Refine
Has Fulltext
- yes (226)
Year of publication
Document Type
- Postprint (226) (remove)
Language
- English (226) (remove)
Keywords
- LIBS (4)
- anomalous diffusion (4)
- living cells (4)
- nanoparticles (4)
- DNA origami (3)
- Diodenlaserspektroskopie (3)
- Fluoreszenz-Resonanz-Energie-Transfer (3)
- Immunoassay (3)
- Kohlendioxid (3)
- biomaterials (3)
Institute
- Institut für Chemie (226) (remove)
Arsenic-containing hydrocarbons are one group of fat-soluble organic arsenic compounds (arsenolipids) found in marine fish and other seafood. A risk assessment of arsenolipids is urgently needed, but has not been possible because of the total lack of toxicological data. In this study the cellular toxicity of three arsenic-containing hydrocarbons was investigated in cultured human bladder (UROtsa) and liver (HepG2) cells. Cytotoxicity of the arsenic-containing hydrocarbons was comparable to that of arsenite, which was applied as the toxic reference arsenical. A large cellular accumulation of arsenic, as measured by ICP-MS/MS, was observed after incubation of both cell lines with the arsenolipids. Moreover, the toxic mode of action shown by the three arsenic-containing hydrocarbons seemed to differ from that observed for arsenite. Evidence suggests that the high cytotoxic potential of the lipophilic arsenicals results from a decrease in the cellular energy level. This first in vitro based risk assessment cannot exclude a risk to human health related to the presence of arsenolipids in seafood, and indicates the urgent need for further toxicity studies in experimental animals to fully assess this possible risk.
We study the thermal Markovian diffusion of tracer particles in a 2D medium with spatially varying diffusivity D(r), mimicking recently measured, heterogeneous maps of the apparent diffusion coefficient in biological cells. For this heterogeneous diffusion process (HDP) we analyse the mean squared displacement (MSD) of the tracer particles, the time averaged MSD, the spatial probability density function, and the first passage time dynamics from the cell boundary to the nucleus. Moreover we examine the non-ergodic properties of this process which are important for the correct physical interpretation of time averages of observables obtained from single particle tracking experiments. From extensive computer simulations of the 2D stochastic Langevin equation we present an in-depth study of this HDP. In particular, we find that the MSDs along the radial and azimuthal directions in a circular domain obey anomalous and Brownian scaling, respectively. We demonstrate that the time averaged MSD stays linear as a function of the lag time and the system thus reveals a weak ergodicity breaking. Our results will enable one to rationalise the diffusive motion of larger tracer particles such as viruses or submicron beads in biological cells.
On the role of fluoro-substituted nucleosides in DNA radiosensitization for tumor radiation therapy
(2014)
Gemcitabine (2′,2′-difluorocytidine) is a well-known radiosensitizer routinely applied in concomitant chemoradiotherapy. During irradiation of biological media with high-energy radiation secondary low-energy (<10 eV) electrons are produced that can directly induce chemical bond breakage in DNA by dissociative electron attachment (DEA). Here, we investigate and compare DEA to the three molecules 2′-deoxycytidine, 2′-deoxy-5-fluorocytidine, and gemcitabine. Fluorination at specific molecular sites, i.e., nucleobase or sugar moiety, is found to control electron attachment and subsequent dissociation pathways. The presence of two fluorine atoms at the sugar ring results in more efficient electron attachment to the sugar moiety and subsequent bond cleavage. For the formation of the dehydrogenated nucleobase anion, we obtain an enhancement factor of 2.8 upon fluorination of the sugar, whereas the enhancement factor is 5.5 when the nucleobase is fluorinated. The observed fragmentation reactions suggest enhanced DNA strand breakage induced by secondary electrons when gemcitabine is incorporated into DNA.
One of the main issues with the use of nickel titanium alloy (NiTi) implants in cardiovascular implants (stents) is that these devices must be of very high quality in order to avoid subsequent operations due to failing stents. For small stents with diameters below ca. 2 mm, however, stent characterization is not straightforward. One of the main problems is that there are virtually no methods to characterize the interior of the NiTi tubes used for fabrication of these tiny stents. The current paper reports on a robust hybrid actuator for the characterization of NiTi tubes prior to stent fabrication. The method is based on a polymer/hydrogel/magnetic nanoparticle hybrid material and allows for the determination of the inner diameter at virtually all places in the raw NiTi tubes. Knowledge of the inner structure of the raw NiTi tubes is crucial to avoid regions that are not hollow or regions that are likely to fail due to defects inside the raw tube. The actuator enables close contact of a magnetic polymer film with the inner NiTi tube surface. The magnetic signal can be detected from outside and be used for a direct mapping of the tube interior. As a result, it is possible to detect critical regions prior to expensive and slow stent fabrication processes.
