Volume 232, Issue 5-6 - Special Issue: Dedicated to Eckart Rühl on the occasion of his 60th birthday / Guest Editors: Helmut Baumgärtel and Christina Graf

Methane permeation through polyamide and polyethylene mono and multilayer films has been measured via direct coupling of a gaschromatograph with a permeation measurement cell. Methane permeabilities [in cm 3 (STP)·mm·d −1 ·bar −1 ·m −2 ] for single films were found to be 335 for polyethylene (PE) at 40°C, 0.64 for polyamide (PA) 6/6.6 with dry gas and 8.7 for PA 6/6.6 with water vapour saturated test gas. As a result, under operating conditions of biogas production facilities (40°C, water vapour saturated), the replacement of PE by PA, as biogas membrane on top of a fermenter, can reduce methane emission through permeation by a factor of about 40.

In biological cells, osmolytes appear as complex mixtures with variable compositions, depending on the particular environmental conditions of the organism. Based on various spectroscopic, thermodynamic and small-angle scattering data, we explored the effect of two different natural osmolyte mixtures, which are found in shallow-water and deep-sea shrimps, on the temperature and pressure stability of a typical monomeric protein, RNase A. Both natural osmolyte mixtures stabilize the protein against thermal and pressure denaturation. This effect seems to be mainly caused by the major osmolyte components of the osmolyte mixtures, i.e. by glycine and trimethylamine- N -oxide (TMAO), respectively. A minor compaction of the structure, in particular in the unfolded state, seems to be largely due to TMAO. Differences in thermodynamic properties observed for glycine and TMAO, and hence also for the two osmolyte mixtures, are most likely due to different solvation properties and interactions with the protein. Different from TMAO, glycine seems to interact with the amino acid side chains and/or the backbone of the protein, thus competing with hydration water and leading to a less hydrated protein surface.

The article reports on the composition, mixing state and water affinity of iron silicate particles which were produced in a non-thermal low-pressure microwave plasma reactor. The particles are intended to be used as meteoric smoke particle analogues. We used the organometallic precursors ferrocene (Fe(C 5 H 5 ) 2 ) and tetraethyl orthosilicate (TEOS, Si(OC 2 H 5 ) 4 ) in various mixing ratios to produce nanoparticles with radii between 1 nm and 4 nm. The nanoparticles were deposited on sample grids and their stoichiometric composition was analyzed in an electron microscope using energy dispersive X-ray spectroscopy (EDS). We show that the pure silicon oxide and iron oxide particles consist of SiO 2 and Fe 2 O 3 , respectively. For Fe:(Fe+Si) ratios between 0.2 and 0.8 our reactor produces (in contrast to other particle sources) mixed iron silicates with a stoichiometric composition according to Fe x Si (1−x) O 3 (0≤x≤1). This indicates that the particles are formed by polymerization of FeO 3 and SiO 3 and that rearrangement to the more stable silicates ferrosilite (FeSiO 3 ) and fayalite (Fe 2 SiO 4 ) does not occur at these conditions. To investigate the internal mixing state of the particles, the H 2 O surface desorption energy of the particles was measured. We found that the nanoparticles are internally mixed and that differential coating resulting in a core-shell structure does not occur.

This study elucidates molecular structures, fragmentation pathways and relative stabilities of isolated trinuclear oxo bridged cobalt complexes of the structural type [Co 3 O(OAc) 6 (Py) n ] + (OAc=acetate, Py=pyridine, n=0, 1, 2, 3). We present infrared multiple photon dissociation (IR-MPD) spectra in combination with quantum chemical calculations. They indicate that the coordination of axial pyridine ligands to the [Co 3 O(OAc) 6 ] + subunit disturbs the triangular geometry of the Co 3 O core. [Co 3 O(OAc) 6 ] + exhibits a nearly equilateral triangular Co 3 O core geometry. The coordination of one or two pyridine ligands disturbs this arrangement resulting in isosceles triangular Co 3 O core geometries (in the cases of n=1 and 2). Coordination of three pyridine ligands (n=3) results in an equilateral triangular Co 3 O core geometry as in the case of n=0. Collision induced dissociation (CID) studies reveal that the complexes undergo a consecutive elimination of pyridine and acetate ligands with increasing excitation energy. Relative stabilities of the complexes decrease with the number of coordinated pyridine ligands. The presented results help to gain a fundamental insight into the molecular structure of trinuclear oxo bridged cobalt complexes void of any external effects such as crystal packing or solvation.

