Ink-structing the future of vascular tissue engineering:a review of the physiological bioink design

Three-dimensional(3D)printing and bioprinting have come into view for a plannable and standardizable generation of implantable tissue-engineered constructs that can substitute native tissues and organs.These tissue-engineered structures are intended to integrate with the patient’s body.Vascular tissue engineering(TE)is relevant in TE because it supports the sustained oxygenization and nutrition of all tissue-engineered constructs.Bioinks have a specific role,representingthenecessarymedium for printability and vascular cell growth.This review aims to understand the requirements for the design of vascular bioinks.First,an in-depth analysis of vascular cell interaction with their native environment must be gained.A physiological bioink suitable for a tissue-engineered vascular graft(TEVG)must not only ensure good printability but also induce cells to behave like in a native vascular vessel,including self-regenerative and growth functions.This review describes the general structure of vascular walls with wall-specific cell and extracellular matrix(ECM)components and biomechanical properties and functions.Furthermore,the physiological role of vascular ECM components for their interaction with vascular cells and the mode of interaction is introduced.Diverse currently available or imaginable bioinks are described from physiological matrix proteins to nonphysiologically occurring but natural chemical compounds useful for vascular bioprinting.The physiological performance of these bioinks is evaluated with regard to biomechanical properties postprinting,with a view to current animal studies of 3D printed vascular structures.Finally,the main challenges for further bioink development,suitable bioink components to create a self-assembly bioink concept,and future bioprinting strategies are outlined.These concepts are discussed in terms of their suitability to be part of a TEVG with a high potential for later clinical use.

官能团化刚性大环的超分子化学

重点介绍具有纳米尺寸的苯炔刚性大环的超分子化学:包括聚集效应,主客体化学、液晶行为及二维、三维超分子结构等.

官能团化稠环芳香烃合成进展

对稠环芳香烃的合成方法、官能团化稠环芳香烃最新合成进展、官能团化稠环芳香烃构建的复杂分子体系(液晶、刚性线型和环状的大分子)及其超分子化学进行了评述.

Effect of humic substances on the precipitation of calcium phosphate

For phosphorus （P） recovery from wastewater, the effect of humic substances （HS） on the precipitation of calcium phosphate was studied. Batch experiments of calcium phosphate precipitation were undertaken with synthetic water that contained 20 mg/L phosphate （as P） and 20 mg/L HS （as dissolved organic carbon, DOC） at a constant pH value in the range of 8.0-10.0. The concentration variations of phosphate, calcium （Ca） and HS were measured in the precipitation process; the crystalline state and compositions of the precipitates were analysed by powder X-ray diffraction （XRD） and chemical methods, respectively. It showed that at solution pH 8.0, the precipitation rate and removal efficiency of phosphate were greatly reduced by HS, but at solution pH ≥9.0, the effect of HS was very small. The Ca consumption for the precipitation of phosphate increased when HS was added; HS was also removed from solution with the precipitation of calcium phosphate. At solution pH 8.0 and HS concentrations ≤3.5 mg/L, and at pH ≥ 9.0 and HS concentrations ≤ 10 mg/L, the final precipitates were proved to be hydroxyapatite （HAP） by XRD. The increases of solution pH value and initial Ca/P ratio helped reduce the influence of HS on the precipitation of phosphate.

Investigation of reinforcement of the modified carbon black from wasted tires by nuclear magnetic resonance

Pyrolysis has the potential of transforming waste into recyclable products. Pyrolytic carbon black (PCB) is one of the most important products from the pyrolysis of used tires. Techniques for surface modifications of PCB have been developed. One of the most significant applications for modified PCB is to reinforce the rubber matrix to obtain high added values. The transverse relaxation and the chain dynamics of vulcanized rubber networks with PCB and modified PCB were studied and compared with those of the commercial carbon blacks using selective 1H transverse relaxation (T2) experiments and dipolar correlation effect (DCE) experiments on the stimulated echo. Demineralization and coupling agent modification not only intensified the interactions between the modified PCB and the neighboring polyisoprene chains, but also increased the chemical cross-link density of the vulcanized rubber with modified PCB. The mechanical testing of the rubbers with different kinds of carbon blacks showed that the maximum strain of the rubber with modified PCB was improved greatly. The mechanical testing results confirmed the conclusion obtained by nuclear magnetic resonance (NMR). PCB modified by the demineralization and NDZ-105 titanate coupling agent could be used to replace the commercial semi-reinforcing carbon black.

