Polyoxopalladate-Loaded Metal-Organic Framework (POP@MOF): Synthesis and Heterogeneous Catalysis.

We report on the synthesis and characterization of the first polyoxo-noble-metalate-containing metal-organic framework (MOF) material, wherein the preformed MIL-101 has been impregnated with the discrete, cuboid-shaped polyoxopalladate [Pd13Se8O32]6- (Pd13Se8), leading to the composite Pd13Se8@MIL-101. This material was characterized by FTIR, TGA, elemental analysis, powder-XRD, N2 sorption (BET), SEM-EDX, and XPS. Furthermore, the Pd13Se8@MIL-101 composite was shown to be an effective, stable, and recyclable heterogeneous precatalyst for the Suzuki-Miyaura cross-coupling reaction at room temperature utilizing environmentally benign solvents, such as water and methanol.

Optimal orientation for angularly segmented multifocal corrections.

PURPOSE: Evaluate the importance of orientation of multifocal lens designs with angular increments of addition. METHODS: Optical properties of one monofocal and three multifocal designs were analysed with the visual Strehl ratio (VSOTF) metric through-focus (-1 to 5 D). Designs were tested in combination with the higher-order aberrations (HOAs) of 782 subjects (1564 eyes). Simulations included one monofocal, one bifocal (eight orientations), one trifocal (four orientations), and a 4-foci design (four orientations). Monocular and binocular performances of all designs were assessed by computing the area under the through-focus VSOTF plots, the through-focus range of acceptable optical performance, and, for binocular combinations, optical disparity between left and right eyes. RESULTS: Under monocular conditions, bifocal designs generated larger areas under the through focus VSOTF than trifocal designs and 4-foci designs. Specifically, bifocal designs divided vertically were optimal for 48% of eyes. Trifocal designs and 4-foci designs offered longer intervals of acceptable through-focus vision. Coma and spherical aberration values were correlated with the optimal orientation of multifocal corrections. The best binocular combination was achieved with a monofocal and a trifocal lens. The orientation of a multifocal design with angular areas affected the final optical properties of the combination (lens plus eye). CONCLUSIONS: The optical aberration distributions for our population of physiologically normal eyes demonstrated improved performance for some lens design orientations (i.e., left-right segments for 2-zone bifocals). Taking into account the HOAs of healthy patients, with special attention to coma and spherical aberration, will increase the optical quality of angularly divided multifocal solutions.

Adsorption mechanism and valency of catechol-functionalized hyperbranched polyglycerols.

Nature often serves as a model system for developing new adhesives. In aqueous environments, mussel-inspired adhesives are promising candidates. Understanding the mechanism of the extraordinarily strong adhesive bonds of the catechol group will likely aid in the development of adhesives. With this aim, we study the adhesion of catechol-based adhesives to metal oxides on the molecular level using atomic force microscopy (AFM). The comparison of single catechols (dopamine) with multiple catechols on hyperbranched polyglycerols (hPG) at various pH and dwell times allowed us to further increase our understanding. In particular, we were able to elucidate how to achieve strong bonds of different valency. It was concluded that hyperbranched polyglycerols with added catechol end groups are promising candidates for durable surface coatings.

Binocular saccades in myopes and emmetropes.

PURPOSE: To compare saccadic eye movements in groups of myopes and emmetropes, as eye movements could have an influence on refractive error development. Individual saccadic eye movement parameters were also compared with subjective refraction and axial length data. METHODS: Horizontal eye movements of 28 participants (14 myopes and 14 emmetropes; mean age [SD], 27.0 [4.7] years) were recorded using a head-mounted eye tracker. To reduce the influence of head movements, a chin rest was used. Two fixation stimuli lying symmetrically at ±10 degrees on either side of the median line were presented on a computer monitor and were alternately displayed for durations of 2 seconds each. The participants alternated their fixation between the target positions immediately after they became aware that the target had changed. Only right eye data were considered for analysis. RESULTS: Durations, amplitudes, and peak velocities of the main saccades and the numbers of overshoots, undershoots, and exact fixations were analyzed. For all analyzed parameters, no significant differences were found between myopes and emmetropes. When analyzing the whole study population or the emmetropic group alone, none of the saccadic eye movement parameters were correlated with axial length or refractive error. In myopes, only the peak velocity showed a weak correlation with refractive error and axial length, but this failed to reach statistical significance when allowance was made for multiple testing. CONCLUSIONS: Because saccadic eye movements seem to be similar in myopes and emmetropes, there is no evidence that saccadic eye movements are involved in myopia development.