Injection of a mixture of HAuCl4 and cellulose dissolved in the ionic liquid (IL) 1-butyl-3-methylimidazolium chloride [Bmim]Cl into aqueous NaBH4 leads to colloidal gold nanoparticle/cellulose hybrid precipitates. This process is a model example for a very simple and generic approach towards (noble) metal/cellulose hybrids, which could find applications in sensing, sterile filtration, or as biomaterials.
From the dichloromethane-methanol (1:1) extract of the seed pods of Derris trifoliata, a new flavanone derivative (S)-lupinifolin 4´-methyl ether was isolated. In addition, the known flavonoids lupinifolin and rotenone were identified. The structures were determined on the basis of spectroscopic evidence. Lupinfolin showed moderate in vitro antiplasmodial activity against the D6 (chloroquine-sensitive) and W2 (chloroquineresistant) strains of Plasmodium falciparum. The different parts of this plant showed larvicidal activities against Aedes aegypti and rotenoids were identified as the active principles.
From the seedpods of Tephrosia elata, a new β-hydroxydihydrochalcone named (S)-elatadihydrochalcone was isolated. In addition, the known flavonoids obovatachalcone, obovatin, obovatin methyl ether and deguelin were identified. The structures were determined on the basis of spectroscopic evidence. The crude extract and the flavonoids obtained from the seedpods of this plant showed antiplasmodial activities. The literature NMR data on β-hydroxydihydrochalcones is reviewed and the identity of some of the compounds assigned β-hydroxydihydrochalcone skeleton is questioned.
BACKGROUND: There is an increased need to replace materials derived from fossil sources by renewables. Sugar-cane derived carbohydrates are very abundant in Brazil and are the cheapest sugars available in the market, with more than 400 million tons of sugarcane processed in the year 2007. The objective of this work was to study the preparation of sugar acrylates from free sugars and free acrylic acid, thus avoiding the previous preparation of protected sugar derivatives, such as glycosides, or activated acrylates, such as vinyl acrylate. RESULTS: Lipase catalyzed esterification of three mono- and two disaccharides with acrylic acid, in the presence or absence of molecular sieves was investigated. The reactions were monitored by high-performance liquid chromatography (HPLC) and the products were analyzed by matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry. The main products are mono- and diacrylates, while higher esters are formed as minor products. The highest conversion to sugar acrylates was observed for the D-glucose and D-fructose, followed by D-xylose and D-maltose. Molecular sieves had no pronounced effect on the conversion CONCLUSIONS: A feasible method is described to produce and to characterize sugar acrylates, including those containing more than two acrylate groups. The process for production of these higher esters could potentially be optimized further to produce molecules for cross-linking in acrylate polymerization and other applications. The direct enzymatic esterification of free carbohydrates with acrylic acid is unprecedented.
Growth of phytopathogenic fungi in the presence of partially acetylated chitooligosaccharides
(2008)
Four phytopathogenic fungi were cultivated up to six days in media containing chitooligosaccharide mixtures differing in average DP and FA. The three different mixtures were named Q3 (which contained oligosaccharides ofDP2–DP10, withDP2–DP7 asmain components), Q2 (which contained oligosaccharides of DP2–DP12, with DP2–DP10 as main components) and Q1 (which derived from Q2 and contained oligomers of DP5–DP8 with hexamer and a heptamer as the main components). The novel aspect of this work is the description of the effect of mixtures of oligosaccharides with different and known composition on fungal growth rates. The growth rate of Alternaria alternata and Rhizopus stolonifer was initially inhibited by Q3 and Q2 at higher concentrations. Q1 had a growth stimulating effect on these two fungi. Growth of Botrytis cinerea was inhibited by Q3 and Q2, while Q1 had no effect on the growth of this fungus. Growth of Penicillium expansum was only slightly inhibited by higher concentrations of sample Q3, while Q2 and Q1 had no effect. The inhibition of growth rates or their resistance toward chitooligosaccharides correlated with the absence or presence of chitinolytic enzymes in the culture media, respectively.
From the roots of the African plant Bulbine frutescens (Asphodelaceae), two unprecedented novel dimeric phenylanthraquinones, named joziknipholones A and B, possessing axial and centrochirality, were isolated, together with six known compounds. Structural elucidation of the new metabolites was achieved by spectroscopic and chiroptical methods, by reductive cleavage of the central bond between the monomeric phenylanthraquinone and -anthrone portions with sodium dithionite, and by quantum chemical CD calculations. Based on the recently revised absolute axial configuration of the parent phenylanthraquinones, knipholone and knipholone anthrone, the new dimers were attributed to possess the P-configuration (i.e., with the acetyl portions below the anthraquinone plane) at both axes in the case of joziknipholone A, whereas in joziknipholone B, the knipholone part was found to be M-configured. Joziknipholones A and B are active against the chloroquine resistant strain K1 of the malaria pathogen, Plasmodium falciparum, and show moderate activity against murine leukemic lymphoma L5178y cells.