We report here on a custom-built time-correlated single photon-counting (TCSPC)-based fluorescence lifetime imaging microscopy (FLIM) setup with a continuously tunable white-light supercontinuum laser combined with acousto-optical tunable filters (AOTF) as an excitation source for simultaneous excitation of multiple spectrally separated fluorophores. We characterized the wavelength dependence of the white-light supercontinuum laser pulse properties and demonstrated the performance of the FLIM setup, aiming to show the experimental setup in depth together with a biomedical application. We herein summarize the physical-technical parameters as well as our approach to map the skin uptake of nanocarriers using FLIM with a resolution compared to spectroscopy. As an example, we focus on the penetration study of indocarbocyanine-labeled dendritic core-multishell nanocarriers (CMS-ICC) into reconstructed human epidermis. Unique fluorescence lifetime signatures of indocarbocyanine-labeled nanocarriers indicate nanocarrier-tissue interactions within reconstructed human epidermis, bringing FLIM close to spectroscopic analysis.

Structural isomers of disubstituted benzenes are difficult to distinguish with most mass spectrometric methods. Consequently, conventional concepts for the distinction of isomers are based on coupling mass spectrometry with a chromatographic method. As an alternative approach, we propose the combination of femtosecond laser ionization with time-of-flight mass spectrometry (fs-LIMS). The possibility of systematic tailoring of fs-laser pulse shapes opens access to a multidimensional analytical technique capable of distinguishing structural isomers of the title molecules.

Intermolecular interactions of pyridine in liquid and in aqueous solution are studied by using soft X-ray absorption spectroscopy (XAS) at the C, N, and O K-edges. XAS of liquid pyridine shows that the N 1s→π* peak is blue shifted and the C 1s→π* peak of the meta and para sites is red shifted, respectively, as compared with XAS of pyridine gas. These shifts in liquid are smaller than those in clusters, indicating that the intermolecular interaction of liquid pyridine is weaker than that of pyridine cluster, as supported by the combination of quantum chemical calculations of the core excitation and molecular dynamics simulations of the liquid structure. On the other hand, XAS spectra of aqueous pyridine solutions (C 5 H 5 N) x (H 2 O) 1− x measured at different molar fractions show that in the pyridine rich region, x >0.7, the C and N 1s→π* peak energies are not so different from pure liquid pyridine ( x =1.0). In this region, antiparallel displaced structures of pyridine molecules are dominant as in pure pyridine liquid. In the O K-edge XAS, the pre-edge peaks sensitive to the hydrogen bond (HB) network of water molecules show the red shift of −0.15 eV from that of bulk water, indicating that small water clusters with no large-scale HB network are formed in the gap space of structured pyridine molecules. In the water rich region, 0.7> x , the N 1s→π* peaks and the O 1s pre-edge peaks are blue shifted, and the C 1s→π* peaks of the meta and para sites are red-shifted by increasing molar fraction of water. The HB network of bulk water is dominant, but quantum chemical calculations indicate that small pyridine clusters with the HB interaction between the H atom in water and the N atom in pyridine are still existent even in very dilute pyridine solutions.

Inner shell excitation spectroscopy is a local probe of the unoccupied electronic structure in the immediate vicinity of the core excited atom. As such, one might expect the inner shell spectrum of a given unit (a molecular fragment or a repeat unit of a solid) to be largely independent of where that unit is located. This is often an implicit assumption in spectral analysis and analytical applications. However, there are situations where inner shell excitation spectra exhibit significant sensitivity to their local environment. Here I categorize the ways in which inner shell spectra are affected by their local environment, and give examples from a career dedicated to developing a better understanding of inner shell excitation spectroscopy, its experimental techniques, and applications.