Succinonitrile-Polymer Composite Electrolytes for Li-Ion Solid-State Batteries-The Influence of Polymer Additives on Thermomechanical and Electrochemical Properties.

A plastic crystalline electrolyte (PCE) consisting of 0.4 mol/L lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in succinonitrile (SN) was blended with poly(ethylene oxide) (PEO), poly(vinylpyrrolidone) (PVP), poly(ethylene carbonate) (PEC), and polyacrylonitrile (PAN). The influences of the regarding polymers on thermomechanical properties of the PCE were studied systematically, utilizing differential scanning calorimetry, thermogravimetric analysis, and oscillation experiments. Depending on the chosen polymer, the melting temperature and overall crystallinity of the PCE were increased. For PCEs containing PEO and PVP, overall crystallinity was enhanced the most resulting in lamellae-like superstructures, identified by light microscopy images. Furthermore, the onset for the sublimation process of SN was shifted to higher temperatures, and the mechanical strength was increased by the presence of some polymers, with exception of PEC. Electrochemical characterization, including electrochemical impedance spectroscopy and linear sweep voltammetry, revealed ionic conductivities of 10-4 S/cm at room temperature for PCE with PAN and extended electrochemical stability windows of ≥4.5 V vs lithiated graphite for PCE with PEO. By correlating the thermomechanical and electrochemical properties, some structure-property relationships were drawn, pointing out great potential for specific tailoring of PCEs by polymer additives. The synergistic effect of increasing both, mechanical stability and ionic conductivity, made the PCE + PAN composition especially attractive for a possible application in batteries.

Synthesis and Application Studies of DOPO-Based Organophosphorous Derivatives to Modify the Thermal Behavior of Polybenzoxazine.

The DOPO-based flame-retardant additives DOPO-HQ, DOPO-AP and DOPO-Van were synthesized in varying numbers of phenolic hydroxyl groups and amine groups. Moreover, their influence on the polymerization of a bisphenol F-based benzoxazine, as well as the thermal properties of the resulting materials, were studied. All DOPO-based derivatives influenced the polymerization temperature onset with a reduction of up to 20 °C, while thermo-mechanical properties remained high. Surprisingly, phosphorous content below 0.4 wt% significantly improved the reaction against small flames yielding an increase in the limited oxygen index by 2% and a V-0 rating in the UL-94 test. DOPO-HQ proved to be the most effective additive regarding the reaction against small flames at an astonishingly low phosphorous concentration of below 0.1 wt%, whereas DOPO-AP and DOPO-Van simultaneously lowered the polymerization temperature.

Multivalent non-covalent interactions lead to strongest polymer adhesion.

Multivalent interactions play a leading role in biological processes such as the inhibition of inflammation or virus internalization. The multivalent interactions show enhanced strength and better selectivity compared to monovalent interactions, but they are much less understood due to their complexity. Here, we detect molecular interactions in the range of a few piconewtons to several nanonewtons and correlate them with the formation and subsequent breaking of one or several bonds and assign these bonds. This becomes possible by performing atomic force microcopy (AFM)-based single molecule force spectroscopy of a multifunctional polymer covalently attached to an AFM cantilever tip on a substrate bound polymer layer of the multifunctional polymer. Varying the pH value and the crosslinking state of the polymer layer, we find that bonds of intermediate strength (non-covalent), like coordination bonds, give the highest multivalent bond strength, even outperforming strong (covalent) bonds. At the same time, covalent bonds enhance the polymer layer density, increasing in particular the number of non-covalent bonds. In summary, we can show that the key for the design of stable and durable polymer coatings is to provide a variety of multivalent interactions and to keep the number of non-covalent interactions at a high level.

