Minimal-Invasive 3D Laser Printing of Microimplants in Organismo.

Multi-photon 3D laser printing has gathered much attention in recent years as a means of manufacturing biocompatible scaffolds that can modify and guide cellular behavior in vitro. However, in vivo tissue engineering efforts have been limited so far to the implantation of beforehand 3D printed biocompatible scaffolds and in vivo bioprinting of tissue constructs from bioinks containing cells, biomolecules, and printable hydrogel formulations. Thus, a comprehensive 3D laser printing platform for in vivo and in situ manufacturing of microimplants raised from synthetic polymer-based inks is currently missing. Here, a platform for minimal-invasive manufacturing of microimplants directly in the organism is presented by one-photon photopolymerization and multi-photon 3D laser printing. Employing a commercially available elastomeric ink giving rise to biocompatible synthetic polymer-based microimplants, first applicational examples of biological responses to in situ printed microimplants are demonstrated in the teleost fish Oryzias latipes and in embryos of the fruit fly Drosophila melanogaster. This provides a framework for future studies addressing the suitability of inks for in vivo 3D manufacturing. The platform bears great potential for the direct engineering of the intricate microarchitectures in a variety of tissues in model organisms and beyond.

Unlocking Enhanced Electrochemical Performance of MBene-MoB Through Controlled Aluminum Dissipation from MoAlB.

2D transition metal borides, known as MBenes, have attracted considerable attention due to their exceptional properties. This study explores the feasibility of aluminum (Al) etching from MoAlB using environmentally friendly and sustainable fluoride-free dilute acidic/alkaline solutions at room temperature, revealing its thermodynamic and kinetic viability. Furthermore, it is found that complete removal of Al can be achieved in dilute alkaline reagent under hydrothermal conditions, yielding pristine single/few-layered MBene-MoB for the first time, while acidic solutions result in ≈33% etching rates. XRD refinement, which tracks aluminum removal from 0% to 100%, reveals transient metastable phases of MoAl1-xB (x < 0.5) in the initial etching stages, evolving into relatively stable pure Mo2AlB2 structures with 50% Al deficiency, serving as a precursor to MBenes. The subsequent loss of Al results in a 2D MBene-MoB structure. DFT calculations confirm excellent conductivity for MoAlB, MoAl1-xB (x = 0-1), and MBene-MoB. Remarkably, MBene-MoB exhibits superior supercapacitor performance with a 4025.60 mF cm-2/201.28 F g-1 capacitance. Simulations validate rapid electrolyte diffusion in layered MBene-MoB, contributing significantly to enhanced capacitance. Additionally, in the hydrogen evolution reaction (HER), MBene-MoB demonstrates superior catalytic activity compared to the precursor MoAlB and commercial MoB. Calculations suggest the potential for enhancing HER through surface modulation, considering its suboptimal hydrogen adsorption energy.

Exploring the Potential of MBenes Supercapacitors: Fluorine-Free Synthesized MoAl1-xB with Ultrahigh Conductivity and Open Space.

The present study describes the synthesis of multilayered MBenes MoAl1-xB with different degrees of Al deintercalation using a mild, fluorine-free approach of dilute alkali to remove Al from MoAlB. We propose an etching route and compare it to conventional fluoride etching products. Additionally, the study explores the possible application and energy storage mechanism of MBenes in supercapacitors, marking the first investigation of its kind. At room temperature, 1/24-MoAl1-xB with terminal groups -OH exhibits ∼25% Al removal in 1 wt % NaOH for 24 h, outperforming traditional etching technology. Increasing the Al removal exposed more open space, resulting in a higher capacitance. Compared to LiF/HCl-MoAl1-xB (etched by LiF + HCl), 1/24-MoAl1-xB has a higher energy storage capability. The multilayered 1/24-MoAl1-xB film electrode exhibits ultrahigh conductivity with a rapid relaxation time of 0.97 s and high areal capacitance (2006.60 mF cm-2) while maintaining 80.2% capacitance after 5000 cycles. The MoAl1-xB all-solid-state supercapacitor (ASSS) delivers a high capacitance of 741.6 mF cm-2 at 1 mV s-1 for a single electrode and exhibits stable capacitance even at a 90° bending angle, highlighting its potential practical use. Our research represents an important step in the synthesis of MBenes and highlights their potential applications in supercapacitors.

