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Yolk@Shell Nanoarchitectures with Bimetallic Nanocores - Synthesis and Electrocatalytic Applications
(2016)
The spatial magnetic properties (Through Space NMR Shieldings - TSNMRS) of a number of Y-shaped structures possessing 4n+2 pi-electrons (i.a. the trimethylenemethane ions TMM2+, TMM2-, the guanidinium cation, substituted and hetero analogues) have been computed, visualized as Isochemical Shielding Surfaces (ICSS) of various size and direction, were examined subject to present Y-aromaticity and the results compared with energetic and geometric criteria obtained already. (C) 2016 Elsevier Ltd. All rights reserved.
In this study, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain carbon nanodots (CNDs) with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch and Tris-acetate-EDTA (TAE) buffer as carbon sources. Three kinds of CNDs are prepared using different sets of above mentioned starting materials. The as-synthesized CNDs: C-CND (starch only), N-CND 1 (starch in TAE) and N-CND 2 (TAE only) exhibit highly homogenous PL and are ready to use without need for further purification. The CNDs are stable over a long period of time (> 1 year) either in solution or as freeze-dried powder. Depending on starting material, CNDs with PL quantum yield (PLQY) ranging from less than 1% up to 28% are obtained. The influence of the precursor concentration, reaction time and type of additives on the optical properties (UV-Vis absorption, PL emission spectrum and PLQY) is carefully investigated, providing insight into the chemical processes that occur during CND formation. Remarkably, upon freeze-drying the initially brown CND-solution turns into a non-fluorescent white/slightly brown powder which recovers PL in aqueous solution and can potentially be applied as fluorescent marker in bio-imaging, as a reduction agent or as a photocatalyst.
In this study, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain carbon nanodots (CNDs) with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch and Tris-acetate-EDTA (TAE) buffer as carbon sources. Three kinds of CNDs are prepared using different sets of above mentioned starting materials. The as-synthesized CNDs: C-CND (starch only), N-CND 1 (starch in TAE) and N-CND 2 (TAE only) exhibit highly homogenous PL and are ready to use without need for further purification. The CNDs are stable over a long period of time (>1 year) either in solution or as freeze-dried powder. Depending on starting material, CNDs with PL quantum yield (PLQY) ranging from less than 1% up to 28% are obtained. The influence of the precursor concentration, reaction time and type of additives on the optical properties (UV-Vis absorption, PL emission spectrum and PLQY) is carefully investigated, providing insight into the chemical processes that occur during CND formation. Remarkably, upon freeze-drying the initially brown CND-solution turns into a non-fluorescent white/slightly brown powder which recovers PL in aqueous solution and can potentially be applied as fluorescent marker in bio-imaging, as a reduction agent or as a photocatalyst.
We characterize the wetting behavior of nano structured wrinkle and gradient wrinkle substrates. Different contact angles on both sides of a water droplet after deposition on a gradient sample induce the self-propelled motion of the liquid toward smaller wrinkle dimensions. The droplet motion is self-limited by the contact angles balancing out. Because of the correlation between droplet motion and contact angles, we investigate the wetting behavior of wrinkle substrates with constant dimensions (wavelengths of 400-1200 nm). Contact angles of water droplets on those substrates increase with increasing dimensions of the underlying substrate. The results are independent of the two measurement directions, parallel and perpendicular to the longitudinal axis of the nanostructure. The presented findings may be considered for designing microfluidic or related devices and initiate ideas for the development of further wrinkle applications.
WavePacket
(2016)
WavePacket is an open-source program package for the numerical simulation of quantum-mechanical dynamics. It can be used to solve time-independent or time-dependent linear Schrödinger and Liouville–von Neumann-equations in one or more dimensions. Also coupled equations can be treated, which allows to simulate molecular quantum dynamics beyond the Born–Oppenheimer approximation. Optionally accounting for the interaction with external electric fields within the semiclassical dipole approximation, WavePacket can be used to simulate experiments involving tailored light pulses in photo-induced physics or chemistry. The graphical capabilities allow visualization of quantum dynamics ‘on the fly’, including Wigner phase space representations. Being easy to use and highly versatile, WavePacket is well suited for the teaching of quantum mechanics as well as for research projects in atomic, molecular and optical physics or in physical or theoretical chemistry. The present Part I deals with the description of closed quantum systems in terms of Schrödinger equations. The emphasis is on discrete variable representations for spatial discretization as well as various techniques for temporal discretization. The upcoming Part II will focus on open quantum systems and dimension reduction; it also describes the codes for optimal control of quantum dynamics. The present work introduces the MATLAB version of WavePacket 5.2.1 which is hosted at the Sourceforge platform, where extensive Wiki-documentation as well as worked-out demonstration examples can be found.