Accommodative response to peripheral stimuli in myopes and emmetropes.

PURPOSE: It has been suggested that peripheral refractive error may influence eye growth and the development of axial refractive error, implying that the peripheral retina is sensitive to defocus. This study aimed to evaluate the steady-state accommodative response to peripheral stimuli in 10 young, adult myopes (mean spherical equivalent error -2.10 ± 1.72 D, median -1.63 D, range -0.83 to -6.00 D) and 10 emmetropes (mean spherical equivalent error -0.02 ± 0.35 D, median +0.08 D, range -0.50 to +0.50 D). METHODS: The subjects were asked to view monocularly the centre of a screen displaying each of a series of eccentric accommodative targets placed at 5, 10 and 15°. An axial target was viewed for comparison purposes. Accommodation was measured using an open-field autorefractor, each stimulus being varied between about 0 and 4 D with spherical trial lenses placed in front of the viewing eye. RESULTS: The results confirm that the peripheral retina is sensitive to optical focus, up to field angles of at least 15°, with accommodative responses weakening as the peripheral angle increases. There is some evidence that peripheral accommodation may be less effective in myopes than emmetropes. CONCLUSIONS: Although peripheral accommodation can be demonstrated in the absence of a central stimulus, the accommodation response is normally dominated by the central stimulus and it seems unlikely that peripheral accommodation effects play an important role in refractive development.

Determining the structure of α-phenylethyl isocyanide in chloroform by VCD spectroscopy and DFT calculations--simple case or challenge?

The present work provides a comprehensive theoretical and experimental study of the vibrational circular dichroism of (S)-α-phenylethyl isocyanide in chloroform. The structure in solution is investigated systematically by density functional theory calculations starting from the isolated molecule and then by considering solvent effects implicitly using the PCM and explicitly by taking into account molecular complexes of the isocyanide molecule and chloroform. Furthermore, the influence of dimerisation is evaluated, and it is finally found that the structure of (S)-α-phenylethyl isocyanide in chloroform is best described assuming a solvated dimer. These results are underlined by a quantitative correlation of the experimentally and theoretically obtained rotational strengths and a robust modes analysis.

VCD study of alpha-methylbenzyl amine derivatives: detection of the unchanged chiral motif.

Chiral alpha-methylbenzyl amine is a well known and often used chiral auxiliary, e.g., in the resolution of racemates or asymmetric catalysis. In this work, alpha-methylbenzyl amine and its derivatives N,alpha-dimethylbenzyl amine, N,N,alpha-trimethylbenzyl amine, and bis[alpha-methylbenzyl] amine were investigated by vibrational circular dichroism (VCD) spectroscopy and density functional theory (DFT). For all compounds, stable low energy conformers were obtained by the DFT calculations and based on those, the theoretical vibrational absorption (VA) and VCD spectra were calculated and compared with experimental spectra. Hence, the absolute configurations and conformational preferences were determined. A qualitative comparison of all the experimental VCD spectra of the investigated chiral molecules supported by the calculated ones is given which clearly shows similarities between the spectra of the different chiral amines. These can be assigned to vibrations of the unchanged chiral center.

Vibrational circular dichroism of 3-(trifluoroacetyl)-camphor and its interaction with chiral amines.

Vibrational circular dichroism (VCD) spectroscopy and density functional theory (DFT) calculations are used to investigate the keto-enol equilibrium of 3-(trifluoroacetyl)-camphor (TFC) and to study the interaction of TFC with chiral amines in deuterated Chloroform. It is shown that the VCD spectra of the enol- and keto forms of TFC can clearly be distinguished and that the enol form is favored. By deprotonation of the TFC enol with chiral amines, no indication of a mutual diasteriomeric influence on the VCD spectra induced by transfer of stereochemical information between the chiral ionic species is found, neither experimentally nor theoretically.