Distinct actin-dependent nanoscale assemblies underlie the dynamic and hierarchical organization of E-cadherin.

Cadherins are transmembrane adhesion proteins required for the formation of cohesive tissues.1-4 Intracellular interactions of E-cadherin with the Catenin family proteins, α- and ß-catenin, facilitate connections with the cortical actomyosin network. This is necessary for maintaining the integrity of cell-cell adhesion in epithelial tissues.5-11 The supra-molecular architecture of E-cadherin is an important feature of its adhesion function; cis and trans interactions of E-cadherin are deployed12-15 to form clusters, both in cis and trans.11,16-21 Studies in Drosophila embryo have also shown that Drosophila E-cadherin (dE-cad) is organized as finite-sized dynamic clusters that localize with actin patches at cell-cell junctions, in continuous exchange with the extra-junctional pool of dE-cad surrounding the clusters.11,19 Here, we use the ectopic expression of dE-cad in larval hemocytes, which lack endogenous dE-cad to recapitulate functional cell-cell junctions in a convenient model system. We find that, while dE-cad at cell-cell junctions in hemocytes exhibits a clustered trans-paired organization similar to that reported previously in embryonic epithelial tissue, extra-junctional dE-cad is also organized as relatively immobile nanoclusters as well as more loosely packed diffusive oligomers. Oligomers are promoted by cis interactions of the ectodomain, and their growth is counteracted by the activity of cortical actomyosin. Oligomers in turn promote assembly of dense nanoclusters that require cortical actomyosin activity. Thus, cortical actin activity remodels oligomers and generates nanoclusters. The requirement for dynamic actin in the organization of dE-cad at the nanoscale may provide a mechanism to dynamically tune junctional strength.

Erbium-Doped Nanoparticle-Polymer Composite Thin Films for Photonic Applications: Structural and Optical Properties.

Erbium-doped nanocrystal (NC)-dispersed polymer thin films are attractive core materials for use in optical waveguides as they can provide high optical gain and enable the formation of compact waveguide amplifiers. Nonetheless, there are significant challenges associated with obtaining good dispersibility of NCs into a polymer matrix and favorable optical properties. Therefore, in this paper, we report the fabrication of Er3+-doped ceria (EGC) NCs employing the Leeds alginate process (LAP) and their incorporation into a siloxane polymer matrix. The surface morphology and compositional, structural, and optical properties of the fabricated films are evaluated to assess the NC dispersion and their suitability for the waveguide amplifier. The photoluminescence (PL) and lifetime measurements of the NCs-polymer nanocomposite thin film samples show intense, broadband PL emission of the Er3+ ions at 1534 nm (4I13/2 → 4I15/3 transition) with a full width at half-maximum (fwhm) of ∼64 nm and lifetime in the range of 2.6-3.0 ms. The inhomogeneously broadened PL spectra and improvement in lifetime of NCs in the polymer are important results that we report. The EGC NCs-polymer nanocomposite thin films also exhibit excellent transparency in the NIR wavelength range and a refractive index in the range of 1.53-1.58 in the visible wavelength. The work presented here clearly demonstrates the potential of using high-quality Er-doped nanocomposite polymer thin films for interesting applications such as compact low-cost waveguide amplifiers and lasers.

Distinct contributions of tensile and shear stress on E-cadherin levels during morphogenesis.

During epithelial morphogenesis, cell contacts (junctions) are constantly remodeled by mechanical forces that work against adhesive forces. E-cadherin complexes play a pivotal role in this process by providing persistent cell adhesion and by transmitting mechanical tension. In this context, it is unclear how mechanical forces affect E-cadherin adhesion and junction dynamics. During Drosophila embryo axis elongation, Myosin-II activity in the apico-medial and junctional cortex generates mechanical forces to drive junction remodeling. Here we report that the ratio between Vinculin and E-cadherin intensities acts as a ratiometric readout for these mechanical forces (load) at E-cadherin complexes. Medial Myosin-II loads E-cadherin complexes on all junctions, exerts tensile forces, and increases levels of E-cadherin. Junctional Myosin-II, on the other hand, biases the distribution of load between junctions of the same cell, exerts shear forces, and decreases the levels of E-cadherin. This work suggests distinct effects of tensile versus shear stresses on E-cadherin adhesion.