Harvesting energy from photochemical reactions has long been studied as an efficient means of renewable energy, a topic that is increasingly gaining importance also for motion at the microscale. Iron oxide has been a material of interest in recent studies. Thus, in this work different synthesis methods and encapsulation techniques were used to try and optimize the photo-catalytic properties of iron oxide colloids. Photodegradation experiments were carried out following the encapsulation of the nanoparticles and the Fenton effect was also verified. The end goal would be to use the photochemical degradation of peroxide to propel an array of swimmers in a controlled manner while utilizing the Fenton effect for the degradation of dyes or waste in wastewater remediation.

Microparticles have attracted much attention for medical, analytical and biological applications. Calcium carbonate (CaCO 3 ) templating method with the advantages of having narrow size distribution, controlled morphology and good biocompatibility that has been widely used for the synthesis of various protein-based microparticles. Despite CaCO 3 template is biocompatible, most of the conventional methods to create stable protein microparticles are mainly driven by chemical crosslink reagents which may induce potential harmful effect and remains undesirable especially for biomedical or clinical applications. In this article, we demonstrate the fabrication of protein microparticles and microcapsules with an innovative method using biomolecular tools such as enzymes and affinity molecules to trigger the assembling of protein molecules within a porous CaCO 3 template followed by a template removal step. We demonstrated the enzyme-assisted fabrication of collagen microparticles triggered by transglutaminase, as well as the affinity-assisted fabrication of BSA-biotin avidin microcapsules triggered by biotin-avidin affinity interaction, respectively. Based on the different protein assemble mechanisms, the collagen microparticles appeared as a solid-structured particles, while the BSA-biotin avidin microcapsules appeared as hollow-structured morphology. The fabrication procedures are simple and robust that allows producing protein microparticles or microcapsules under mild conditions at physiological pH and temperature. In addition, the microparticle morphologies, protein compositions and the assemble mechanisms were studied. Our technology provides a facile approach to design and fabricate protein microparticles and microcapsules that are useful in the area of biomaterials, pharmaceuticals and analytical chemistry.

Metallic nanoparticles have been used as catalysts for various reactions, and the huge literature on the subject is hard to overlook. In many applications, the nanoparticles must be affixed to a colloidal carrier for easy handling during catalysis. These “passive carriers” (e.g. dendrimers) serve for a controlled synthesis of the nanoparticles and prevent coagulation during catalysis. Recently, hybrids from nanoparticles and polymers have been developed that allow us to change the catalytic activity of the nanoparticles by external triggers. In particular, single nanoparticles embedded in a thermosensitive network made from poly(N-isopropylacrylamide) (PNIPAM) have become the most-studied examples of such hybrids: immersed in cold water, the PNIPAM network is hydrophilic and fully swollen. In this state, hydrophilic substrates can diffuse easily through the network, and react at the surface of the nanoparticles. Above the volume transition located at 32°C, the network becomes hydrophobic and shrinks. Now hydrophobic substrates will preferably diffuse through the network and react with other substrates in the reaction catalyzed by the enclosed nanoparticle. Such “active carriers”, may thus be viewed as true nanoreactors that open new ways for the use of nanoparticles in catalysis. In this review, we give a survey on recent work done on these hybrids and their application in catalysis. The aim of this review is threefold: we first review hybrid systems composed of nanoparticles and thermosensitive networks and compare these “active carriers” to other colloidal and polymeric carriers (e.g. dendrimers). In a second step we discuss the model reactions used to obtain precise kinetic data on the catalytic activity of nanoparticles in various carriers and environments. These kinetic data allow us to present a fully quantitative comparison of different nanoreactors. In a final section we shall present the salient points of recent efforts in the theoretical modeling of these nanoreactors. By accounting for the presence of a free-energy landscape for the reactants’ diffusive approach towards the catalytic nanoparticle, arising from solvent-reactant and polymeric shell-reactant interactions, these models are capable of explaining the emergence of all the important features observed so far in studies of nanoreactors. The present survey also suggests that such models may be used for the design of future carrier systems adapted to a given reaction and solvent.