Watching the Vibration and Cooling of Ultrathin Gold Nanotriangles by Ultrafast X-ray Diffraction
(2016)
We study the vibrations of ultrathin gold nanotriangles upon optical excitation of the electron gas by ultrafast X-ray diffraction. We quantitatively measure the strain evolution in these highly asymmetric nano-objects, providing a direct estimation of the amplitude and phase of the excited vibrational motion. The maximal strain value is well reproduced by calculations addressing pump absorption by the nanotriangles and their resulting thermal expansion. The amplitude and phase of the out-of-plane vibration mode with 3.6 ps period dominating the observed oscillations are related to two distinct excitation mechanisms. Electronic and phonon pressures impose stresses with different time dependences. The nanosecond relaxation of the expansion yields a direct temperature sensing of the nano-object. The presence of a thin organic molecular layer at the nanotriangle/substrate interfaces drastically reduces the thermal conductance to the substrate.
Sixteen new ionic liquids (ILs) with tetraethylammonium, 1-butyl-3-methylimidazolium, 3-methyl-1-octylimidazolium and tetrabutylphosphonium cations paired with 2-substituted 4,5-dicyanoimidazolate anions (substituent at C2 = methyl, trifluoromethyl, pentafluoroethyl, N,N′-dimethyl amino and nitro) have been synthesized and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The effects of cation and anion type and structure of the resulting ILs, including several room temperature ionic liquids (RTILs), are reflected in the crystallization, melting points and thermal decomposition of the ILs. ILs exhibited large liquid and crystallization ranges and formed glasses on cooling with glass transition temperatures in the range of −22 to −71 °C. We selected one of the newly designed ILs due to its bigger size, compared to the common conventional IL anion and high electron-withdrawing nitrile group leads to an overall stabilization anion that may stabilize the metal nanoparticles. Stable and better separated iron and silver nanoparticles are obtained by the decomposition of corresponding Fe2(CO)9 and AgPF6, respectively, under N2-atmosphere in newly designed nitrile functionalized 4,5-dicyanoimidazolate anion based IL. Very small and uniform size for Fe-nanoparticles of about 1.8 ± 0.6 nm were achieved without any additional stabilizers or capping molecules. Comparatively bigger size of Ag-nanoparticles was obtained through the reduction of AgPF6 by hydrogen gas. Additionally, the AgPF6 precursor was decomposed under microwave irradiation (MWI), fabricating nut-in-shell-like, that is, core-separated-from-shell Ag-nano-structures.
Sixteen new ionic liquids (ILs) with tetraethylammonium, 1-butyl-3-methylimidazolium, 3-methyl-1-octylimidazolium and tetrabutylphosphonium cations paired with 2-substituted 4,5-dicyanoimidazolate anions (substituent at C2 = methyl, trifluoromethyl, pentafluoroethyl, N,N′-dimethyl amino and nitro) have been synthesized and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The effects of cation and anion type and structure of the resulting ILs, including several room temperature ionic liquids (RTILs), are reflected in the crystallization, melting points and thermal decomposition of the ILs. ILs exhibited large liquid and crystallization ranges and formed glasses on cooling with glass transition temperatures in the range of −22 to −71 °C. We selected one of the newly designed ILs due to its bigger size, compared to the common conventional IL anion and high electron-withdrawing nitrile group leads to an overall stabilization anion that may stabilize the metal nanoparticles. Stable and better separated iron and silver nanoparticles are obtained by the decomposition of corresponding Fe2(CO)9 and AgPF6, respectively, under N2-atmosphere in newly designed nitrile functionalized 4,5-dicyanoimidazolate anion based IL. Very small and uniform size for Fe-nanoparticles of about 1.8 ± 0.6 nm were achieved without any additional stabilizers or capping molecules. Comparatively bigger size of Ag-nanoparticles was obtained through the reduction of AgPF6 by hydrogen gas. Additionally, the AgPF6 precursor was decomposed under microwave irradiation (MWI), fabricating nut-in-shell-like, that is, core-separated-from-shell Ag-nano-structures.
Inspired by the application of ultrasonic cavitation based mechanical force (CMF) to open small channels in natural soft materials (skin or tissue), it is explored whether an artificial polymer network can be created, in which shape-changes can be induced by CMF. This concept comprises an interconnected macroporous rhodium-phosphine (Rh-P) coordination polymer network, in which a CMF can reversibly dissociate the Rh-P microphases. In this way, the ligand exchange of Rh-P coordination bonds in the polymer network is accelerated, resulting in a topological rearrangement of molecular switches. This rearrangement of molecular switches enables the polymer network to release internal tension under ultrasound exposure, resulting in a CMF-induced shape-memory capability. The interconnected macroporous structure with thin pore walls is essential for allowing the CMF to effectively permeate throughout the polymer network. Potential applications of this CMF-induced shape-memory polymer can be mechanosensors or ultrasound controlled switches.