Plasma and nanoparticle shielding during pulsed laser ablation in liquids cause ablation efficiency decrease

Understanding shielding cross-effects is a prerequisite for maximal power-specific nanosecond laser ablation in liquids(LAL).However,discrimination between cavitation bubble(CB),nanoparticle(NP),and shielding,e.g.,by the plasma or a transient vapor layer,is challenging.Therefore,CB imaging by shadowgraphy is performed to better understand the plasma and laser beam-NP interaction during LAL.By comparing the fluence-dependent CB volume for ablations performed with 1 ns pulses with reports from the literature,we find larger energy-specific CB volumes for 7 ns-ablation.The increased CB for laser ablation with higher ns pulse durations could be a first explanation of the efficiency decrease reported for these laser systems having higher pulse durations.Consequently,1 ns-LAL shows superior ablation efficiency.Moreover,a CB cascade occurs when the focal plane is shifted into the liquid.This effect is enhanced when NPs are present in the fluid.Even minute amounts of NPs trapped in a stationary layer decrease the laser energy significantly,even under liquid flow.However,this local concentration in the sticking film has so far not been considered.It presents an essential obstacle in high-yield LAL,shielding already the second laser pulse that arrives and presenting a source of satellite bubbles.Hence,measures to lower the NP concentration on the target must be investigated in the future.

Liquid marbles containing petroleum and their properties

Liquid marbles （non-stick droplets） containing crude petroleum are reported. Liquid marbles were ob- tained by use of fluorinated decyl polyhedral oligomeric silsequioxane （FD-POSS） powder. Marbles containing crude petroleum remained stable on a broad diversity of solid and liquid supports. The effective surface tension of marbles filled with petroleum was established. The mechanism of friction of the marbles is discussed. Actuation of liquid marbles containing crude petroleum with an electric field is presented.

Experimental investigation of fluidized-bed reactor performance for oxidative coupling of methane

Performance of the oxidative coupling of methane in fluidized-bed reactor was experimentally investigated using Mn-Na2WO4/SiO2,La2O3/CaO and La2O3-SrO/CaO catalysts.These catalysts were found to be stable,especially Mn-Na2WO4/SiO2 catalyst.The effect of sodium content of this catalyst was analyzed and the challenge of catalyst agglomeration was addressed using proper catalyst composition of 2%Mn2.2%Na2WO4/SiO2.For other two catalysts,the effect of Lanthanum-Strontium content was analyzed and 10%La2O 3-20%SrO/CaO catalyst was found to provide higher ethylene yield than La2O3/CaO catalyst.Furthermore,the effect of operating parameters such as temperature and methane to oxygen ratio were also reviewed.The highest ethylene and ethane （C2） yield was achieved with the lowest methane to oxygen ratio around 2.40.5% selectivity to ethylene and ethane and 41% methane conversion were achieved over La2O3-SrO/CaO catalyst while over Mn-Na2WO4 /SiO2 catalyst,40% and 48% were recorded,respectively.Moreover,the consecutive effects of nitrogen dilution,ethylene to ethane production ratio and other performance indicators on the down-stream process units were qualitatively discussed and Mn-Na2WO4/SiO2 catalyst showed a better performance in the reactor and process scale analysis.

Liquid Phase Hydrogenation of Benzalacet0phen0ne:Effect of Solvent,Catalyst Support,Catalytic M etal and Reaction Conditions

Innovative catalysts based on a "porous glass" support material were developed and investigated for the reduction of benzalace-tophenone. The easy preparation conditions and possibility to use different metals (e.g. Pd, Pt, Rh) for impregnation gave a broad variety of these catalysts. Hydrogenation experiments with these supported catalysts were carried out under different hydrogen pressures and temperatures. Porous glass catalysts with Pd as the active component gave chemoselective hydrogenation of benzalacetophenone, while Pt- and Rh-catalysts tended to further reduce the carbonyl group, especially at elevated hydrogen pressures and temperatures. Kinetic analysis of the reactions revealed these had zero order kinetics, which was independent of the type of porous glass support and solvent used.

Time resolved studies reveal the origin of the unparalleled high efficiency of one nanosecond laser ablation in liquids

Laser ablation in liquid is a scalable nanoparticle production method with applications in areas like catalysis and biomedicine.Due to laser-liquid interactions,different energy dissipation channels such as absorption by the liquid and scattering at the ablation plume and cavitation bubble lead to reduced laser energy available for nanoparticle production.Ultrashort pulse durations cause unwanted nonlinear effects in the liquid,and for ns pulses,intra-pulse energy deposition attenuation effects are to be expected.However,intermediate pulse durations ranging from hundreds of picoseconds up to one nanosecond have rarely been studied in particular in single-pulse settings.In this study,we explore the pico-to nanosecond pulse duration regimes to find the pulse duration with the highest ablation efficiency.We find that pulse durations around 1-2 ns enable the most efficient laser ablation in liquid since the laser beam shielding by the ablation plume and cavitation bubble sets in only at longer pulse durations.Furthermore,pump-probe microscopy imaging reveals that the plume dynamics in liquids start to differ from plume dynamics in air at about 2 ns after pulse impact.