Short-Term Impact of FS-LASIK and SMILE on Dry Eye Metrics and Corneal Nerve Morphology.

PURPOSE: To analyze the short-term (up to 1 month) clinical outcomes in patients undergoing corneal laser refractive surgery and the impact on dry eye disease (DED) metrics and corneal nerves using in vivo confocal microscopy (IVCM). METHODS: The unaided distance visual acuity, corrected distance visual acuity, and spherical equivalent refraction (SEQ) were determined in 16 and 13 patients undergoing FS-LASIK and SMILE, respectively. DED metrics assessed were Ocular Surface Disease Index, Dry Eye Questionnaire 5-items (DEQ-5), tear film osmolarity, tear meniscus height, noninvasive keratograph breakup time (NIKBUT), ocular staining, and meibomian gland atrophy. An automated analysis of corneal nerve fiber density, corneal nerve branch density, corneal nerve fiber length (CNFL), and corneal nerve fiber fractal dimension were obtained from the IVCM scans using ACCMetrics software (University of Manchester). RESULTS: Both surgical techniques provided good refractive and visual outcomes. DED symptoms were found to be higher after FS-LASIK compared with SMILE (P < 0.05). A decrease in tear meniscus height (∼31%) and NIKBUT (∼40%) was reported after FS-LASIK (P = 0.005 and P = 0.001, respectively) but not after SMILE. Both procedures affected corneal nerve fiber density, corneal nerve branch density, CNFL, and corneal nerve fiber fractal dimension, but the impact was significantly greater with FS-LASIK (P = 0.001). Only CNFL correlated with the reported symptoms (DEQ-5) after FS-LASIK (r = -0.545, P = 0.029). CONCLUSIONS: FS-LASIK and SMILE provided good refractive and visual outcomes. There was an increased impact on DED symptoms after FS-LASIK compared with SMILE, although there were no significant differences between the procedures for most of the other ocular surface metrics assessed. The IVCM findings showed that SMILE had less impact on corneal nerves compared with FS-LASIK.

In-situ determination of time-dependent alginate-hydrogel formation by mechanical texture analysis.

Although alginate-based hydrogels are widely used, determining their mechanical properties and explaining their ability to form a hydrogel in situ remains a challenge. A new method of external gelation using calcium chloride (CaCl2) is proposed to quantify the formation of alginate hydrogel and its mechanical properties as well as to observe its temporal behaviour. To this end, small inhomogeneous alginate beads were formed, which comprised a shell and a core. The bead's shell consisted of calcium alginate hydrogel, while its core was sodium alginate sol. The beads were mechanically tested with a texture analyser to provide a detailed description of the structure. Different alginate samples could be clearly identified, and the M(mannuron)/G(guluron) acid ratios could be extrapolated quickly and easily from the test results if calibrated by NMR. This enables a fast and cost-effective characterisation of different alginates with regard to their composition and gel formation properties.

Current State of Bone Adhesives-Necessities and Hurdles.

The vision of gluing two bone fragments with biodegradable and biocompatible adhesives remains highly fascinating and attractive to orthopedic surgeons. Possibly shorter operation times, better stabilization, lower infection rates, and unnecessary removal make this approach very appealing. After 30 years of research in this field, the first adhesive systems are now appearing in scientific reports that may fulfill the comprehensive requirements of bioadhesives for bone. For a successful introduction into clinical application, special requirements of the musculoskeletal system, challenges in the production of a bone adhesive, as well as regulatory hurdles still need to be overcome. In this article, we will give an overview of existing synthetic polymers, biomimetic, and bio-based adhesive approaches, review the regulatory hurdles they face, and discuss perspectives of how bone adhesives could be efficiently introduced into clinical application, including legal regulations.

Vibrational circular dichroism spectroscopy of solid polymer films: effects of sample orientation.

