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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.
In this study, the stable conformers of neutral anserine were searched by molecular dynamics simulations and energy minimization calculations using the MM2 force field. Thermochemical calculations at B3LYP/6-31G(d) level of theory followed these preliminary calculations. The results confirmed that neutral anserine has quite a flexible structure and many stable gauche and trans conformers at room temperature. Nevertheless, two are considerably more favourable in energy than the others and expected to dominate the gas-phase and matrix IR spectra of the molecule. The corresponding structural and vibrational spectral data for these two conformers of neutral anserine, whose relative stabilities were also examined by high-accuracy energy calculations carried out using G3MP2B3 method, and for the most stable conformer of anserine in zwitterion form were calculated at B3LYP/6-311++G(d,p) level of theory. The calculated harmonic force constants were refined using the Scaled Quantum Mechanical Force Field (SQM-FF) method and then used to produce the refined wavenumbers, potential energy distributions (PEDs) and IR and Raman intensities. These refined data together with the scaled harmonic wavenumbers obtained using another method, Dual Scale factors (DS), enabled us to correctly analyse the observed IR and Raman spectra of anserine and revealed the effects of conformation and zwitterionic tautomerism on its structural and vibrational spectral data. (C) 2016 Elsevier B.V. All rights reserved.
Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several “onium” cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g|| and gK) of the tensors could be determined and information on the structural changes in the [CuBr4]2- anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids.
Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several "onium" cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g|| and g(perpendicular to)) of the tensors could be determined and information on the structural changes in the [CuBr4](2-) anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids.
alpha-Methylene-gamma-butyrolactone and alpha-methylene-gamma-valerolactone undergo Pd-catalyzed Matsuda-Heck couplings with arene diazonium salts to alpha-benzyl butenolides or pentenolides, respectively, or to alpha-benzylidene lactones. The observed regioselectivity is strongly ring size dependent, with six-membered rings giving exclusively alpha-benzyl pentenolides, whereas the five-membered alpha-methylene lactone reacts to mixtures of regioisomers with a high proportion of (E)-alpha-benzylidene-gamma-butyrolactones. DFT calculations suggest that the reasons for these differences are not thermodynamic but kinetic in nature. The relative energies of the conformers of the Pd sigma-complexes resulting from insertion into the Pd-aryl bond were correlated with the dihedral angles between Pd and endo-beta-H. This correlation revealed that in the case of the six-membered lactone an energetically favorable conformer adopts a nearly synperiplanar Pd/endo-beta-H arrangement, whereas for the analogous Pd sigma-complex of the five-membered lactone the smallest Pd/endo-beta-H dihedral angle is observed for a conformer with a comparatively high potential energy. The optimized conditions for Matsuda-Heck arylations of exo-methylene lactones were eventually applied to the synthesis of the natural product anemarcoumarin A.
Polysarcosine (M-n = 3650-20 000 g mol(-1), D similar to 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator.
Polysarcosine (Mn = 3650–20 000 g mol−1, Đ ∼ 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator.
Allyl, dimethylallyl, crotyl, and prenyl ethers of various aromatic ortho-hydroxy carbonyl compounds undergo a tandem sequence of Claisen rearrangement, carbonyl olefination, and cyclization upon microwave irradiation in the presence of a stabilized ylide. The products are multiply substituted 6- or 8-allylated or prenylated coumarins (2H-chromen-2-ones).
A convenient and general synthesis of 2-thiocarbohydrates via cerium ammonium nitrate oxidation of the thiocyanate ion is described. Radical addition to glycals proceeds with excellent regio- and good stereoselectivities in only one step, deprotection affords water-soluble 2-thio saccharides. Binding studies to Con A have been performed by isothermal titration calorimetry (ITC) and saturation transfer difference (STD) NMR spectroscopy. The 2-thiomannose derivative binds even stronger to Con A than the natural substrate, offering opportunities for new lectin or enzyme inhibitors.
