Engineering proteolytically-degradable artificial extracellular matrices

Hydrogels are widely used as provisional matrices for tissue engineering and regenerative medicine, showing also great promise as platforms for 3D cell culture. Different bio-functionalization strategies have been proposed to enhance the biological performance of hydrogels, particularly when they lack intrinsic bioactivity. In this context, the design of artificial materials that mimic structural and functional features of the natural extracellular matrix (ECM) has been pursued. This review presents an overview on bioengineering approaches of integrating protease-sensitive motifs into hydrogels, for the creation of cell-responsive biomimetic scaffolding materials that degrade in response to their proteolytic microenvironment. The successful incorporation of protease-sensitive motifs in several synthetic and natural polymers, which has been achieved using various chemical routes, is described. In each case, the selected peptide sequences and their target proteases are highlighted, along with the main achievements of the study. A critical analysis of current limitations and recent advances is also provided, along with suggestions for further improvements.     

自组装膜在生物矿化中的应用

文章综述了自组装膜在生物矿化中的应用研究进展。介绍了有机硅烷类、有机硫化物类、脂肪羧酸类和醇胺类等自组装膜体系。概述了自组装膜在碳酸钙、草酸钙和羟基磷灰石研究中的现状,并对其今后的发展趋势进行了展望。     

谈钢结构单层工业厂房的质量控制要点

以门式钢架结构单层工业厂房的工程为实例,阐述了钢结构单层工业厂房施工中原材料、钢构件的出厂或进场验收、高强度螺栓连接副安装、钢结构安装的质量控制要点,从而促进工程质量的提高.     

Nano-tribological characteristics of lanthanum-based thin films on sulfonated self-assembled monolayer of 3-mercaptopropyl trimethoxysilane

Silane coupling reagent （3-mercaptopropyl trimethoxysilane （MPTS）） was prepared on silicon substrate to form two-dimensional Self-Assembled Monolayer （SAM） and the terminal -SH group in the film was in situ oxidized to -SO3H group to endow the film with good chemisorption ability. Thus, lanthanum-based thin films were deposited on oxidized MPTS-SAM to form rare earth composite thin films （RE thin films）, making use of the chemisorption ability of the -SO3H group. Atomic Force Microscope （AFM）, X-ray Photoelectron Spectrometry （XPS）, and contact angle measurements were used to characterize the RE thin films. Adhesive force and friction force of the RE thin films and silicon substrate were measured under various applied normal loads and scanning speed of AFM tip. The results showed that the friction force increased with applied normal loads and scanning speed of AFM tip. To study the effect of capillary force, tests were performed in various relative humidities. The results showed that the adhesive force of silicon substrate increased with relative humidity and the adhesive force of RE thin films only increased slightly with relative humidity. Research showed that surfaces with higher hydrophobic property reveal lowered adhesive and friction forces.     

Investigation of damage threshold to TiO2 coatings at different laser wavelength and pulse duration

Laser-induced damages to TiO₂ single layers and TiO₂/SiO₂ high reflectors at laser wavelength of 1064 nm, 800 nm, 532 nm, and pulse width of 12 ns, 220 ps, 50 fs, 8 ns are investigated. All films are prepared by electron beam evaporation. The relations among microstructure, chemical composition, optical properties and laser-induced damage threshold (LIDT), have been researched. The dependence of damage mechanism on laser wavelength and pulse width is discussed. It is found that from 1064 nm to 532 nm, LIDT is mainly absorption related, which is determined by film's extinction coefficient and stoichiometric defects. The rapid decrease of LIDT at 800 nm is due to the pulse width factor. TiO₂ coatings are mainly thermally by damaged at long pulse (τ ≥ 220 ps). The damage shows ablation feature at 50 fs.     

Impedimetric Measurements for Monitoring Avidin-Biotin Interaction on Self-Assembled Monolayer

Avidin-biotin has been controllable immobilized on the surface of gold electrodes using mercaptopropionic acid as self-assembled monolayer. Electrochemical impedance spectroscopy (EIS) was employed to investigate the changes that appear at the electrode surface in the presence of a redox mediator, K₃[Fe(CN)₆]. An electrical model more complex than that in other studies was used to interpret the EIS measurements (Randles circuit). This model is very useful because it takes into consideration both the transfer of electrons at the electrode/electrolyte interface and the diffusion of redox species through the double layer. The model allowed us to determine some important parameters like solution resistance R_sol, charge-transfer resistance R_ct, double-layer capacitance C_dl, Warburg resistance R_W, and the diffusion time constant τ. The EIS results proved that immobilization of avidin-biotin increased the charge-transfer resistance R_ct, due to the insulating character of these molecules.     

