Self-assembly of focal point oligo-catechol ethylene glycol dendrons on titanium oxide surfaces: adsorption kinetics, surface characterization, and nonfouling properties

This work covers the synthesis of second-generation, ethylene glycol dendrons covalently linked to a surface anchor that contains two, three, or four catechol groups, the molecular assembly in aqueous buffer on titanium oxide surfaces, and the evaluation of the resistance of the monomolecular adlayers against nonspecific protein adsorption in contact with full blood serum. The results were compared to those of a linear poly(ethylene glycol) (PEG) analogue with the same molecular weight. The adsorption kinetics as well as resulting surface coverages were monitored by ex situ spectroscopic ellipsometry (VASE), in situ optical waveguide lightmode spectroscopy (OWLS), and quartz crystal microbalance with dissipation (QCM-D) investigations. The expected compositions of the macromolecular films were verified by X-ray photoelectron spectroscopy (XPS). The results of the adsorption study, performed in a high ionic strength ("cloud-point") buffer at room temperature, demonstrate that the adsorption kinetics increase with increasing number of catechol binding moieties and exceed the values found for the linear PEG analogue. This is attributed to the comparatively smaller and more confined molecular volume of the dendritic macromolecules in solution, the improved presentation of the catechol anchor, and/or their much lower cloud-point in the chosen buffer (close to room temperature). Interestingly, in terms of mechanistic aspects of "nonfouling" surface properties, the dendron films were found to be much stiffer and considerably less hydrated in comparison to the linear PEG brush surface, closer in their physicochemical properties to oligo(ethylene glycol) alkanethiol self-assembled monolayers than to conventional brush surfaces. Despite these differences, both types of polymer architectures at saturation coverage proved to be highly resistant toward protein adsorption. Although associated with higher synthesis costs, dendritic macromolecules are considered to be an attractive alternative to linear polymers for surface (bio)functionalization in view of their spontaneous formation of ultrathin, confluent, and nonfouling monolayers at room temperature and their outstanding ability to present functional ligands (coupled to the termini of the dendritic structure) at high surface densities.

Nonequilibrium hysteresis and spin relaxation in the mixed-anisotropy dipolar-coupled spin-glass LiHo0.5Er0.5F4

We present a study of the model spin-glass LiHo0.5Er0.5F4 using simultaneous ac susceptibility, magnetization, and magnetocaloric effect measurements along with small angle neutron scattering (SANS) at sub-Kelvin temperatures. All measured bulk quantities reveal hysteretic behavior when the field is applied along the crystallographic c axis. Furthermore, avalanchelike relaxation is observed in a static field after ramping from the zero-field-cooled state up to 200–300 Oe. SANS measurements are employed to track the microscopic spin reconfiguration throughout both the hysteresis loop and the related relaxation. Comparing the SANS data to inhomogeneous mean-field calculations performed on a box of one million unit cells provides a real-space picture of the spin configuration. We discover that the avalanche is being driven by released Zeeman energy, which heats the sample and creates positive feedback, continuing the avalanche. The combination of SANS and mean-field simulations reveal that the conventional distribution of cluster sizes is replaced by one with a depletion of intermediate cluster sizes for much of the hysteresis loop.

Osseointegration of titanium implants functionalised with phosphoserine-tethered poly(epsilon-lysine) dendrons: a comparative study with traditional surface treatments in sheep

The aim of this study was to analyse the osseointegrative potential of phosphoserine-tethered dendrons when applied as surface functionalisation molecules on titanium implants in a sheep model after 2 and 8 weeks of implantation. Uncoated and dendron-coated implants were implanted in six sheep. Sandblasted and etched (SE) or porous additive manufactured (AM) implants with and without additional dendron functionalisation (SE-PSD; AM-PSD) were placed in the pelvic bone. Three implants per group were examined histologically and six implants were tested biomechanically. After 2 and 8 weeks the bone-to-implant contact (BIC) total values of SE implants (43.7 ± 12.2; 53.3 ± 9.0 %) and SE-PSD (46.7 ± 4.5; 61.7 ± 4.9 %) as well as AM implants (20.49 ± 5.1; 43.9 ± 9.7 %) and AM-PSD implants (19.7 ± 3.5; 48.3 ± 15.6 %) showed no statistically significant differences. For SE-PSD and AM-PSD a separate analysis of only the cancellous BIC demonstrated a statistically significant difference after 2 and 8 weeks. Biomechanical findings proved the overall increased stability of the porous implants after 8 weeks. Overall, the great effect of implant macro design on osseointegration was further supported by additional phosphoserine-tethered dendrons for SE and AM implants.

From the chiral magnetic wave to the charge dependence of elliptic flow

The quark-gluon plasma formed in heavy ion collisions contains charged chiral fermions evolving in an external magnetic field. At finite density of electric charge or baryon number (resulting either from nuclear stopping or from fluctuations), the triangle anomaly induces in the plasma the Chiral Magnetic Wave (CMW). The CMW first induces a separation of the right and left chiral charges along the magnetic field; the resulting dipolar axial charge density in turn induces the oppositely directed vector charge currents leading to an electric quadrupole moment of the quark-gluon plasma. Boosted by the strong collective flow, the electric quadrupole moment translates into the charge dependence of the elliptic flow coefficients, so that $v_2(\pi^+) < v_2(\pi^-)$ (at positive net charge). Using the latest quantitative simulations of the produced magnetic field and solving the CMW equation, we make further quantitative estimates of the produced $v_2$ splitting and its centrality dependence. We compare the results with the available experimental data.

