@article{vonKlitzingStehlPogrzebaetal.2017, author = {von Klitzing, Regine and Stehl, Dimitrij and Pogrzeba, Tobias and Schoma{\"a}cker, Reinhard and Minullina, Renata and Panchal, Abhishek and Konnova, Svetlana and Fakhrullin, Rawil and Koetz, Joachim and Moehwald, Helmuth and Lvov, Yuri}, title = {Halloysites Stabilized Emulsions for Hydroformylation of Long Chain Olefins}, series = {Advanced materials interfaces}, volume = {4}, journal = {Advanced materials interfaces}, number = {1}, publisher = {Wiley}, address = {Hoboken}, issn = {2196-7350}, doi = {10.1002/admi.201600435}, pages = {8}, year = {2017}, abstract = {Halloysites as tubular alumosilicates are introduced as inexpensive natural nanoparticles to form and stabilize oil-water emulsions. This stabilized emulsion is shown to enable efficient interfacial catalytic reactions. Yield, selectivity, and product separation can be tremendously enhanced, e.g., for the hydroformylation reaction of dodecene to tridecanal. In perspective, this type of formulation may be used for oil spill dispersions. The key elements of the described formulations are clay nanotubes (halloysites) which are highly anisometric, can be filled by helper molecules, and are abundantly available in thousands of tons, making this technology scalable for industrial applications.}, language = {en} } @article{CuiXiaMitzscherlingetal.2015, author = {Cui, Qianling and Xia, Bihua and Mitzscherling, Steffen and Masic, Admir and Li, Lidong and Bargheer, Matias and Moehwald, Helmuth}, title = {Preparation of gold nanostars and their study in selective catalytic reactions}, series = {Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects}, volume = {465}, journal = {Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0927-7757}, doi = {10.1016/j.colsurfa.2014.10.028}, pages = {20 -- 25}, year = {2015}, abstract = {In this work, gold nanostars (AuNSs) with size around 90 nm were prepared through an easy one-step method. They show excellent catalytic activity and large surface-enhanced Raman scattering (SERS) activity at the same time. Surprisingly, they exhibited different catalytic performance on the reduction of aromatic nitro compounds with different substituents on the para position. To understand such a difference, the SERS spectra were recorded, showing that the molecular orientation of reactants on the gold surface were different. We anticipate that this research will help to understand the relationship of the molecular orientation with the catalytic activity of gold nanoparticles.}, language = {en} } @article{CuiYashchenokLietal.2015, author = {Cui, Qianling and Yashchenok, Alexey and Li, Lidong and Moehwald, Helmuth and Bargheer, Matias}, title = {Mechanistic study on reduction reaction of nitro compounds catalyzed by gold nanoparticles using in situ SERS monitoring}, series = {Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects}, volume = {470}, journal = {Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0927-7757}, doi = {10.1016/j.colsurfa.2015.01.075}, pages = {108 -- 113}, year = {2015}, abstract = {Surface-enhanced Raman scattering (SERS) spectroscopy has emerged in recent years as a promising and powerful technique to investigate the reaction mechanism of heterogeneous catalysis. In this work, the reduction reaction of 4-nitrothiophenol (4-NTP) to its corresponding amino derivate catalyzed by gold took place between the gold nanoshell and gold nanostar. Due to the strong binding of thiol group to the gold surface, the molecular configuration of 4-NTP was fixed with NO2 group towards outside. The direct contact of NO2 group with catalytic gold nanostars ensured the reduction reaction went smoothly, which was monitored by SERS spectroscopy. The NO2 vibration Raman band showed a unique blue-shift without any appearance of dimerization product, indicating this catalytic reaction might follow a monomolecular mechanistic pathway. (C) 2015 Elsevier B.V. All rights reserved.}, language = {en} } @article{CuiYashchenokZhangetal.2014, author = {Cui, Qianling and Yashchenok, Alexey and Zhang, Lu and Li, Lidong and Masic, Admir and Wienskol, Gabriele and Moehwald, Helmuth and Bargheer, Matias}, title = {Fabrication of Bifunctional Gold/Gelatin Hybrid Nanocomposites and Their Application}, series = {ACS applied materials \& interfaces}, volume = {6}, journal = {ACS applied materials \& interfaces}, number = {3}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/am5000068}, pages = {1999 -- 2002}, year = {2014}, abstract = {Herein, a facile method is presented to integrate large gold nanoflowers (similar to 80 nm) and small gold nanoparticles (2-4 nm) into a single entity, exhibiting both surface-enhanced Raman scattering (SERS) and catalytic activity. The as-prepared gold nanoflowers were coated by a gelatin layer, in which the gold precursor was adsorbed and in situ reduced into small gold nanoparticles. The thickness of the gelatin shell is controlled to less than 10 nm, ensuring that the small gold nanoparticles are still in a SERS-active range of the inner Au core. Therefore, the reaction catalyzed by these nanocomposites can be monitored in situ using label-free SERS spectroscopy. In addition, these bifunctional nanocomposites are also attractive candidates for application in SERS monitoring of bioreactions because of their excellent biocompatibility.