Through the reactions of 1- or 2-naphthol and 4,5-dihydro-3H-benz[c]azepine or 6,7-dihydrothieno[3,2-c]pyridine, new aminonaphthol derivatives were prepared. The syntheses were extended by using N-containing naphthol analogues such as 5-hydroxyisoquinoline and 6-hydroxyquinoline. The ring closures of the novel bifunctional compounds were also achieved, resulting in new naphth[2,1-e][1,3]oxazines, naphth[1,2-e][1,3]oxazines, isoquinolino[5,6-e][1,3]oxazines and quinolino[5,6-e][1,3]oxazines. H-1 NMR spectra of the target heterocycles 16, 20 and 21 were sufficiently resolved to indentify the present stereochemistry; therefore, beside computed structures, spatial experimental (dipolar coupling-NOE) and computed (ring current effect of the naphthyl moiety-TSNMRS) NMR studies were employed. The studied heterocycles exist exclusively as S(14b),R(N), R(14b),S(N), and S(16b)S(N) isomers, respectively. The flexible moieties of the studied compounds prefer. (C) 2016 Elsevier Ltd. All rights reserved.
Fluorescent molecular probes for metal ions have a raft of potential applications in chemistry and biomedicine. We report the synthesis and photophysical characterisation of 1,8-disubstituted-cyclam/naphthalimide conjugates and their zinc complexes. An efficient synthesis of 1,8-bis-(2-azidoethyl)cyclam has been developed and used to prepare 1,8-disubstituted triazolyl-cyclam systems, in which the pendant group is connected to triazole C4. UV/Vis and fluorescence emission spectra, zinc binding experiments, fluorescence quantum yield and lifetime measurements and pH titrations of the resultant bis-naphthalimide ligand elucidate a complex pattern of photophysical behaviour. Important differences arise from the inclusion of two fluorophores in the one probe and from the variation of triazole substitution pattern (dye at C4 vs. N1). Introducing a second fluorophore greatly extends fluorescence lifetimes, whereas the altered substitution pattern at the cyclam amines exerts a major influence on fluorescence output and metal binding. Crystal structures of two key zinc complexes evidence variations in triazole coordination that mirror the solution-phase behaviour of these systems.
Synchrotron-radiation XPS analysis of ultra-thin silane films: Specifying the organic silicon
(2016)
The analysis of chemical and elemental in-depth variations in ultra-thin organic layers with thicknesses below 5 nm is very challenging. Energy- and angle-resolved XPS (ER/AR-XPS) opens up the possibility for non-destructive chemical ultra-shallow depth profiling of the outermost surface layer of ultra-thin organic films due to its exceptional surface sensitivity. For common organic materials a reliable chemical in-depth analysis with a lower limit of the XPS information depth z(95) of about 1 nm can be performed. As a proof-of-principle example with relevance for industrial applications the ER/AR-XPS analysis of different organic monolayers made of amino- or benzamidosilane molecules on silicon oxide surfaces is presented. It is demonstrated how to use the Si 2p core-level region to non-destructively depth-profile the organic (silane monolayer) - inorganic (SiO2/Si) interface and how to quantify Si species, ranging from elemental silicon over native silicon oxide to the silane itself. The main advantage of the applied ER/AR-XPS method is the improved specification of organic from inorganic silicon components in Si 2p core-level spectra with exceptional low uncertainties compared to conventional laboratory XPS. (C) 2015 Elsevier B.V. All rights reserved.
It has long been appreciated that material chemistry and topology profoundly affect cell adhesion and migration. Here, aqueous poly(N- isopropyl acrylamide) nanogels are designed, synthesized and printed in form of colloidal arrays on glass substrates using wrinkled polydimethylsiloxane templates. Using low-temperature plasma treatment, nanogels are chemically grafted onto glass supports thus leading to highly stable nanogel layers in cell culture media. Liquid cell atomic force microscopy investigations show that surface-grafted nanogels retain their swelling behavior in aqueous media and that extracellular matrix protein coating do not alter their stability and topography. It is demonstrated that surface-grafted nanogels could serve as novel substrates for the analysis of cell adhesion and migration. Nanogels influence size, speed, and dynamics of focal adhesions and cell motility forcing cells to move along highly directional trajectories. Moreover, modulation of nanogel state or spacing serves as an effective tool for regulation of cell motility. It is suggested that nanogel arrays deposited on solid surfaces could be used to provide a precise and tunable system to understand and control cell migration. Additionally, such nanogel arrays will contribute to the development of implantable systems aimed at supporting and enhancing cell migration during, for instance, wound healing and tissue regeneration.