Role of proton MR for the study of muscle lipid metabolism

1H-MR spectroscopy (MRS) of intramyocellular lipids (IMCL) became particularly important when it was recognized that IMCL levels are related to insulin sensitivity. While this relation is rather complex and depends on the training status of the subjects, various other influences such as exercise and diet also influence IMCL concentrations. This may open insight into many metabolic interactions; however, it also requires careful planning of studies in order to control all these confounding influences. This review summarizes various historical, methodological, and practical aspects of 1H-MR spectroscopy (MRS) of muscular lipids. That includes a differentiation of bulk magnetic susceptibility effects and residual dipolar coupling that can both be observed in MRS of skeletal muscle, yet affecting different metabolites in a specific way. Fitting of the intra- (IMCL) and extramyocellular (EMCL) signals with complex line shapes and the transformation into absolute concentrations is discussed. Since the determination of IMCL in muscle groups with oblique fiber orientation or in obese subjects is still difficult, potential improvement with high-resolution spectroscopic imaging or at higher field strength is considered. Fat selective imaging is presented as a possible alternative to MRS and the potential of multinuclear MRS is discussed. 1H-MRS of muscle lipids allows non-invasive and repeated studies of muscle metabolism that lead to highly relevant findings in clinics and patho-physiology.

Distribution of intramyocellular lipids in human calf muscles as determined by MR spectroscopic imaging

In this study the distribution of intramyocellular lipids (IMCL) in human calf muscles was determined by 1H-MR spectroscopic imaging (MRSI) measurements. An obstacle for MRSI measurements in the calf, including different muscles, is the inevitable inclusion of regions with high concentrations of extramyocellular lipids (EMCL). This can lead to signal bleeding and consequently to unpredictable overlaps of IMCL resonances with EMCL in voxels of interest. The results of this study show that signal bleeding from EMCL can be substantially reduced in voxels from calf muscles by the application of a lipid extrapolation (LE) procedure (Haupt et al., Magn Reson Med 1996;35:678). The spectra of all voxels located within muscle tissue were fitted, and the metabolite values were assigned to one of 10 different muscles based on image segmentation. Significant IMCL differences between some muscles were obtained, with high values in m. soleus and two to three times lower values in the tibialis anterior, tibialis posterior, and gastrocnemius muscles. In addition to gross differences between muscles, significant intersubject differences were observed in both IMCL content and distribution over different muscles. A significant correlation between fiber orientation (obtained from orientation-dependent dipolar coupling of creatine and taurine resonances) and IMCL content was found, indicating that IMCL content is directly correlated to biomechanical properties.

Overview of analytical approaches

The general model The aim of this chapter is to introduce a structured overview of the different possibilities available to display and analyze brain electric scalp potentials. First, a general formal model of time-varying distributed EEG potentials is introduced. Based on this model, the most common analysis strategies used in EEG research are introduced and discussed as specific cases of this general model. Both the general model and particular methods are also expressed in mathematical terms. It is however not necessary to understand these terms to understand the chapter. The general model that we propose here is based on the statement made in Chapter 3, stating that the electric field produced by active neurons in the brain propagates in brain tissue without delay in time. Contrary to other imaging methods that are based on hemodynamic or metabolic processes, the EEG scalp potentials are thus “real-time,” not delayed and not a-priori frequency-filtered measurements. If only a single dipolar source in the brain were active, the temporal dynamics of the activity of that source would be exactly reproduced by the temporal dynamics observed in the scalp potentials produced by that source. This is illustrated in Figure 5.1, where the expected EEG signal of a single source with spindle-like dynamics in time has been computed. The dynamics of the scalp potentials exactly reproduce the dynamics of the source. The amplitude of the measured potentials depends on the relation between the location and orientation of the active source, its strength and the electrode position.

Phase diagram with an enhanced spin-glass region of the mixed Ising–XY magnet LiHo{x}Er{1-x}F{4}

We present the experimental phase diagram of LiHoxEr1-xF4, a dilution series of dipolar-coupled model magnets. The phase diagram was determined using a combination of ac susceptibility and neutron scattering. Three unique phases in addition to the Ising ferromagnet LiHoF4 and the XY antiferromagnet LiErF4 have been identified. Below x = 0.86, an embedded spin-glass phase is observed, where a spin glass exists within the ferromagnetic structure. Below x = 0.57, an Ising spin glass is observed consisting of frozen needlelike clusters. For x ∼ 0.3–0.1, an antiferromagnetically coupled spin glass occurs. A reduction of TC(x) for the ferromagnet is observed which disobeys the mean-field predictions that worked for LiHoxY1-xF4.

Liquid-Crystalline Dendrimers Designed by Click Chemistry

Liquid-crystalline dendrimers have been prepared from second-generation Percec-type poly(benzyl ether) dendrons or second-generation poly(aryl ester) dendrons carrying cyanobiphenyl mesogens. The Janus dendrimer, which combines the two types of dendromesogens, has also been synthesized. Those compounds have been prepared under copper-catalyzed azide–alkyne cycloaddition conditions. The mesomorphic properties have been studied by thermal analysis (POM, DSC) and small-angle X-ray scattering. Smectic A, nematic, and columnar phases have been observed depending on the dendritic building blocks. The click reaction has proven to be a powerful and elegant synthetic tool for the design of complex dendritic liquid-crystalline architectures.