}, language = {en} } @article{CuiShenYanetal.2014, author = {Cui, Qianling and Shen, Guizhi and Yan, Xuehai and Li, Lidong and Moehwald, Helmuth and Bargheer, Matias}, title = {Fabrication of Au@Pt multibranched nanoparticles and their application to in situ SERS monitoring}, series = {ACS applied materials \& interfaces}, volume = {6}, journal = {ACS applied materials \& interfaces}, number = {19}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/am504709a}, pages = {17075 -- 17081}, year = {2014}, abstract = {Here, we present an Au@Pt core-shell multibranched nanoparticle as a new substrate capable of in situ surface-enhanced Raman scattering (SERS), thereby enabling monitoring of the catalytic reaction on the active surface. By careful control of the amount of Pt deposited bimetallic Au@Pt, nanoparticles with moderate performance both for SERS and catalytic activity were obtained. The Pt-catalyzed reduction of 4-nitrothiophenol by borohydride was chosen as the model reaction. The intermediate during the reaction was captured and clearly identified via SERS spectroscopy. We established in situ SERS spectroscopy as a promising and powerful technique to investigate in situ reactions taking place in heterogeneous catalysis.}, language = {en} } @article{BelovaShchukinGorinetal.2011, author = {Belova, Valentina and Shchukin, Dmitry G. and Gorin, Dmitry A. and Kopyshev, Alexey and Moehwald, Helmuth}, title = {A new approach to nucleation of cavitation bubbles at chemically modified surfaces}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {13}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, number = {17}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c1cp20218a}, pages = {8015 -- 8023}, year = {2011}, abstract = {Cavitation at the solid surface normally begins with nucleation, in which defects or assembled molecules located at a liquid-solid interface act as nucleation centers and are actively involved in the evolution of cavitation bubbles. Here, we propose a simple approach to evaluate the behavior of cavitation bubbles formed under high intensity ultrasound (20 kHz, 51.3 W cm (2)) at solid surfaces, based on sonication of patterned substrates with a small roughness (less than 3 nm) and controllable surface energy. A mixture of octadecylphosphonic acid (ODTA) and octadecanethiol (ODT) was stamped on the Si wafer coated with different thicknesses of an aluminium layer (20-500 nm). We investigated the growth mechanism of cavitation bubble nuclei and the evolution of individual pits (defects) formed under sonication on the modified surface. A new activation behavior as a function of Al thickness, sonication time, ultrasonic power and temperature is reported. In this process cooperativity is introduced, as initially formed pits further reduce the energy to form bubbles. Furthermore, cavitation on the patterns is a controllable process, where up to 40-50 min of sonication time only the hydrophobic areas are active nucleation sites. This study provides a convincing proof of our theoretical approach on nucleation.}, language = {en} } @article{HaaseGrigorievMoehwaldetal.2011, author = {Haase, Martin F. and Grigoriev, Dmitry and Moehwald, Helmuth and Tiersch, Brigitte and Shchukin, Dmitry G.}, title = {Nanoparticle modification by weak polyelectrolytes for pH-sensitive pickering emulsions}, series = {Langmuir}, volume = {27}, journal = {Langmuir}, number = {1}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/la1027724}, pages = {74 -- 82}, year = {2011}, abstract = {The affinity of weak polyelectrolyte coated oxide particles to the oil-water interface can be controlled by the degree of dissociation and the thickness of the weak polyelectrolyte layer. Thereby the oil in water (o/w) emulsification ability of the particles can be enabled. We selected the weak polyacid poly(methacrylic acid sodium salt) and the weak polybase poly(allylamine hydrochloride) for the surface modification of oppositely charged alumina and silica colloids, respectively. The