The extracellular matrix (ECM) is a nano-structured, highly complex hydrogel, in which the macromolecules are organized primarily by non-covalent interactions. Here, in a biomimetic approach, the decorin-derived collagen-binding peptide LSELRLHNN was grafted to hyaluronic acid (HA) in order to enable the formation of a supramolecular hydrogel network together with collagen. The storage modulus of a mixture of collagen and HA was increased by more than one order of magnitude (G′ = 157 Pa) in the presence of the HA-grafted peptide compared to a mixture of collagen and HA (G′ = 6 Pa). The collagen fibril diameter was decreased, as quantified using electron microscopy, in the presence of the HA-grafted peptide. Here, the peptide mimicked the function of decorin by spatially organizing collagen. The advantage of this approach is that the non-covalent crosslinks between collagen molecules and the HA chains created by the peptide form a reversible and dynamic hydrogel, which could be employed for a diverse range of applications in regenerative medicine.
Statement of Significance
Biopolymers of the extracellular matrix (ECM) like collagen or hyaluronan are attractive starting materials for biomaterials. While in biomaterial science covalent crosslinking is often employed, in the native ECM, stabilization and macromolecular organization is primarily based on non-covalent interactions, which allows dynamic changes of the materials. Here, we show that collagen-binding peptides, derived from the small proteoglycan decorin, grafted to hyaluronic acid enable supramolecular stabilization of collagen hydrogels. These hydrogels have storage moduli more than one order of magnitude higher than mixtures of collagen and hyaluronic acid. Furthermore, the peptide supported the structural organization of collagen. Such hydrogels could be employed for a diverse range of applications in regenerative medicine. Furthermore, the rational design helps in the understanding ECM structuring.
Arene diazonium salts undergo Matsuda-Heck reactions with vinylsulfonates and -sulfonamides to give styrylsulfonic acid derivatives in high to excellent yields and with high to excellent selectivities. By quantifying the evolution of nitrogen over time in a gas-meter apparatus, the reactivities of ethylvinylsulfonate and the benchmark olefin methyl acrylate were compared for an electron-rich and an -deficient arene diazonium salt. Tertiary sulfonamides react in Matsuda-Heck couplings with high conversions, but require long reaction times, which prevents the determination of kinetic data through the measurement of nitrogen evolution. Secondary sulfonamides were found to be unreactive. From these results, the following order of reactivity could be deduced: H2C=CHCO2Me > H2C=CHSO2OEt > H2C=CHSO2N(Me)Bn >> H2C=CHSO2NHBn. Through the Matsuda-Heck coupling of 5-indolyldiazonium salt and a tertiary vinylsulfonamide, the synthesis of the C-5-substituted indole part of the antimigraine drug naratriptan was accomplished in high yield.
An extended member of the isoreticular family of metal-imidazolate framework structures, IFP-6 (IFP=imidazolate framework Potsdam), based on cadmium metal and an in situ functionalized 2-methylimidazolate-4-amide-5-imidate linker is reported. A porous 3D framework with 1D hexagonal channels with accessible pore windows of 0.52nm has been synthesized by using an ionic liquid (IL) linker precursor. IFP-6 shows significant gas uptake capacity only for CO2 and CH4 at elevated pressure, whereas it does not adsorb N-2, H-2, and CH4 under atmospheric conditions. IFP-6 is assumed to deteriorate at the outside of the material during the activation process. This closing of the metal-organic framework (MOF) pores is proven by positron annihilation lifetime spectroscopy (PALS), which revealed inherent crystal defects. PALS results support the conservation of the inner pores of IFP-6. IFP-6 has also been successfully loaded with luminescent trivalent lanthanide ions (Ln(III)=Tb, Eu, and Sm) in a bottom-up one-pot reaction through the in situ generation of the linker ligand and in situ incorporation of photoluminescent Ln ions into the constituting network. The results of photoluminescence investigations and powder XRD provide evidence that the Ln ions are not doped as connectivity centers into the frameworks, but are instead located within the pores of the MOFs. Under UV light irradiation, Tb@IFP-6 and Eu@IFP-6 ((exc)=365nm) exhibit observable emission changes to a greenish and reddish color, respectively, as a result of strong Ln 4f emissions.