Hair follicles can serve as an effective reservoir for dermal drug delivery upon the topical application of particulate substances. Here, the follicular penetration of an indodicarbocyanine-labelled thermoresponsive nanogel (189 nm) having a cloud point temperature of 34°C and linked via an acid-labile linker to the model drug indocarbocyanine was investigated. In total, 227 hair follicles of porcine ear skin were examined after topical application of the thermoresponsive nanogels at room temperature (21°C), physiological skin surface temperature (32°C) and core body temperature (37°C) for the follicular penetration depths of indodicarbocyanine and indocarbocyanine using confocal laser scanning microscopy. The results showed a significantly increased mean follicular penetration of the carrier to a depth of 298.8±85.8 μm after incubation at 37°C compared to samples incubated at 21°C and 32°C with mean follicular penetration depths of 202.7±81.7 μm and 219.4±52.9 μm, respectively (p<0.001). Possibly structural changes in the thermoresponsive nanogel induced by the increased incubation temperature led to an enhancement of follicular penetration. Therefore, thermoresponsive nanogels may be suitable for the temperature-enhanced penetration into the hair follicles under physiological conditions.

For the application of iron oxide nanoparticles from thermal decomposition approaches as contrast agents in magnetic resonance imaging (MRI), their initial hydrophobic ligands have to be replaced by hydrophilic ones. This exchange can influence the surface oxidation state and the magnetic properties of the particles. Here, the effect of the anchor group of three organic ligands, citric acid and two catechols, dihydrocaffeic acid and its nitrated derivative nitro dihydrocaffeic acid on iron oxide nanoparticles is evaluated. The oleate ligands of Fe 3 O 4 /γ-Fe 2 O 3 nanoparticles prepared by the thermal decomposition of iron oleate were exchanged against the hydrophilic ligands. X-ray absorption spectroscopy, especially X-ray magnetic circular dichroism (XMCD) measurements in the total electron yield (TEY) mode was used to investigate local magnetic and electronic properties of the particles’ surface region before and after the ligand exchange. XMCD was combined with charge transfer multiplet calculations which provide information on the contributions of Fe 2+ and Fe 3+ at different lattice sites, i.e. either in tetrahedral or octahedral environment. The obtained data demonstrate that nitro hydrocaffeic acid leads to least reduction of the magnetizability of the surface region of the iron oxide nanoparticles compared to the two other ligands. For all hydrophilic samples, the proportion of Fe 3+ ions in octahedral sites increases at the expense of the Fe 2+ in octahedral sites whereas the percentage of Fe 3+ in tetrahedral sites hardly changes. These observations suggest that an oxidation process took place, but a selective decrease of the Fe 2+ ions in octahedral sites ions due to surface dissolution processes is unlikely. The citrate ligand has the least oxidative effect, whereas the degree of oxidation was similar for both catechol ligands regardless of the nitro group. Twenty-four hours of incubation in isotonic saline has nearly no influences on the magnetic properties of the nanoparticles, the least on those with the nitrated hydrocaffeic acid ligand.

The dissociative photoionization of quinoline was studied by photoionization mass spectrometry and ion yield measurements over a synchrotron photon excitation energy range 7–26 eV. The ionic and neutral products were identified with the aid of thermochemical calculations that, in some cases, led to deeper understanding of photodissociation pathways and the determination of upper limits of heats of formation of ionic and neutral dissociation products. A detailed comparison between the 20 eV photon excitation and 70 eV electron impact mass spectra, coupled with estimation of thermochemical appearance energies, leads to assignment of the dissociative ionization cation and neutral products for each detected ion. Reaction schemes for formation of these products are proposed in a number of cases. Ion intensities in the photon and electron impact mass spectra were used to consider extending a rule of charge retention in simple bond cleavage to more complex cases of dissociative ionization.