We present an approach to the correlated dynamics of many-electron systems. We show, that the twoelectron reduced density matrix (2RDM) can provide a suitable description of the real time evolution of a system. To achieve this, the hierarchy of equations of motion must be truncated in a practical way. Also, the computational effort, given that the 2RDM is represented by products of two-electron determinants, is discussed, and numerical model calculations are presented.
The piezoelectric and pyroelectric properties of oriented films possessing dipole moments are increasingly being used in pressure, acoustic, thermal and optical devices. The performance of these devices in many applications may be enhanced by thin-film technology.The developing Langmuir-Blodgett thin-film deposition technique offers the opportunity to obtain highly oriented and uniform organic-based films in the 10–5000 nm thickness range. Special techniques must be used, however, to assemble these molecules in such a way as to result in polar multilayer films. Several possible deposition techniques are investigated, with one resulting in a polar and pyroelectric film about 50 nm thick.
The molecular packing and spatial correlations of two isomeric zwitterionic polymethacrylates and one polyacrylate analog are studied by means of X-ray analysis and conformational calculations. The analysis of the correlation functions and density distribution profiles suggest a double-layered molecular packing which is discussed for the three polymers investigated, with respect to their different chemical structures. Whereas the zwitterionic polymethacrylates studied exhibit liquid-like short-range order, the polyacrylate analog exhibits an ordered double-layered superstructure.
A variety of polymerizable lipids containing a hydrophilic spacer group between the reactive group and the main amphiphilic structure have been synthesized. They were investigated in monolayers, liposomes, and multilayers. When the spacer concept was used, efficient decoupling of the motions of the polymeric chain and the amphiphilic side groups is achieved. Thus, the often found loss of the important fluid phases by polymerization is avoided. Polymeric monolayers of the spacer lipid, prepared either by polymerization in the monolayer or by spreading of prepolymerized lipid, exhibit nearly identical surface pressure-area diagrams. Most distinctly, the successful decoupling of the motions of the polymer main chain and the membrane forming amphiphilic side groups is demonstrated by the self-organization of bulk polymerized spacer lipids to polymeric liposomes. In addition, spacer lipids are able to build polymeric Langmuir-Blodgett multilayers. The decoupling of the polymer main chain and the membrane-forming amphiphilic side groups enables the deposition of already polymeric monolayers onto supports to form defined multilayers. If, alternatively, monomeric monolayers are deposited and polymerized on the support, defects in the layers due to structural changes during the polymerization are avoided by the flexible spacer group.
Dielectric spectroscopy is employed to analyze the molecular dynamics and the charge transport in mixtures of zwitterionic polymers of the type poly{3 [N(-methacryloyloxyalkyl)] N, [N-dimethylammonio propanesulfonate] with sodium iodide in the frequency range of 10²Hz-10(up)7 Hz and in the temperature range of 110 K-400 K. The amount of inorganic salt added varies from 0-200 mol-% relative to the number of zwitterionic groups present in the polymer, contributing strongly to the conductivity. One relaxation process is observed whose relaxation rate depends strongly on the length of the aliphatic spacer between the polymethacrylate main chain and the zwitterionic group. Exhibiting an Arrhenius-like temperature depence with activation energy EA = 47 KJ/mol, this relaxation process is assigned to fluctuation of the quaternary ammonium groups in the side chains. At higher temperatures, the dielectric properties and the conductivity are primarily dominated by the mobile inorganic ions: conductivity strongly depends on the salt concentration, showing a pronounced electrode polarization effect. The frequency and salt concentration, dependences of the conductivity can be quantitatively described as hopping of charge carriers being subject to spatially randomly varying energy barriers. For the low-frequency regime and for the critical frequency marking the onset of the conductivity's dispersion, the Barton-Nakajima-Namikawa (BNN) relationship is fulfilled.
Several zwitterionic polymers were prepared by radical homopolymerization of surfactant monomers which bear diallyl, diene or vinylcyclopropane moieties. These polymer systems were complemented by alternating copolymers of appropriate zwitterionic vinyl compounds. Thus, polymers with reduced (as compared with simple vinylic homopolymers, or statistical copolymers) and well defined density of surfactant side groups are obtained. The solubilities found for these polymers are dominated by polymer geometry rather than by the balance of hydrophilic and hydrophobic fragments, thus corroborating a main-chain spacer model proposed recently. All water-soluble polymers exhibit characteristic features of classical polysoaps, as shown by surface tension measurements and by solubilization of hydrophobic dyes. In contrast, the water-insoluble copolymers are capable to form stable monolayers at the air-water interface.
This article describes recent achievements in the field of micellar polymers, or polysoaps. Taking advantage of zwitterionic model polymers, systematic variations of the molecular architecture have provided an improved understanding of the relationship between the molecular structure of the polymers and their key properties such as surface activity and solubilization capacity. Useful rules are established, which take into account much of the previous data in the literature.