Cryogenic transmission electron microscopy (cryo-TEM) studies suggest that TTBC molecules self-assemble in aqueous solution to form single-walled tubes with a diameter of about 35 A. In order to reveal the arrangement and mutual orientations of the individual molecules in the tube, we combine information from crystal structure data of this dye with a calculation of linear absorbance and linear dichroism spectra and molecular dynamics simulations. We start with wrapping crystal planes in different directions to obtain tubes of suitable diameter. This set of tube models is evaluated by comparing the resulting optical spectra with experimental data. The tubes that can explain the spectra are investigated further by molecular dynamics simulations, including explicit solvent molecules. From the trajectories of the most stable tube models, the short-range ordering of the dye molecules is extracted and the optimization of the structure is iteratively completed. The final structural model is a tube of rings with 6-fold rotational symmetry, where neighboring rings are rotated by 30 and the-transition dipole moments of the chromophores form an angle of 74 with respect to the symmetry axis of the tube. This model is in agreement with cryo-TEM images and can explain the optical spectra, consisting of a sharp red-shifted J-band that is polarized parallel to to the symmetry axis of the tube and a broad blue-shifted H-band polarized perpendicular to this axis. The general structure of the homogeneous spectrum of this hybrid HJ-aggregate is described by an analytical model that explains the difference in redistribution of oscillator strength inside the vibrational manifolds of the J- and H-bands and the relative intensities and excitation energies of those bands. In addition to the-particular system investigated here, the present methodology can be expected to aid the structure prediction for a wide range of self-assembled dye aggregates.
In the reconstruction and regeneration of bone tissue, a primary goal is to initiate bone growth and to stabilize the surrounding bone. In this regard, a potentially useful component in biomaterials for bone tissue engineering is strontium, which acts as cationic active agent, triggering certain intracellular pathways and acting as so called dual action bone agent which inhibits bone resorption while stimulating bone regeneration. In this study we established a novel processing for the foaming of a polymer (poly-epsilon-caprolactone) and simultaneous chemical reaction of a mixture of calcium and strontium hydroxides to the respective carbonates using supercritical carbon dioxide. The resultant porous composite scaffold was optimized in composition and strontium content and was characterized via different spectroscopic (infrared and Raman spectroscopy, energy dispersive X-ray spectroscopy), imaging (SEM, mu CT), mechanical testing and in vitro methods (fluorescence vital staining, MTT-assay). As a result, the composite scaffold showed good in vitro biocompatibility with partly open pore structure and the expected chemistry. First mechanical testing results indicate sufficient mechanical stability to support future in vivo applications. (C) 2016 Elsevier B.V. All rights reserved.
Polyelectrolyte multilayers (PEMs) with stratification of the internal structure were assembled from statistical amphiphilic copolyelectrolytes of opposite charges. These polyelectrolytes organize in aqueous solutions into micellar structures with fluoroalkyl and aromatic nanodomains, respectively, that were also preserved after deposition as thin films via layer-by-layer (LbL) electrostatic self-assembly. The unimolecular micelles, formed due to statistical compositions of amphiphilic polyelectrolytes used, were shown to suppress chain interdiffusion between adjacent layers in resulting micellar PEMs, as evidenced by spectroscopic ellipsometry, atomic force microscopy (AFM), and neutron reflectometry (NR) measurements. Additionally, hydrophobic cores of the micelles were used as hosts for photoactive molecules, namely, ferrocene and perfluorinated magnesium phthalocyanine. Stratified micellar multilayers were then deposited as hollow capsules using CaCO3 microparticles as templates. Photoinduced electron transfer (PET) between ferrocene and phthalocyanine solubilized in the polymer micelles was demonstrated to occur efficiently inside the stratified, polyelectrolyte walls of the capsules, due to the polarity gradient created by the incompatible aromatic and fluoroalkyl domains. The obtained results present a new approach to construct well-organized, self-assembled nanostructured materials for solar energy conversion.
Stereoselective Synthesis of 2Z,4E-Configured Dienoates through Tethered Ring Closing Metathesis
(2016)
Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides
(2016)
The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control.
A convenient synthesis of gamma-spirolactams in only two steps was developed. Birch reduction of benzoic acids and immediate alkylation with chloroacetonitrile afforded cyclohexadienes in high yields. The products could be isolated by crystallization on a large scale in analytically pure form. Subsequent hydrogenation with platinum(IV) oxide as the catalyst reduced the nitrile functionality and the double bonds in the same step with excellent stereoselectivity. The relative configurations were determined unequivocally by X-ray analyses. Direct cyclization of the intermediary formed amino acids afforded the desired gamma-spirolactams in excellent overall yields. The procedure is characterized by few steps, cheap reagents, and can be performed on a large scale, interesting for industrial processes.