isoelectric point and the pH range of colloidal stability of both particle-polyelectrolyte composites depend on the thickness of the weak polyelectrolyte layer. The pH-dependent wettability of a weak polyelectrolyte-coated oxide surface is characterized by contact angle measurements. The o/w emulsification properties of both particles for the nonpolar oil dodecane and the more polar oil diethylphthalate are investigated by measurements of the droplet size distributions. Highly stable emulsions can be obtained when the degree of dissociation of the weak polyelectrolyte is below 80\%. Here the average droplet size depends on the degree of dissociation, and a minimum can be found when 15 to 45\% of the monomer units are dissociated. The thickness of the adsorbed polyelectrolyte layer strongly influences the droplet size of dodecane/water emulsion droplets but has a less pronounced impact on the diethylphthalate/water droplets. We explain the dependency of the droplet size on the emulsion pH value and the polyelectrolyte coating thickness with arguments based on the particle-wetting properties, the particle aggregation state, and the oil phase polarity. Cryo-SEM visualization shows that the regularity of the densely packed particles on the oil-water interface correlates with the degree of dissociation of the corresponding polyelectrolyte.}, language = {en} } @article{HaaseGrigorievMoehwaldetal.2010, author = {Haase, Martin F. and Grigoriev, Dmitry and Moehwald, Helmuth and Tiersch, Brigitte and Shchukin, Dmitry G.}, title = {Encapsulation of amphoteric substances in a pH-sensitive pickering emulsion}, issn = {1932-7447}, doi = {10.1021/Jp104052s}, year = {2010}, abstract = {Oil-in-water (o/w) Pickering emulsions stabilized with silica nanoparticles were prepared. Droplets of diethyl phthalate (oil phase) act as reservoirs for 8-hydroxyquinoline (8-HQ), which is used as (a) the hydrophobizing agent for the silica particles and (b) an encapsulated corrosion inhibitor for application in active feedback coatings. The hydrophobization of silica nanoparticles with 8-HQ is determined by the amount of this agent adsorbed on the nanoparticle surface. The latter is governed by the 8-HQ concentration in the aqueous phase, which in turn depends on the degree of protonation and fir ally on the pH. We observe three ranges of 8-HQ adsorption value with respect to nanoparticle hydophobization: (I) insufficient, (2) sufficient, and (3) excessive adsorption by the formation of an 8-HQ bilayer, where only case 2 leads to the necessary nanoparticle hydrophobization. Hence emulsions stable in a narrow pH window between pH 5.5 and 4.4 follow. Here functional molecules are sufficiently charged to compensate for the charges on silica nanoparticles to make them interfacially active and thus able to stabilize an emulsion but they are still to a large extent uncharged and thereby remain in the oil phase. The emulsification is reversible upon changing the pH to a value beyond the stability region.}, language = {en} } @article{WegerichTuranoAllegrozzietal.2009, author = {Wegerich, Franziska and Turano, Paola and Allegrozzi, Marco and Moehwald, Helmuth and Lisdat, Fred}, title = {Cytochrome c mutants for superoxide biosensors}, issn = {0003-2700}, doi = {10.1021/Ac802571h}, year = {2009}, abstract = {The effect of introducing positive charges (lysines) in human cytochrome c (cyt c) on the redox properties and reaction rates of cyt c with superoxide radicals was studied. The mutated forms of this electron-transfer protein are used as sensorial recognition elements for the amperometric detection of the reactive oxygen radical. The proteins were prepared by site-directed mutagenesis focusing on amino acids near the heme edge. The 11 mutants of human cyt c expressed in the course of this research have been characterized by UV-vis spectroscopy, circular dichroism, and NMR spectroscopy to verify overall structure integrity as well as axial coordination of the heme iron. The mutants are investigated voltammetrically using promoter-modified gold electrodes with respect to redox activity and formal redox potential. The rate constants for the reaction with superoxide have been determined spectrophotometrically. Four mutants show a higher reaction rate with the radical as compared to the wild type. These mutants are used for the construction of superoxide sensors based on thiol-modified gold electrodes and covalently fixed proteins. We found that the E66K mutant-based electrode has a clearly higher sensitivity in comparison with the wild-type-based sensor while retaining the high selectivity and showing a good storage stability.}, language = {en} }