The synthesis and photophysical properties of two new FRET pairs based on coumarin as a donor and DBD dye as an acceptor are described. The introduction of a bromo atom dramatically increases the two-photon excitation (2PE) cross section providing a 2PE-FRET system, which is also suitable for 2PE-FLIM.
Due to the adsorption of biomolecules, the control of the biodistribution of nanoparticles is still one of the major challenges of nanomedicine. Poly(2-ethyl-2-oxazoline) (PEtOx) for surface modification of nanoparticles is applied and both protein adsorption and cellular uptake of PEtOxylated nanoparticles versus nanoparticles coated with poly(ethylene glycol) (PEG) and non-coated positively and negatively charged nanoparticles are compared. Therefore, fluorescent poly(organosiloxane) nanoparticles of 15 nm radius are synthesized, which are used as a scaffold for surface modification in a grafting onto approach. With multi-angle dynamic light scattering, asymmetrical flow field-flow fractionation, gel electrophoresis, and liquid chromatography-mass spectrometry, it is demonstrated that protein adsorption on PEtOxylated nanoparticles is extremely low, similar as on PEGylated nanoparticles. Moreover, quantitative microscopy reveals that PEtOxylation significantly reduces the non-specific cellular uptake, particularly by macrophage-like cells. Collectively, studies demonstrate that PEtOx is a very effective alternative to PEG for stealth modification of the surface of nanoparticles.
Total protein concentration (TPC) is a key parameter in many biochemical experiments and its quantification is often necessary for isolation, separation, and analysis of proteins. A sensitive and rapid nanobead-based TPC quantification assay based on Forster Resonance Energy Transfer (FRET) has been developed. A new, highly luminescent Tb(III) complex has been synthesised and applied as donor in this FRET assay with an organic dye (Cy5) as acceptor. FRET-induced changes in luminescence have been investigated both at donor and acceptor emission wavelength using time-resolved luminescence spectroscopy with time-gated detection. In the assay, the Tb(III) complex and fine-tuned polyglycidyl methacrylate (PGMA) nanobeads ensure that an improvement in sensitivity and background reduction is achieved. Using 40 nm large PGMA nanobeads loaded with the Tb(III) complex, it is possible to determine TPC down to 50 ng mL(-1) in just 10 minutes. Through specific assay components the sensitivity has been improved when compared to existing nanobead-based assays and to currently known commercial methods. Additionally, the assay is relatively insensitive to the presence of contaminants, such as non-ionic detergents commonly found in biological samples. Due to no need for any centrifugal steps, this mix-and-measure bioassay can easily be implemented into routine TPC quantification protocols in biochemical laboratories.
Responsive inverse opal hydrogels functionalized by boroxole moieties were synthesized and explored as sensor platforms for various low molar mass as well as polymeric diols and polyols, including saccharides, glycopolymers and catechols, by exploiting the diol induced modulation of their structural color. The underlying thermoresponsive water-soluble copolymers and hydrogels exhibit a coil-to-globule or volume phase transition, respectively, of the LCST-type. They were prepared from oligoethylene oxide methacrylate (macro)monomers and functionalized via copolymerization to bear benzoboroxole moieties. The resulting copolymers represent weak polyacids, which can bind specifically to diols within an appropriate pH window. Due to the resulting modulation of the overall hydrophilicity of the systems and the consequent shift of their phase transition temperature, the usefulness of such systems for indicating the presence of catechols, saccharides, and glycopolymers was studied, exploiting the diol/polyol induced shifts of the soluble polymers’ cloud point, or the induced changes of the hydrogels’ swelling. In particular, the increased acidity of benzoboroxoles compared to standard phenylboronic acids allowed performing the studies in PBS buffer (phosphate buffered saline) at the physiologically relevant pH of 7.4. The inverse opals constructed of these thermo- and analyte-responsive hydrogels enabled following the binding of specific diols by the induced shift of the optical stop band. Their highly porous structure enabled the facile and specific optical detection of not only low molar mass but also of high molar mass diol/polyol analytes such as glycopolymers. Accordingly, such thermoresponsive inverse opal systems functionalized with recognition units represent attractive and promising platforms for the facile sensing of even rather big analytes by simple optical means, or even by the bare eye.