Promising solid electrolyte material for an IT-SOFC: crystal structure of the cerium gadolinium holmium oxide Ce0.8Gd0.1Ho0.1O1.9 between 295 and 1023†K.

The crystal structure of Ce0.8Gd0.1Ho0.1O1.9 (cerium gadolinium holmium oxide) has been determined from powder X-ray diffraction data. This is a promising material for application as a solid electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFCs). Nanoparticles were prepared using a novel sodium alginate sol-gel method, where the sodium ion was exchanged with ions of interest and, after washing, the gel was calcined at 723 K in air. The crystallographic features of Gd and Ho co-doped cerium oxide were investigated around the desired operating temperatures of IT-SOFCs, i.e. 573 ≤ T ≤ 1023 K. We find that the crystal structure is a stable fluorite structure with the space group Fm-3m in the entire temperature range. In addition, the trend in lattice parameters shows that there is a monotonic increase with increasing temperature.

Influence of sodium chloride content in electrolyte solution on electrochemical impedance measurements of human dentin.

BACKGROUND: The aim of this study was to investigate the influence of sodium chloride (NaCl) content in electrolyte solution on electrochemical impedance measurements of human dentin by employing electrochemical impedance spectroscopy. MATERIALS AND METHODS: Dentin samples were prepared from extracted molars. Electrochemical impedance measurements were carried out over a wide frequency range (0.01Hz-10MHz). After measurements, samples were characterized using scanning electron microscopy. RESULTS: Electrochemical impedance measurements showed that the mean values of dentin electrical resistance were 4284, 2062, 1336, 53 and 48kΩ at different NaCl contents in electrolyte solution. One-way ANOVA test of mean values of dentin electrical resistance revealed a significant difference (P < 0.0001) as a function of NaCl content in electrolyte solution. Comparing electrical resistance values of dentin samples at 0.05% w/v and 0.9% w/v concentrations were found to be significantly different (P < 0.05 at 95% confidence level). Scanning electron microscopy revealed structure of dentin sample with intertubular dentin matrix and distribution of patent dentinal tubules. CONCLUSION: This in vitro study indicated, through electrochemical impedance spectroscopy measurements, that electrical resistance of dentin was affected by the concentration of NaCl in electrolyte solution. It is clear from the current study that NaCl concentration in electrolyte solution has a marked influence on dentin electrical resistance. Therefore, this baseline data need to be considered in any future study on dental samples.

Treatment of refractory ulcerative necrobiosis lipoidica diabeticorum with oral thalidomide.

Ulcerative necrobiosis lipoidica (NL) in diabetic patients is a rare, painful condition. It is a difficult-to-treat condition, impairing quality of life of patients. Although various drugs have been tried, none of them is consistently effective. Biologics in the form of TNF-alpha inhibitors show promising results in the treatment. But because of their high cost we chose thalidomide, which also has TNF-alpha inhibiting properties to successfully treat a long-standing case of ulcerative NL, which was refractory to various treatment modalities.

Glucose oxidase encapsulated polyvinyl alcohol-silica hybrid films for an electrochemical glucose sensing electrode.

An amperometric glucose enzyme electrode was developed by the immobilization of glucose oxidase (GOD) in a composite material based on polyvinyl alcohol (PVA) and partially prehydrolyzed tetraethyl orthosilicate (pphTEOS) on the surface of "in-house" fabricated graphite electrodes. For comparison, silver and gold nanoparticles (Ag/AuNPs) embedded in the PVA-pphTEOS matrix was prepared through a novel method via sol-gel process based on the in situ chemical reduction of Ag or Au ions using PVA as a reducing agent and stabilizer. The successful incorporation of Ag and AuNPs ranging from 5 to 7.5 and 4.5-11 nm, respectively, in the PVA-pphTEOS matrix was confirmed by UV-Vis spectroscopy, TEM, and EDX analysis. The PVA-TEOS matrix was also characterized by FTIR spectroscopy. The analytical performance of the enzyme electrodes were studied in terms of linear ranges, sensitivities, response times, limits of detection, reproducibility and stability.

Sporocidic properties of poly(vinyl alcohol)/silver nanoparticles/TEOS thin hybrid films.

