobutylene (PMMA-l-PIB) conetworks was prepared and investigated. Two Tgs were found for the conetworks by DSC. Fox-Flory type dependence between Tg and Mc of the PMMA component (Tg = Tg,∞ - K/Mc) was observed. The K constants for the PMMA homopolymer and for the PMMA in the conetworks were the same in the margin of error. AFM images indicated disordered bicontinuous, mutually nanoconfined morphology with average domain sizes of 5-20 nm, but the correlation between Tg and domain sizes was not found. These new results indicate that the macrocrosslinkers act like molecular scissors (scissors effect), and the Tg of PMMA depend exclusively on the Mc in the conetworks. Consequently, these findings mean that the scissors effect is presumably a general phenomenon in nanophase-separated polymer conetworks, and this finding could be utilized in designing, processing, and applications of these novel materials.

17.
Polymers (Basel) ; 12(10)2020 Oct 07.
Article in English | MEDLINE | ID: mdl-33036354

ABSTRACT

Despite the great interest in nanoconfined materials nowadays, nanocompartmentalized poly(ionic liquid)s (PILs) have been rarely investigated so far. Herein, we report on the successful alkylation of poly(1-vinylimidazole) with methyl iodide in bicontinuous nanophasic poly(1-vinylimidazole)-l-poly(tetrahydrofuran) (PVIm-l-PTHF) amphiphilic conetworks (APCNs) to obtain nanoconfined methylated PVImMe-l-PTHF poly(ionic liquid) conetworks (PIL-CNs). A high extent of alkylation (~95%) was achieved via a simple alkylation process with MeI at room temperature. This does not destroy the bicontinuous nanophasic morphology as proved by SAXS and AFM, and PIL-CNs with 15-20 nm d-spacing and poly(3-methyl-1-vinylimidazolium iodide) PIL nanophases with average domain sizes of 8.2-8.4 nm are formed. Unexpectedly, while the swelling capacity of the PIL-CN dramatically increases in aprotic polar solvents, such as DMF, NMP, and DMSO, reaching higher than 1000% superabsorbent swelling degrees, the equilibrium swelling degrees decrease in even highly polar protic (hydrophilic) solvents, like water and methanol. An unprecedented Gaussian-type relationship was found between the ratios of the swelling degrees versus the polarity index, indicating increased swelling for the nanoconfined PVImMe-l-PTHF PIL-CNs in solvents with a polarity index between ~6 and 9.5. In addition to the nanoconfined structural features, the unique selective superabsorbent swelling behavior of the PIL-CNs can also be utilized in various application fields.

18.
Chemistry ; 15(39): 10047-59, 2009 Oct 05.
Article in English | MEDLINE | ID: mdl-19697371

ABSTRACT

Gold nanoparticles (Au-NPs) were reproducibly obtained by thermal, photolytic, or microwave-assisted decomposition/reduction under argon from Au(CO)Cl or KAuCl(4) in the presence of n-butylimidazol dispersed in the ionic liquids (ILs) BMIm(+)BF(4)(-), BMIm(+)OTf(-), or BtMA(+)NTf(2)(-) (BMIm(+) = n-butylmethylimidazolium, BtMA(+) = n-butyltrimethylammonium, OTf(-) = (-)O(3)SCF(3), NTf(2)(-) = (-)N(O(2)SCF(3))(2)). The ultra small and uniform nanoparticles of about 1-2 nm diameter were produced in BMIm(+)BF(4)(-) and increased in size with the molecular volume of the ionic liquid anion used in BMIm(+)OTf(-) and BtMA(+)NTf(2)(-). Under argon the Au-NP/IL dispersion is stable without any additional stabilizers or capping molecules. From the ionic liquids, the gold nanoparticles can be functionalized with organic thiol ligands, transferred, and stabilized in different polar and nonpolar organic solvents. Au-NPs can also be brought onto and stabilized by interaction with a polytetrafluoroethylene (PTFE, Teflon) surface. Density functional theory (DFT) calculations favor interactions between IL anions instead of IL cations. This suggests a AuF interaction and anionic Au(n) stabilization in fluorine-containing ILs. The (19)F NMR signal in BMIm(+)BF(4)(-) shows a small Au-NP concentration-dependent shift. Characterization of the dispersed and deposited gold nanoparticles was done by transmission electron microscopy (TEM/HRTEM), transmission electron diffraction (TED), dynamic light scattering (DLS), UV/Vis absorbance spectroscopy, scanning electron microscopy (SEM), electron spin resonance (ESR), and electron probe micro analyses (EPM, SEM/EDX).

19.
Chem Commun (Camb) ; (15): 1789-91, 2008 Apr 21.
Article in English | MEDLINE | ID: mdl-18379694

ABSTRACT

Stable chromium, molybdenum and tungsten nanoparticles are obtained reproducibly by thermal or photolytic decomposition under argon from mononuclear metal carbonyl precursors M(CO)(6) (M=Cr, Mo, W) suspended in the ionic liquids BMim(+)BF(4)(-), BMim(+)OTf(-) and BtMA(+)Tf(2)N(-) (BMim(+)=n-butyl-methyl-imidazolium, BtMA(+)=n-butyl-trimethyl-ammonium, Tf(2)N=N(O(2)SCF(3))(2), OTf=O(3)SCF(3)) with a very small and uniform size of 1 to 1.5 nm in BMim(+)BF(4)(-) which increases with the molecular volume of the ionic liquid anion to approximately 100 nm in BtMA(+)Tf(2)N(-) [characterization by transmission electron microscopy (TEM), dynamic light scattering and transmission electron diffraction (TED) analysis].

20.
Nanoscale ; 10(4): 1877-1884, 2018 Jan 25.
Article in English | MEDLINE | ID: mdl-29313048

ABSTRACT

In this work, reduced graphene oxide (rGO) based electrode materials were developed to achieve a hybrid supercapacitor (SC) function. Therefore, several synthesis methods were developed to prepare a cost effective and environmentally friendly rGO. Additionally, to maintain the high surface area, spinel lithium titanate (sLTO) nanoparticles (NPs) were synthesized and deposited on the rGO surface to inhibit the restacking of the rGO layers on graphite. Furthermore, the adequate Fe-doping of sLTO increased the ionic conductivity and the intercalation capacity, which is necessary for a SC performance. The sLTO/rGO-composites were electrochemically analysed by chronopotentiometry and electrochemical impedance spectroscopy (EIS) to determine the stability during charge/discharge cycling and the capacity, respectively. To overcome the drawback of LTO's low conductivity values, its value has been drastically increased by Fe-doping. The results demonstrated the remarkable cycling performance of the Fe:LTO/rGO composite as well as a higher capacity compared to LTO/rGO and pure rGO-electrodes. The thermal stability, degradation and weight loss of the sLTO/rGO in the temperature range between 20 °C and 800 °C were investigated by thermogravimetry (TG)/DTA. As a conclusion, it can be stated that, increasing the ionic conductivity by Fe-doping drastically increases the hybrid capacity of the SC electrodes.

SELECTION OF CITATIONS
SEARCH DETAIL