Non-equilibrium simulation of optically trapped colloidal particles at liquid interfaces

A theoretical study of the non-equilibrium behaviour of colloidal particle monolayers under the influence of the displacement of a single, optically trapped colloidal particle is presented. Two different types of monolayer (i.e., one relatively rigid and the other relatively soft) confined to a liquid–liquid interface are investigated using the Stokesian dynamics simulation technique. An effective dipole–dipole interaction is assumed to act between the colloidal particles and viscous drag forces acting on the particles are taken into account. The calculations reveal periodic oscillations of the net force on the trapped particle for the soft monolayer and highly non-linear, non-monotonic variations for the rigid monolayer. The highly non-linear variations of the net force for the rigid monolayer are concomitant with rapid, cooperative particle rearrangements and large oscillations in the global orientational order parameter of the monolayer. These findings, combined with the results of optical-tweezer experiments, should be useful for the rheology of liquid interfaces and the investigation of Pickering emulsions.     

Electrochemical response of ferrocenium filled calix[4]arene capsules in solution and immobilized on gold

Hydrogen-bonded dimers of tetra-urea calix[4]arenes are able to include ferrocenium ions as a guest. Heterodimeric capsules are exclusively formed in 1:1 mixtures of tetra-arylurea calix[4]arene 1 with tetra-tosylurea calix[4]arene 2. Sulfide groups attached via spacers on the urea rim of 1 allow their binding to metal surfaces rendering simultaneously their dissociation more difficult. Thus, the electrochemical response of encapsulated ferrocenium could be studied in a self-assembled monolayer (SAM) in addition to the solution electrochemistry with cyclic voltammetry. The stability of the electrochemically active monolayers was tested after a heat treatment (225 °C for 30 min in N₂ atmosphere) and multiple cycling (up to 1200 cycles), which could be required for a possible application as molecular based information storage.     

Stereospecificity in redox reactions of catechins at gold electrodes modified with self-assembled monolayers of homocysteine

The stereospecificity of a self-assembled monolayer (SAM) of homocysteine formed on the (1 1 1)-oriented gold surface toward the molecules with two chiral centers was investigated. Redox behaviors of catechins, which are electrochemically active molecules with two chiral centers, were analyzed with cyclic voltammetry by using a gold electrode modified with one enantiomeric form of homocysteine. The homocysteine SAM of one enantiomeric form was demonstrated to block the redox reaction of one enantiomer of catechin or epicatechin greater than that of the other, with cross inversion for the other enantiomer, in acidic solution. In addition, the homocysteine SAM on the gold electrode was suggested to recognize the chirality of one of the two chiral centers in catechin and epicatechin.     

Self-assembled nano-arrays of single-walled carbon nanotube-octa(hydroxyethylthio)phthalocyaninatoiron(II) on gold surfaces: Impacts of SWCNT and solution pH on electron transfer kinetics

The construction by sequential self-assembly process of reproducible, highly stable and pH-responsive redox-active nanostructured arrays of single-walled carbon nanotubes (SWCNTs) integrated with octa(hydroxyethylthio)phthalocyaninatoiron(II) (FeOHETPc) via ester bonds on a gold surface (Au-Cys-SWCNT-FeOHETPc) is investigated and discussed. The successful construction of this electrode is confirmed using atomic force microscopy and X-ray photoelectron spectroscopy as well as from the distinct cyclic voltammetric and electrochemical impedance spectroscopic profiles. The Au-Cys-SWCNT-FeOHETPc electrode exhibited strong dependence on the reaction of the head groups and the pH of the working electrolytes, the surface pK_a is estimated as 7.3. The high electron transfer capability of the Au-Cys-SWCNT-FeOHETPc electrode over other electrodes (Au-Cys-SWCNT or the Au-Cys-FeOHETPc or the Au-FeOHETPc) suggests that SWCNT greatly improves the electronic communication between FeOHETPc and the bare gold electrode. The electron transfer rate constant (k_app) of Au-Cys-SWCNT-FeOHETPc in pH 4.8 conditions (∼1.7 × 10⁻² cm⁻² s⁻¹) over that of the electrode obtained from SWCNT integrated with tetraaminophthalocyninatocobalt(II) (Au-Cys-SWCNT-CoTAPc) (5.1 × 10⁻³ cm⁻² s⁻¹) is attributed to the possible effect of the central metal on the phthalocyanine core and substituents on the peripheral positions of the phthalocyanine rings. We also prove that aligned SWCNT arrays exhibit much faster electron transfer kinetics to redox-active species in solutions compared to the randomly dispersed (drop-dried) SWCNTs.