Quantum dynamics of H-2(+) excited by two-cycle laser pulses with laser carrier frequencies corresponding to the wavelengths lambda(1) = 800 and 200 nm (corresponding to the periods tau(1) = 2.667 and 0.667 fs, respectively) and being linearly polarized along the molecular axis have been studied by the numerical solution of the non-Born-Oppenheimer time-dependent Schrodinger equation within a three-dimensional (3D) model, including the internuclear distance R and electron coordinates z and rho. The amplitudes of the pulses have been chosen such that the energies of H-2(+) after the ends of the laser pulses, < E > approximate to-0.515 au, were close to the dissociation threshold of H-2(+). It is found that there exists a certain characteristic oscillation frequency omega(osc) = 0.2278 au (corresponding to the period tau(osc) = 0.667 fs and the wavelength lambda(osc) = 200 nm) that plays the role of a "carrier" frequency of temporally shaped oscillations of the expectation values <-partial derivative V/partial derivative z) emerging after the ends of the laser pulses, both at lambda(1) = 800 nm and at lambda(1) = 200 nm. Moreover, at lambda(1) = 200 nm, the expectation value < z > also demonstrates temporally shaped oscillations after the end of the laser pulse. In contrast, at lambda(1) = 800 nm, the characteristic oscillation frequency omega(osc) = 0.2278 au appears as the frequency of small-amplitude oscillations of the slowly varying expectation value < z > which makes, after the end of the pulse, an excursion with an amplitude of about 4.5 au along the z axis and returns back to < z > approximate to 0 afterward. It is found that the period of the temporally shaped post-field oscillations of <-partial derivative V/partial derivative z > and < z >, estimated as tau(shp) approximate to 30 fs, correlates with the nuclear motion. It is also shown that vibrational excitation of H-2(+) is accompanied by the formation of "hot" and "cold" vibrational ensembles along the R degree of freedom. Power spectra related to the electron motion in H-2(+) calculated for both the laser-driven z and optically passive rho degrees of freedom in the acceleration form proved to be very interesting. In particular, both odd and even harmonics can be observed.
2-Fluoroadenine ((2F)A) is a therapeutic agent, which is suggested for application in cancer radiotherapy. The molecular mechanism of DNA radiation damage can be ascribed to a significant extent to the action of low-energy (<20 eV) electrons (LEEs), which damage DNA by dissociative electron attachment. LEE induced reactions in (2F)A are characterized both isolated in the gas phase and in the condensed phase when it is incorporated into DNA. Information about negative ion resonances and anion-mediated fragmentation reactions is combined with an absolute quantification of DNA strand breaks in (2F)A-containing oligonucleotides upon irradiation with LEEs. The incorporation of (2F)A into DNA results in an enhanced strand breakage. The strand-break cross sections are clearly energy dependent, whereas the strand-break enhancements by (2F)A at 5.5, 10, and 15 eV are very similar. Thus, (2F)A can be considered an effective radiosensitizer operative at a wide range of electron energies.
Rotational Barriers of Substituted BIPHEP Ligands: A Comparative Experimental and Theoretical Study
(2016)
The interconversion barriers of 14 different 3,3- and 5,5-disubstituted tropos BIPHEP [2,2-bis(diphenylphosphino)-1,1-biphenyl] and BIPHEP(O) [2,2-bis(diphenylphosphoryl)-1,1-biphenyl] ligands were investigated by enantioselective dynamic high performance liquid chromatography (DHPLC) and DFT calculations using the B3LYP/6-31G* and M06-2X/6-31G* levels of theory. The experimentally determined enantiomerization barriers varied from 86.8 to 101.4 kJmol(-1) and were found to be in excellent agreement with the calculated data. The root-mean-square deviations are 7.3 kJmol(-1) for the B3LYP functional and 11.3 kJmol(-1) for the M06-2X method.
For Vibrio cholerae, the coordinated import and export of Na+ is crucial for adaptation to habitats with different osmolarities. We investigated the Na+-extruding branch of the sodium cycle in this human pathogen by in vivo Na-23-NMR spectroscopy. The Na+ extrusion activity of cells was monitored after adding glucose which stimulated respiration via the Na+-translocating NADH:quinone oxidoreductase (Na+-NQR). In a V. cholerae deletion mutant devoid of the Na+-NQR encoding genes (nqrA-F), rates of respiratory Na+ extrusion were decreased by a factor of four, but the cytoplasmic Na+ concentration was essentially unchanged. Furthermore, the mutant was impaired in formation of transmembrane voltage (Delta psi, inside negative) and did not grow under hypoosmotic conditions at pH 8.2 or above. This growth defect could be complemented by transformation with the plasmid encoded nqr operon. In an alkaline environment, Na+/H+ antiporters acidify the cytoplasm at the expense of the transmembrane voltage. It is proposed that, at alkaline pH and limiting Na+ concentrations, the Na+-NQR is crucial for generation of a transmembrane voltage to drive the import of H+ by electrogenic Na+/H+ antiporters. Our study provides the basis to understand the role of the Na+-NQR in pathogenicity of V. cholerae and other pathogens relying on this primary Na+ pump for respiration. (C) 2015 Elsevier B.V. All rights reserved.