The authors report on the fabrication of a thermoresponsive biosensor for the amperometric detection of glucose. Screen printed electrodes with heatable gold working electrodes were modified by a thermoresponsive statistical copolymer [polymer I: poly(omega-ethoxytriethylenglycol methacrylate-omega-3-(N,N-dimethyl-N-2-methacryloyloxyethyl ammonio) propanesulfonate-co-omega-butoxydiethylenglycol methacrylate-co-2-(4-benzoyl-phenoxy)ethyl methacrylate)] with a lower critical solution temperature of around 28 degrees C in aqueous solution via electrochemically induced codeposition with a pH-responsive redox-polymer [polymer II: poly(glycidyl methacrylate-co-allyl methacrylate-co-poly(ethylene glycol) methacrylate-co-butyl acrylate-co-2-(dimethylamino) ethyl methacrylate)-[Os(bpy)(2)(4-(((2-(2-(2-aminoethoxy) ethoxy) ethyl) amino) methyl)-N,N-dimethylpicolinamide)](2+)] and pyrroloquinoline quinone-soluble glucose dehydrogenase acting as biological recognition element. Polymer II bears covalently bound Os-complexes that act as redox mediators for shuttling electrons between the enzyme and the electrode surface. Polymer I acts as a temperature triggered immobilization matrix. Probing the catalytic current as a function of the working electrode temperature shows that the activity of the biosensor is dramatically reduced above the phase transition temperature of polymer I. Thus, the local modulation of the temperature at the interphase between the electrode and the bioactive layer allows switching the biosensor from an on-to an off-state without heating of the surrounding analyte solution. (C) 2015 American Vacuum Society.
A series of hydrophobically end-capped linear triblock copolymers as well as of three-arm and four-arm star block copolymers was synthesized in a one-pot procedure from N,N-dimethylacrylamide (DMA) and N, N-diethylacrylamide (DEA). The sequential reversible addition-fragmentation chain transfer (RAFT) polymerization of these monomers via the R-approach using bi-, tri- and tetrafunctional chain transfer agents (CrAs) bearing hydrophobic dodecyl moieties proceeded in a well-controlled manner up to almost quantitative conversion. Polymers with molar masses up to 150 kDa, narrow molar mass distribution (PDI <= 1.3) and high end group functionality were obtained, which are thermoresponsive in aqueous solution showing a LCST (lower critical solution temperature) transition. The temperature-dependent associative behavior of the polymers was examined using turbidimetry, static and dynamic light scattering (SLS, DLS), and small angle neutron scattering (SANS) for structural analysis. At 25 degrees C, the polymers form weak transient networks, and rather small hydrophobic domains are already present for polymer concentrations of 5 wt%. However, when heating above the LCST transition (35-40 degrees C) of the PDEA blocks, the enhanced formation of hydrophobic domains is observed by means of light and neutron scattering. These domains have a size of about 12-15 nm and must be effectively physically cross-linked as they induce high viscosity for the more concentrated samples. SANS shows that these domains are ordered as evidenced by the appearance of a correlation peak. The copolymer architecture affects in particular the extent of ordering as the four-arm star block copolymer shows much more repulsive interactions compared to the analogous copolymers with a lower number of arms. (C) 2016 Elsevier Ltd. All rights reserved.
Block copolypeptoids comprising a thermosensitive, crystallizable poly(N-(n-propyl)glycine) block and a watersoluble poly(N-methylglycine) block, P70My (y = 23, 42, 76, 153, and 290), were synthesized bY ring-opening polymerization of the corresponding N-alkylglycine N-carboxyanhydrides (NCAs) and examined according to their thermo-induced aggregation and crystallization in water by turbidimetty, micro-differential scanning calorimetry (micro-DSC); cryogenic scanning electron microscopy (cryo-SEM), analytical ultracentrifugation (AUC), and static light scattering (SLS). At a temperature above the cloud point temperature, the initially formed micellar aggregates started to crystallize and grow into larger complex assemblies of about 100-500 nm, exhibiting flower-like (P70M23), ellipsoidal (P70M42 and P70M72) or irregular shapes (P70M153 and.P70M290).
The interplay of an enzyme with a multiblock copolymer PDLCL containing two segments of different hydrophilicity and degradability is explored in thin films at the air-water interface. The enzymatic degradation was studied in homogenous Langmuir monolayers, which are formed when containing more than 40 wt% oligo(epsilon-caprolactone) (OCL). Enzymatic degradation rates were significantly reduced with increasing content of hydrophobic oligo(omega-pentadecalactone) (OPDL). The apparent deceleration of the enzymatic process is caused by smaller portion of water-soluble degradation fragments formed from degradable OCL fragments. Beside the film degradation, a second competing process occurs after adding lipase from Pseudomonas cepacia into the subphase, namely the enrichment of the lipase molecules in the polymeric monolayer. The incorporation of the lipase into the Langmuir film is experimentally revealed by concurrent surface area enlargement and by Brewster angle microscopy (BAM). Aside from the ability to provide information about the degradation behavior of polymers, the Langmuir monolayer degradation (LMD) approach enables to investigate polymer-enzyme interactions for non-degradable polymers. (C) 2016 Elsevier Ltd. All rights reserved.