Vibrational circular dichroism (VCD) spectra of anisotropic thin solid samples are often superimposed with large contributions of linear birefringence and linear dichroism. In this study a theoretical approach is given on how to extract the true VCD spectrum out of such superimposed spectra. To verify this approach, the VCD spectra of achiral polymer films were examined. The polymers are supposed to give a zero line as VCD spectrum after eliminating the linear contributions. Applying our approach, in which four VCD spectra in different but selected sample orientations are recorded, and calculating their average, leads to the expected result, i.e., a zero line for achiral polymers. The advantage of this method for the elimination of artifacts from solid-state VCD spectra is that no further measurements are required (e.g., linear dichroism measurements or the determination of the orientation with the maximum anisotropy).

Dry eye following cataract surgery: The effect of light exposure using an in-vitro model.

PURPOSE: Cataract surgery can lead to the temporary development or worsening of dry eye symptoms. Contributing factors may include corneal incisions, agents used before, during or after surgery, light from the operating microscope, disruption of ocular surface tissues and inflammatory processes. The purpose of this study was to observe the effect of light exposure on conjunctival fibroblasts in order to determine whether light has an effect on wound healing closure, assuming that operating microscopes might have an effect on the ocular surface. METHOD: An in vitro scratch assay was performed on porcine conjunctival fibroblasts. Ten minutes of light exposure from a light microscope with a halogen bulb was performed after the scratch assay. Fibroblasts were kept in culture for 48 hours post-exposure and the wound closure rates were visualized by live/dead staining. The fibroblasts which were exposed to light were compared to those without light exposure. Cell viability was also analysed by MTT assay. RESULTS: A Slower wound closure rate was found when fibroblasts were exposed to light compared to the non-light exposed controls. Cell viability reduced by 20% with light exposure compared to controls in p3 cells (p = 0.04; however, the trend was not observed with p4 and p5 cells (p > 0.05). CONCLUSIONS: These results suggest that light exposure might be one of the possible contributory factors for dry eye after ophthalmic surgery. Further evaluation of light effects should be carried out with different ocular surface cells.

Early clinical outcomes after small incision lenticule extraction surgery (SMILE).

PURPOSE: Dry eye is known to impact on clinical outcomes after laser vision correction and the use of a newer 'all femtosecond laser' surgical approach may be associated with less impact on the ocular surface post-operatively. The purpose of this study was to evaluate the early clinical outcomes and tear instability after the first small incision lenticule extraction (SMILE) cases undertaken by three surgeons at a single site in the UK. METHODS: Retrospective audit. Seventy-one eyes of 37 patients underwent SMILE surgery using the Zeiss VisuMax laser system (Carl Zeiss Meditec, Germany). Uncorrected and corrected distance visual acuity, spherical equivalent refraction, fluorescein enhanced tear break up time, simulated keratometry and complications were evaluated pre- and post-operatively where applicable. RESULTS: The study population consisted of 21 males and 16 females. The mean±standard deviation age was 33±8years. The results showed that 100% of eyes achieved 20/40 or better and 88% achieved 20/20 or better uncorrected distance visual acuity. The spherical equivalent refraction after surgery was within ±0.50D in 82% of eyes at three months. There was no significant difference in tear break up time from pre-operative levels at three months. Complications were infrequent. CONCLUSIONS: This early data from surgeons' first SMILE procedures suggest SMILE provides good outcomes in terms of refractive predictability and visual acuity with minimal impact on the tear film. Longitudinal research will further improve our understanding of the longer-term impact of SMILE on clinical outcomes, ocular surface metrics and patient reported outcomes.

Structural and tribometric characterization of biomimetically inspired synthetic "insect adhesives".