Oligospirothioketal (OSTK) rods are presented as an adjustable scaffold for optical membrane probes. The OSTK rods are readily incorporated into lipid bilayers due to their hydrophobic backbones. Because of their high length-over-diameter aspect ratio, only a minimal disturbance of the lipid bilayer is caused. OSTK rods show outstanding rigidity and allow defined labeling with fluorescent dyes, yielding full control of the orientation between the dye and OSTK skeleton. This. allows the construction of novel Forster resonance energy transfer probes with highly defined relative orientations of the transition dipole moments of the donor and acceptor dyes and makes the class of OSTK probes a power-fill, flexible toolbox for optical biosensing applications. Data on steady-state and time-resolved fluorescence experiments investigating the incorporation of coumarin- and [1,3]-dioxolo[4,5-f][1,3]benzo-dioxole-labeled OSTKs in large unilamellar vesicles are presented as a show case.
Poly(2-alkyl-2-oxazoline)s (PAOx) exhibit different crystallization behavior depending on the length of the alkyl side chain. PAOx having methyl, ethyl, or propyl side chains do not show any bulk crystallization. Crystallization in the heating cycle, that is, cold crystallization, is observed for PAOx with butyl and pentyl side chains. For PAOx with longer alkyl side chains crystallization occurs in the cooling cycle. The different crystallization behavior is attributed to the different polymer chain mobility in line with the glass transition temperature (T-g) dependency on alkyl side chain length. The decrease in chain mobility with decreasing alkyl side chain length hinders the relaxation of the polymer backbone to the thermodynamic equilibrium crystalline structure. Double melting behavior is observed for PButOx and PiPropOx which is explained by the melt-recrystallization mechanism. Isothermal crystallization experiments of PButOx between 60 and 90 degrees C and PiPropOx between 90 and 150 degrees C show that PAOx can crystallize in bulk when enough time is given. The decrease of Tg and the corresponding increase in chain mobility at T > T-g with increasing alkyl side chain length can be attributed to an increasing distance between the polymer backbones and thus decreasing average strength of amide dipole interactions. (C) 2015 Wiley Periodicals, Inc.
Time- and temperature-resolved in situ birefringence measurements were applied to analyze the effect of nanoparticles on the electric field-induced alignment of a microphase separated solution of poly(styrene)-block-poly(isoprene) in toluene. Through the incorporation of isoprene-confined CdSe quantum dots the reorientation behavior is altered. Particle loading lowers the order-disorder transition temperature, and increases the defect density, favoring nucleation and growth as an alignment mechanism over rotation of grains. The temperature dependent alteration in the reorientation mechanism is analyzed via a combination of birefringence and synchrotron SAXS. The detailed understanding of the effect of nanoparticles on the reorientation mechanism is an important prerequisite for optimization of electricfield-induced alignment of block copolymer/nanoparticle composites where the block copolymer guides the nanoparticle self-assembly into anisotropic structures.
The aggregation kinetics of thermoresponsive core-shell micelles with a poly(N-isopropyl acrylamide) shell in pure water or in mixtures of water with the cosolvents methanol or ethanol at mole fractions of 5% is investigated during a temperature jump across the respective cloud point. Characteristically, these mixtures give rise to cononsolvency behavior. At the cloud point, aggregates are formed, and their growth is followed with time-resolved small-angle neutron scattering. Using the reversible association model, the interaction potential between the aggregates is determined from their growth rate in dependence on the cosolvents. The effect of the cosolvent is attributed to the interaction potential on the structured layer of hydration water around the aggregates. It is surmised that the latter is perturbed by the cosolvent and thus the residual repulsive hydration force between the aggregates is reduced. The larger the molar volume of the cosolvent, the more pronounced is the effect. This framework provides a molecular-level understanding of solvent-mediated effective interactions in polymer solutions and new opportunities for the rational control of self-assembly in complex soft matter systems.