The sporocidic activity of hybrid materials based on PVA/AgNps/TEOS thin films has been investigated. Deep Agar Method has been applied to study the sporocidic properties of these hybrid materials with different silver concentrations. This method has been used because of the lack of standard methods for testing the sporocidic activity in such materials and due to the specific characteristics of bacterial spore. Clear and pronounced presence of sporocidic activity of the hybrid materials towards spores of control strains Bacillus subtilis ATCC 6633 and Geobacillus stearothermophilus ATCC 7953 has been established. The use of chromatographic paper disks impregnated with PVA/AgNps/TEOS showed the advantages in testing the biological properties of the hybrid material in comparison to the disks obtained by directly cutting the PVA/AgNps/TEOS films. The highest sporocidic activity, although with small deviation of 0.5-1.0 mm, was established at the PVA/AgNps/TEOS hybrid films with concentration of silver precursor 9.2 mg/mL and 18.3 mg/mL. The experiments were performed with the aim to reveal the opportunities for a practical application of the material.

Synthesis, characterisation and antibacterial activity of PVA/TEOS/Ag-Np hybrid thin films.

Novel hybrid material thin films based on polyvinyl alcohol (PVA)/tetraethyl orthosilicate (TEOS) with embedded silver nanoparticles (AgNps) were synthesized using sol-gel method. Two different strategies for the synthesis of silver nanoparticles in PVA/TEOS matrix were applied based on reduction of the silver ions by thermal annealing of the films or by preliminary preparation of silver nanoparticles using PVA as a reducing agent. The successful incorporation of silver nanoparticles ranging from 5 to 7nm in PVA/TEOS matrix was confirmed by TEM and EDX analysis, UV-Vis spectroscopy and XRD analysis. The antibacterial activity of the synthesized hybrid materials against etalon strains of three different groups of bacteria -Staphylococcus aureus (gram-positive bacteria), Escherichia coli (gram-negative bacteria), Pseudomonas aeruginosa (non-ferment gram-negative bacteria) has been studied as they are commonly found in hospital environment. The hybrid materials showed a strong bactericidal effect against E. coli, S. aureus and P. aeruginosa and therefore have potential applications in biotechnology and biomedical science.

(Ba(x)La(1-x)(2))In(2)O(5+x) (0.4 < or = x < or = 0.6) electrolyte-supported mixed-potential CO sensors.

The dense (Ba(x)La(1-x)(2))In(2)O(5+x) electrolytes with different compositions (x = 0.4, 0.5, 0.6) were synthesized by Pechini method. The obtained sintered (Ba(x)La(1-x)(2))In(2)O(5+x) electrolytes showed a high relative density of approximately 98%, and the major phase of three electrolyte compositions was indexed as a cubic phase. The CO sensing properties of as-fabricated planar-type (Ba(x)La(1-x)(2))In(2)O(5+x)-based sensors coupled with ITO and Pt as the sensing electrode and reference electrode, respectively, were investigated. The effects of factors such as gas flow rate, chemical compositions, and density of the electrolytes on the sensing performance were investigated. The sensors showed good sensitivity to different concentrations of CO from approximately 100 to approximately 500 ppm and excellent selectivity over low concentrations of methane (<500 ppm). Linear relationships between emf of the sensors and CO gas concentrations from approximately 100 to approximately 400 ppm were observed. However, the sensors indicated more sluggish response compared with the sensors coupled with a corresponding porous electrolyte. The probable reason has been discussed. The long-term stability of the sensor for the detection of CO was also investigated, which indicated a reasonably stable sensor signal after an initial decline during the incubation period.

Electrochemical NO2 sensor using a NiFe1.9Al0.1O4 oxide spinel electrode.

A novel solid-state electrochemical sensor using (Sc2O3)0.08(ZrO2)0.92 (ScSZ) electrolyte solid and a NiFe1.9Al0.1O4 oxide spinel electrode was tested for the detection of NO2 at temperatures greater than 700 degrees C for automobile applications. The sensor was found to respond rapidly, reproducibly, and selectively to NO2 at 703 and 740 degrees C. The response time of the sensor was approximately 8 s, and the recovery time was 10 s at both 703 and 741 degrees C. The response of the sensor was highly reproducible to the change in concentration of NO2 and also showed negligible cross-sensitivity to potentially interfering gases such as O2, CO, and CH4 in the gas stream.