Amyloid β and free heme：bloody new insights into the pathogenesis of Alzheimer＇s disease

The cerebral formation of Amyloid β（Aβ） is a critical pathological feature of Alzheimer＇s disease（AD）.An accumulation of this peptide as senile plaques（SP） was already reported by Alois Alzheimer,the discoverer of the disease.Yet the exact contribution of Aβ to AD development remains elusive.Moreover,while extensive cerebral Aβ formation leads to fibril formation in many species,AD-like symptoms apparently depend on the highly conserved N-terminal residues R5,Y10 and H13.The amino acids were also shown to lead to the formation of Aβ-heme complexes,which exhibit peroxidase activity in the presence of H_2O_2.Taking together these observations we propose that the formation and enzymatic activity of the named complexes may represent an essential aspect of AD pathology.Furthermore,Aβ is also known to lead to cerebral micro-vessel destruction（CAA） as well as to hemolytic events.Thus we suggest that the Aβ-derived cerebral accumulation of blood-derived free heme represents a likely precondition for the subsequent formation of Aβ-heme complexes.

Ionic Liquid Assisted Extraction of Nitrogen and Sulphur-Containing Air Pollutants from Model Oil and Regeneration of the Spent Ionic Liquid

Removal of air pollutants, such as nitrogen and sulphur containing compounds from a model oil (dodecane) was studied. An ionic liquid (1-ethyl-3-methylimidazolium chloride [C2mim] [Cl]) was used as an extractant. Liquid-liquid extraction by using 1-ethyl-3-methylimidazolium chloride [C2mim] [Cl] was found to be a very promising method for the removal of N- and S-compounds. This was evaluated by using a model oil (dodecane) with indole as a neutral nitrogen compound and pyridine as a basic nitrogen compound. Dibenzothiophene (DBT) was used as a sulphur compound. An extraction capacity of up to 90 wt% was achieved for the model oil containing pyridine, while only 76 wt% of indole in the oil was extracted. The extraction capacity of a model sulphur compound DBT was found to be up to 99 wt%. Regeneration of the spent ionic liquid was carried out with toluene back-extraction. A 1:1 toluene-to-IL wt ratio was performed at room temperature. It was observed that, for the spent ionic liquid containing DBT as a model compound more than 85 wt% (corresponding 3852 mg/kg) could be removed from the oil. After the second regeneration cycle, 86 wt% of the DBT was recovered from the ionic liquid to toluene. In the case of indole as the nitrogen containing species, more than 99 wt%, (corresponding to 2993 mg/kg) of the original indole was transferred from the model oil to the ionic liquid. After the first-regeneration cycle of the spent ionic liquid, 54 wt% of the indole–in-IL was transferred to toluene. Thus, both extractions of nitrogen and sulphur model compounds were successfully carried out from model oil and the back-extraction of these compounds from the ionic liquids to toluene demonstrated the proved the concept of the regeneration point of view.

GAS TRANSPORT PROPERTIES OF A POLYIMIDE BASED ON 2, 2-BIS (3, 4-DECARBOXYPHENYL) HEXAFLUOROPROPANE AND meta-PHENYLENEDIAMINE

By means of a vacuum time-lag method, gas transport properties of a polyimide based on 2,2-bis(3,4-decarboxyphenyl) hexafluoropropane dianhydride (6FDA) and meta-phenylenediamine (mPDA) have been measured as a function of upstream pressure and temperature. The results show that no gas-induced plasticization occurs for this polyimide in the upstream pressure range from 1 atm to 20 atm. The temperature dependence of P and D can be described by the Arrhenius equations. The activation energies of permeation and diffusion were obtained for the gas/polymer pair studied and correlated with the size of penetrant gas.

Synthesis and Characterization of Poly(isoprene-b-butyl methacrylate) Block Copolymer in the Presence of Rare Earth Catalyst

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Synthesis and Mesophase Properties of Intraanular Functionized Shape-persistent Macrocycles Containing Dibenzo[fg,op]naphthacenes

On the basis of the C-C coupling reactions of dibenzo [ fg, op ] naphthacene bistriflate, which was obtained by the condensation of phenylacetates with 4-aryl-2,6-bis（2-bromo-4-methoxy-phenyl） pyrylium salts followed by palladium-catalyzed dehydrohalogenation, three shape-persistent macrocycles with dibenzonaphthacene corner pieces, a nanometer interior void, and intraanular oligoalkyl side groups were synthesized by the oxidative cyclization of the corresponding bisacetylenes under high-dilution conditions. Their thermotropic liquid crystalline properties were investigated by using polarizing microscopy and differential scanning calorimetry. All the three compounds showed nematic mesophases and belonged to discotic liquid crystals with inverted topology.