Spin-labeling active compounds is a convenient way to prepare them for EPR spectroscopy with minimal alteration of the target molecule. In this study we present the labeling reaction of dexamethasone (Dx) with either TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) or PCA (3-(carboxy)-2,2,5,5-tetramethyl-1-pyrrolidinyloxy) with high yields. According to NMR data, both labels are attached at the primary hydroxy group of the steroid. In subsequent spin-stability measurements both compounds were applied onto HaCaT cells. When the signal of Dx-TEMPO decreased below the detection limit within 3 h, the signal of Dx-PCA remained stable for the same period of time.

We have used X-ray photoemission spectroscopy to study the interaction of gold (Au) with novel boron carbide-based semiconductors grown by plasma-enhanced chemical vapor deposition (PECVD). Both n- and p-type films have been investigated and the PECVD boron carbides are compared to those containing aromatic compounds. In the case of the p-type semiconducting PECVD hydrogenated boron carbide samples, the binding energy of the B(1s) core level shows a shift to higher binding energies as the Au is deposited, an indication of band bending and possibly Schottky barrier formation. In the case of the n-type boron carbide semiconductors the interaction at the interface is more typical of an ohmic contact. Addition of the aromatic compounds increases the change in binding energies on both n-type and p-type PECVD boron carbide semiconductors, and the gold appears to diffuse into the PECVD boron carbides alloyed with aromatic moieties.

Changes in spectral distribution of oscillator strength for core-to-valence transitions probed by X-ray absorption and total electron yield (TEY) modes are studied in more detail. The quantitative analysis of their redistribution in TEY due to the saturation effect is performed by applying the model M˜$\tilde M$-function method suggested by Flesch et al. J. Chem. Phys. 138 (2013) 144302. The model M˜$\tilde M$-function method is generalized to account for the saturation-induced distortion of the line shape of the transitions embedded into the core ionization continua and located below them. It is shown that TEY measurements produce essential changes not only in the relative intensity of the transitions but also shift upward the transition energy, broaden the Lorentzian and Gaussian widths and enhance the line asymmetry. The Gaussian width of the TEY signal undergoes the most substantial broadening though the Lorentzian width increases significantly too. The saturation-induced distortion of the line shapes is not negligible even if the well-known escape-to-penetration condition is valid.

Background: Refined encapsulation approaches in dermatotherapy gain increased interest. There is need of reproducible in vitro systems representing disease features to screen drug delivery systems for preclinical assessment. Inflammatory human skin diseases are commonly accompanied by abnormal epidermal differentiation and barrier impairment. Serine proteases (SPs) and their inhibitors play a critical role in such dysfunctional differentiation. SPs also initiate cellular pathways via activation of protease-activated receptors, which contribute to inflammation. Thus, function and activity of SPs should be considered for the design of new therapies of such disorders. Objectives: Herein, we established a novel simplified cell culture model, based on SP-mediated inflammation suitable to assess nanocarriers loaded with anti-inflammatory drugs. Methods: SP-mediated inflammation and the regulatory effect of free or encapsulated dexamethasone were determined by measuring interleukin-6 and interleukin-8 in culture medium of HaCaT (human adult low calcium temperature)-keratinocytes. Additionally, radical formation was analyzed by electron paramagnetic resonance spectroscopy. Cellular uptake of core-multishell nanocarriers was investigated by fluorescence microscopy. Cytotoxicity of all additives was determined by a viability assay. Results: SP-Stimulation of keratinocytes resulted in increased radical production and release of inflammatory cytokines without affecting cell viability. Induced inflammation was successfully downregulated by addition of free or encapsulated dexamethasone. Conclusion: SP-addition can be used as inflammatory stimulus in cell culture to mimic effects of aberrant enzymatic activities found in skin of atopic dermatitis patients. The set-up is appropriate as a preliminary test to examine the effectiveness of new molecules or delivery-systems to counteract serine protease-mediated inflammatory processes prior to skin studies.