Information about the strength of donor-acceptor interactions in push-pull alkenes is valuable, as this so-called "push-pull effect' influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the CQC double bond to quantify the push-pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in C-13 NMR chemical shifts of the two carbons constituting the CQC double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor-acceptor interactions in the push-pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters ( apparent activation energy Ea and frequency factor A) and activation parameters ( Delta S-double dagger, Delta H-double dagger and Delta G(double dagger)), were determined from the data of the experimentally studied configurational isomerization of ( E)-9a. These results were compared to previously published related data for other two compounds, ( Z)-1b and ( 2E, 5Z)-7, showing that experimentally determined Delta G(double dagger) values are a good indicator of the strength of push-pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated CQC bond lengths and corroborate the applicability of Delta G(double dagger) for estimation of the strength of the push-pull effect in these and related systems.
Unwanted shrinkage behaviors or failure in structural functions such as mechanical strength or deformability of polymeric products related to their thermomechanical history are a major challenge in production of plastics. Here, we address the question whether we can turn this challenge into an opportunity by creating defined thermomechanical histories in polymers, represented by a specific morphology and nanostructure, to equip polymeric shaped bodies with desired functions, e.g. a temperature-memory, by hot, warm or cold deformation into multiblock copolymers having two partially overlapping melting transitions. A copolyesterurethane named PDLCL, consisting of poly(epsilon-caprolactone) (PCL) and poly(omega-pentadecalactone) (PPDL) crystalline domains, exhibiting a pronounced phase-segregated morphology and partially overlapping melting transitions was selected for this study. Different types of PCL and PPDL crystals as well as distinct degrees of orientation in both amorphous and crystalline domains were obtained after deformation at 20 or 40 degrees C and to a lower extent at 60 degrees C. The generated non-isotropic structures were stable at ambient temperature and represent the different stresses stored. Stress-free heating experiments showed that the relaxation in both amorphous and crystalline phases occurred predominantly with melting of PCL crystals. When the switching temperature, which was similar to the applied deformation temperature (temperature-memory), was exceeded in stress-free heating experiments, the implemented thermomechanical history could be reversed. In contrast, during constant-strain heating to 60 degrees C the generated structural features remained almost unchanged. These findings provide insights about the structure function relation in multiblock copolymers with two crystalline phases exhibiting a temperature-memory effect by implementation of specific thermomechanical histories, which might be a general principle for tailoring other functions like mechanical strength or deformability in polymers. (C) 2016 Elsevier Ltd. All rights reserved.
The enzymatic degradation of oligo(epsilon-caprolactone) (OCL) based films at the air-water interface is investigated by Langmuir monolayer degradation (LMD) experiments to elucidate the influence of the molecular architecture and of the chemical structure on the chain scission process. For that purpose, the interactions of 2D monolayers of two star-shaped poly(epsilon-caprolactone)s (PCLs) and three linear OCL based copolyesterurethanes (P(OCL-U)) with the lipase from Pseudomonas cepacia are evaluated in comparison to linear OCL. While the architecture of star-shaped PCL Langmuir layers slightly influences their degradability compared to OCL films, significantly retarded degradations are observed for P(OCL-U) films containing urethane junction units derived from 2, 2 (4), 4-trimethyl hexamethylene diisocyanate (TMDI), hexamethylene diisocyanate (HDI) or lysine ethyl ester diisocyanate (LDI). The enzymatic degradation of the OCL based 2D structures is related to the presence of hydrophilic groups within the macromolecules rather than to the packing density of the film or to the molecular weight. The results reveal that the LMD technique allows the parallel analysis of both the film/enzyme interactions and the degradation process on the molecular level. (C) 2016 Elsevier Ltd. All rights reserved.
An atomic scale molecular dynamics simulation (100 ns) was carried out to reveal the conformational features of a cationic polyelectrolyte, i.e., hyperbranched polyethyleneimine (PEI), inside of water-in-oil microemulsion droplets stabilized by the anionic sodium dodecyl sulfate surfactant (SDS) layer. Simulations show that the polymer reorients very quickly and is localized at the headgroup region, i.e., the polymer nitrogens are close to SDS sulfur atoms. In spite of the availability of surface roughness caused by the polymer, we track a stable inverse micelle during the production run. In overall, the obtained parameters are well compared with experimental findings. (C) 2016 Elsevier B.V. All rights reserved.