Age-related changes in ac-impedance spectroscopy studies of normal human dentine.

Non-destructive methods, such as the ac-impedance technique, have recently been applied to early caries detection and to identify micro-leakage between tooth structure and filling materials. However, in vitro impedance measurements are affected by a number of external factors. The purpose of present study was to investigate the effect of the age of teeth on impedance measurements of human dentine by employing electrical impedance spectroscopy (EIS). Fully hydrated dentine samples were prepared from extracted third molars of 20 and 50 year old patients. Ac-impedance measurements were carried out over a wide frequency range. Impedance measurements showed that there were differences in impedance between young and older dentine. In their circuit models, both resistance and capacitance were found to be significantly different (p < 0.05) for the two age groups. One of the age-related changes in dentine is the formation of peritubular dentine on the inner walls of dentinal tubules and we propose that this is responsible for the differences in impedance. Sample or patient age therefore must be considered when making impedance measurements on any tooth.

Electrochemical screening of anti-microbial peptide LL-37 interaction with phospholipids.

LL-37 is an alpha-helical antimicrobial peptide of human origin. It is a 37 residue cathelicidin peptide. This paper explores the use of electrochemical methods to investigate the interaction of LL-37 with phospholipid and lipid A monolayers on a mercury drop electrode. Experiments were carried out in Dulbecco's phosphate buffered saline at pH approximately 7.6. The capacity-potential curves of the coated electrode in the presence and absence of LL-37 were measured using out-of-phase ac voltammetry. The frequency dependence of the complex impedance of the coated electrode in the presence and absence of LL-37 was estimated at -0.4 V versus Ag/AgCl 3.5 mol dm(-3) KCl. The monolayer permeability to ions was studied by following the reduction of Tl(I) to Tl(Hg) at the coated electrode. LL-37 shows no significant interaction with DOPC. However, LL-37 shows a small interaction with DOPG and lipid A within a DOPC monolayer where the monolayer permeability is marginally increased and the zero frequency capacitance (ZFC) is marginally decreased in both cases. LL-37 shows a significant interaction with a lipid A monolayer thereby decreasing the ZFC by 30%. The results concur with the known membrane active properties of LL-37 and establish this electrochemical approach as a key technique for screening peptides.

Lipid headgroup discrimination by antimicrobial peptide LL-37: insight into mechanism of action.

Interaction of the human antimicrobial peptide LL-37 with lipid monolayers has been investigated by a range of complementary techniques including pressure-area isotherms, insertion assay, epifluorescence microscopy, and synchrotron x-ray scattering, to analyze its mechanism of action. Lipid monolayers were formed at the air-liquid interface to mimic the surface of the bacterial cell wall and the outer leaflet of erythrocyte cell membrane by using phosphatidylglycerol (DPPG), phosphatidylcholine (DPPC), and phosphatidylethanolamine (DPPE) lipids. LL-37 is found to readily insert into DPPG monolayers, disrupting their structure and thus indicating bactericidal action. In contrast, DPPC and DPPE monolayers remained virtually unaffected by LL-37, demonstrating its nonhemolytic activity and lipid discrimination. Specular x-ray reflectivity data yielded considerable differences in layer thickness and electron-density profile after addition of the peptide to DPPG monolayers, but little change was seen after peptide injection when probing monolayers composed of DPPC and DPPE. Grazing incidence x-ray diffraction demonstrated significant peptide insertion and lateral packing order disruption of the DPPG monolayer by LL-37 insertion. Epifluorescence microscopy data support these findings.

In vitro analysis of 'smear layer' on human dentine using ac-impedance spectroscopy.

OBJECTIVE: To analyse smear layers on human dentine using ac-impedance spectroscopy. METHODS: Dentine samples were prepared from extracted, sound, third molars. Impedance measurements were carried out on dentine samples before and after etching. After measuring, samples were examined under scanning electron microscope (SEM) to correlate electrical measurements with structure. RESULTS: Marked differences in impedance before and after etching were demonstrated. SEM investigation showed that a smear layer overlies dentine surfaces before etching, but completely disappeared after etching, leaving open dentinal tubules. CONCLUSIONS: The clinical removal of smear layers is still subjective. This objective method, based on combined ac-impedance and admittance measurement in vitro, has the potential to allow development of standardised techniques and if developed further may be of use in vivo.