Background: Based on previous chemical analyses of insect tarsal adhesives, we prepared 12 heterogeneous synthetic emulsions mimicking the polar/non-polar principle, analysed their microscopical structure and tested their adhesive, frictional, and rheological properties. Results: The prepared emulsions varied in their consistency from solid rubber-like, over soft elastic, to fluid (watery or oily). With droplet sizes >100 nm, all the emulsions belonged to the common type of macroemulsions. The emulsions of the first generation generally showed broader droplet-size ranges compared with the second generation, especially when less defined components such as petrolatum or waxes were present in the lipophilic fraction of the first generation of emulsions. Some of the prepared emulsions showed a yield point and were Bingham fluids. Tribometric adhesion was tested via probe tack tests. Compared with the "second generation" (containing less viscous components), the "first generation" emulsions were much more adhesive (31-93 mN), a finding attributable to their highly viscous components, i.e., wax, petrolatum, gelatin and poly(vinyl alcohol). In the second generation emulsions, we attained much lower adhesivenesses, ranging between 1-18 mN. The adhesive performance was drastically reduced in the emulsions that contained albumin as the protein component or that lacked protein. Tribometric shear tests were performed at moderate normal loads. Our measured friction forces (4-93 mN in the first and 0.1-5.8 mN in the second generation emulsions) were comparatively low. Differences in shear performance were related to the chemical composition and emulsion structure. Conclusion: By varying their chemical composition, synthetic heterogeneous adhesive emulsions can be adjusted to have diverse consistencies and are able to mimic certain rheological and tribological properties of natural tarsal insect adhesives.

Adhesion and friction of the smooth attachment system of the cockroach Gromphadorhina portentosa and the influence of the application of fluid adhesives.

Two different measurement techniques were applied to study the attachment of the smooth foot pads of the Madagascar hissing cockroach Gromphadorhina portentosa The attachment of the non-manipulated adhesive organs was compared with that of manipulated ones (depletion or substitution by artificial secretions). From measurements of the friction on a centrifuge, it can be concluded that on nanorough surfaces, the insect appears to benefit from employing emulsions instead of pure oils to avoid excessive friction. Measurements performed with a nanotribometer on single attachment organs showed that, in the non-manipulated euplantulae, friction was clearly increased in the push direction, whereas the arolium of the fore tarsus showed higher friction in the pull direction. The surface of the euplantulae shows an imbricate appearance, whereupon the ledges face distally, which might contribute to the observed frictional anisotropy in the push direction. Upon depletion of the tarsal adhesion-mediating secretion or its replacement by oily fluids, in several cases, the anisotropic effect of the euplantula disappeared due to the decrease of friction forces in push-direction. In the euplantulae, adhesion was one to two orders of magnitude lower than friction. Whereas the tenacity was slightly decreased with depleted secretion, it was considerably increased after artificial application of oily liquids. In terms of adhesion, it is concluded that the semi-solid consistence of the natural adhesion-mediating secretion facilitates the detachment of the tarsus during locomotion. In terms of friction, on smooth to nanorough surfaces, the insects appear to benefit from employing emulsions instead of pure oils to avoid excessive friction forces, whereas on rougher surfaces the tarsal fluid rather functions in improving surface contact by keeping the cuticle compliable and compensating surface asperities of the substratum.

Baseline peripheral refractive error and changes in axial refraction during one year in a young adult population.

PURPOSE: To determine whether the initial characteristics of individual patterns of peripheral refraction relate to subsequent changes in refraction over a one-year period. METHODS: 54 myopic and emmetropic subjects (mean age: 24.9±5.1 years; median 24 years) with normal vision were recruited and underwent conventional non-cycloplegic subjective refraction. Peripheral refraction was also measured at 5° intervals over the central 60° of horizontal visual field, together with axial length. After one year, measurements of subjective refraction and axial length were repeated on the 43 subjects who were still available for examination. RESULTS: In agreement with earlier studies, higher myopes tended to show greater relative peripheral hyperopia. There was, however, considerable inter-subject variation in the pattern of relative peripheral refractive error (RPRE) at any level of axial refraction. Across the group, mean one-year changes in axial refraction and axial length did not differ significantly from zero. There was no correlation between changes in these parameters for individual subjects and any characteristic of their RPRE. CONCLUSION: No evidence was found to support the hypothesis that the pattern of RPRE is predictive of subsequent refractive change in this age group.