This paper focused on the synthesis of triangular nanoplatelets in the presence of a tubular network structure. The tubular network structure is formed by adding a strongly alternating polyampholyte, i.e., PalPhBisCarb, to a mixed vesicle system with a negatively charged bilayer containing phosphatidylcholin and AOT. Using the tubular network as a reducing agent in a one-step procedure, triangular and hexagonal nanoplatelets are formed. One can show that the nanoplatelet yield is enhanced by increasing the temperature and decreasing the reaction time. The platelet edge length can be decreased by heating the system up to 100 A degrees C. Due to specific interactions between PalPhBisCarb and the AOT/phospholipid bilayer, stacking and welding effects lead to the formation of ordered platelet structures. The reaction pathway to flat gold nanotriangles is discussed with regard to the twin plane growth model of gold nanoplates.
Owing to its rod-like alpha-helical secondary structure, the synthetic polypeptide poly(gamma-benzyl-L-glutamate) (PBLG) can form physical and thermoreversible gels in helicogenic solvents such as toluene. The versatility of PBLG can be increased by introducing functionalizable comonomers, such as allylglycine (AG). In this work we examined the secondary structure of PBLG and a series of statistical poly(gamma-benzyl-L-glutamate-co-allylglycine) copolypeptides, varying in composition and chain length, by circular dichroism (CD), Fourier-transform infrared (FTIR) and Raman spectroscopy, and wide-angle X-ray scattering (WAXS). The secondary structure of PBLG and the copolypeptides presented dissimilarities that increased with increasing AG molar fraction, especially when racemic AG units were incorporated. The physical gelation behavior of these copolypeptides was analyzed by temperature-sweep H-1 NMR and rheological measurements. The study revealed that both copolypeptide composition and chain length affected secondary structure, gelation temperature, and gel stiffness.
The optical properties of semiconductor nanocrystals (SC NCs) are largely controlled by their size and surface chemistry, i.e., the chemical composition and thickness of inorganic passivation shells and the chemical nature and number of surface ligands as well as the strength of their bonds to surface atoms. The latter is particularly important for CdTe NCs, which – together with alloyed CdxHg1−xTe – are the only SC NCs that can be prepared in water in high quality without the need for an additional inorganic passivation shell. Aiming at a better understanding of the role of stabilizing ligands for the control of the application-relevant fluorescence features of SC NCs, we assessed the influence of two of the most commonly used monodentate thiol ligands, thioglycolic acid (TGA) and mercaptopropionic acid (MPA), on the colloidal stability, photoluminescence (PL) quantum yield (QY), and PL decay behavior of a set of CdTe NC colloids. As an indirect measure for the strength of the coordinative bond of the ligands to SC NC surface atoms, the influence of the pH (pD) and the concentration on the PL properties of these colloids was examined in water and D2O and compared to the results from previous dilution studies with a set of thiol-capped Cd1−xHgxTe SC NCs in D2O. As a prerequisite for these studies, the number of surface ligands was determined photometrically at different steps of purification after SC NC synthesis with Ellman's test. Our results demonstrate ligand control of the pH-dependent PL of these SC NCs, with MPA-stabilized CdTe NCs being less prone to luminescence quenching than TGA-capped ones. For both types of CdTe colloids, ligand desorption is more pronounced in H2O compared to D2O, underlining also the role of hydrogen bonding and solvent molecules.
The mechanism of nanotriangle formation in multivesicular vesicles (MMV) is investigated by using time-dependent SAXS measurements in combination with UV-vis spectroscopy, light, and transmission electron microscopy. In the first time period 6.5 nm sized spherical gold nanoparticles are formed inside of the vesicles, which build up soft nanoparticle aggregates. a) In situ SAXS experiments show a linear increase of the volume and molar mass of nanotriangles in the second time period. The volume growth rate of the triangles is 16.1 nm(3)/min, and the growth rate in the vertical direction is only 0.02 nm/min. Therefore, flat nanotriangles with a thickness of 7 nm and a diameter of 23 nm are formed. This process can be described by a diffusion limited Ostwald ripening growth mechanism. TEM micrographs visualize soft coral-like structures with thin nanoplatelets at the periphery of the aggregates, which disaggregate in the third time period into nanotriangles and spherical particles. The 16 times faster growth of nanotriangles in the lateral than that in the vertical direction is related to the adsorption of symmetry breaking components, i.e., AOT and the polyampholyte PalPhBisCarb, on the {111} facets of the gold nanoplatelets in combination with confinement effects of the vesicular template phase.