Degradation study on tin- and bismuth-based gas-diffusion electrodes during electrochemical CO_(2) reduction in highly alkaline media

This work investigated the degradation of tin – based gas-diffusion electrodes (GDE) and also a promising Bi2O3 GDE in electrochemical CO_(2) reduction in highly alkaline media which has not been studied before. The contributions of the electrode wetting (or flooding, if excessively) and catalyst leaching on the degradation were analyzed. Therefore, electrochemical impedance spectroscopy was used to monitor the wetted surface area of the GDE in combination with post-mortem analysis of the penetration depth by visualizing the electrolyte’s cation in the GDE cross-section. Furthermore, to reveal a possible degradation of the electrocatalyst, its distribution was mapped in the GDEs cross-section after operation while the catholyte was additionally analyzed via ICP-MS. The results clearly demonstrate that the SnO_(2) catalyst dissolves in the reaction zone inside the GDE and might be partially redeposited near the GDEs surface. Since the redeposition process occurs only partially a steady loss of catalyst was observed impeding a clear distinction of the two degradation phenomena. Nevertheless, the deterioration of the electrode performance measured as faraday efficiency (FE) of the parasitic hydrogen evolution reaction (HER) qualitatively correlates with the differential double layer capacitance (Cdl). A significant difference of the rate of increase for the hydrogen FE and Cdl can be ascribed to the superposition of both above-mentioned degradation mechanisms. The demonstrated instability of SnO_(2) contrasts with the behavior of Bi2O3 GDE which is stabilized during CO_(2) conversion by redeposition of the diluted dissolved species as metallic Bi which is active for the CO_(2) reduction reaction.

<i>In-Situ</i>Hydroelectrothermal Deposition of Silicate Layers on Stainless Steel Surfaces

The deposition of zeolites on solid support materials is possible by means of electrochemical methods, impregnation processes, as well as in-situ syntheses. Electrochemical deposition of zeolites has been reported as well, however with readily synthesized zeolite structures. Adhesive deposition of zeolites on stainless steel (S316) has been reported. This report investigates the feasibility of the deposition of silicates by in-situ hydroelectrothermal means. The investigation was done in aqueous solutions of pH = 7 to 13 at different temperatures (25°C to 70°C) by linear sweep method. Deposition was done at a saturated H2 atmosphere to ensure prior deposition of thin iron oxide film on the surface and formation of Fe-O-Si-linkages. This was proven by Raman measurement of the samples. Further linear sweep experiments in the presence of silica show monodentate and bidentate Fe-O-Si linkages on the surface, proven by IR-measurements. Presence of dissolved silica was done by UV-Vis with the molybdate yellow method. The best results are achieved at 70°C at pH 13 and ﹣4 mV (vs Ag/AgCl) or 200 mV (vs SHE). Discontinuous homogeneous layers are found on the stainless steel surface observed by SEM, EDX measurements and electrochemical measurements. Layer discontinuties are caused due to low silica concentration at equilibrium hydrothermal conditions, especially in the absence of silicic acid. All results shown are for the best results achieved except for linear sweep measurements and solubility constants of dissolved silica.

Synthesis and Structure of Ferrocenol Esters

N-Heterocyclic carbene-catalyzed oxidative esterification of ferroceneboronic acid by aromatic and heteroaromatic aldehydes affords the new ferrocenol hetaryl and aryl esters 1 - 4, 6 - 8 and 9 - 11. The reaction takes place under mild conditions. The X-ray crystal structure of ferrocenyl esters 3, 6, 11 was determined.

Characterizing bubble interaction effects in synchronous-double-pulse laser ablation for enhanced nanoparticle synthesis

To further advance nanomaterial applications and reduce waste production during synthesis,greener and sustainable production methods are necessary.Pulsed laser ablation in liquid(PLAL)is a green technique that enables the synthesis of nanoparticles.This study uses synchronous-double-pulse PLAL to understand bubble interaction effects on the nanoparticle size.By adjusting the lateral separation of the pulses relative to the maximum bubble size,an inter-pulse separation is identified where the nanoparticle size is fourfold.The cavitation bubble pair interaction is recorded using a unique coaxial diffuse shadowgraphy system.This system allows us to record the bubble pair interaction from the top and side,enabling the identification of the bubble’s morphology,lifetime,volumetric,and displacement velocity.It is found that the collision and collapse of the bubbles generated at a certain inter-pulse separation results in a larger nanoparticle size.These results mark a significant advancement by controlling the abundance of larger nanoparticles in PLAL,where previous efforts were primarily focused on reducing the average nanoparticle size.The experimentally observed trends are confirmed by numerical simulations with high spatial and temporal resolution.This study serves as a starting point to bridge the gap between upscaled multi-bubble practices and fundamental knowledge concerning the determinants that define the final nanoparticle size.