Efficient bioproduction of poly(3-hydroxypropionate) homopolymer using engineered Escherichia coli strains.

This study focuses on the development of a scalable method for producing poly(3-hydroxypropionate), a homopolymer with significant physico-mechanical properties, through the use of metabolically-engineered Escherichia coli K12 (MG1655) and externally supplied 3-hydroxypropionate. The polymer synthesis pathway was established and optimized through synthetic biology techniques, including the effects of overexpressing phasin and cell division proteins. The optimized strain achieved unprecedented production titers of 9.5 g/L in flask cultures and 80 g/L in fed-batch bioreactors within 45 h. The analysis of poly(3-hydroxypropionate) polymer properties revealed it possesses excellent elasticity (Young's modulus < 6 MPa) and tensile strength (∼80 MPa), positioning it within the category of elastomers or flexible plastics. These findings suggest a viable path for the sustainable, large-scale production of the poly(3-hydroxypropionate) biopolymer.

Alteration of Neural Network and Hippocampal Slice Activation through Exosomes Derived from 5XFAD Nasal Lavage Fluid.

Exosomes, key mediators of intercellular transmission of pathogenic proteins, such as amyloid-beta and tau, significantly influence the progression and exacerbation of Alzheimer's disease (AD) pathology. Present in a variety of biological fluids, including cerebrospinal fluid, blood, saliva, and nasal lavage fluid (NLF), exosomes underscore their potential as integral mediators of AD pathology. By serving as vehicles for disease-specific molecules, exosomes could unveil valuable insights into disease identification and progression. This study emphasizes the imperative to investigate the impacts of exosomes on neural networks to enhance our comprehension of intracerebral neuronal communication and its implications for neurological disorders like AD. After harvesting exosomes derived from NLF of 5XFAD mice, we utilized a high-density multielectrode array (HD-MEA) system, the novel technology enabling concurrent recordings from thousands of neurons in primary cortical neuron cultures and organotypic hippocampal slices. The ensuing results revealed a surge in neuronal firing rates and disoriented neural connectivity, reflecting the effects provoked by pathological amyloid-beta oligomer treatment. The local field potentials in the exosome-treated hippocampal brain slices also exhibited aberrant rhythmicity, along with an elevated level of current source density. While this research is an initial exploration, it highlights the potential of exosomes in modulating neural networks under AD conditions and endorses the HD-MEA as an efficacious tool for exosome studies.

Capillary instability in screen-printed micropatterns.

Screen printing (SP) has been extensively studied owing to its widespread industrial applications; however, only a few studies have focused on the substrate effect. Herein, we demonstrate that a screen-printed line can undergo a broadening effect or lateral undulation, which is determined by the substrate and printed dimensions. The degree of spreading was systematically investigated by employing 1D and 2D geometrical parameters. Based on the liquidity of the ink, we developed a simple inviscid theory with imposed perturbation to analyze the instability of screen-printed lines. The dispersion relation was derived to estimate the geometry of the laterally undulated lines and compared with the experimental results. The proposed argument is particularly applicable to a regime in which SP inks have greater liquidity. The screen-printed patterns exhibited unique undulated shapes and were utilized as photomasks for the facile fabrication of raccoon-type microchannels.

Nanoparticles Are Separated in a Different Pattern from Microparticles with Focused Flow Control.

Separation of particles is essential to ensure the reliability and reproducibility of experiments for nanometer-scale materials. There are several methods, such as ultracentrifugation, precipitation, filtration, etc., for separation. However, the separation of nanoparticles in a continuous operation has not been examined widely. Here, we report the separation of nanometer-scale particles on a microfluidic system and related separation phenomena of nanoparticles from microparticles. We also describe not-yet-confirmed reversed behaviors of nanoparticle separation in the process of continuous operation. The present system along with elucidated operational conditions could be applied to treat relatively large quantities of nanometer-scale particles.

Exosomes derived from chemically induced human hepatic progenitors inhibit oxidative stress induced cell death.

The emerging field of regenerative medicine has revealed that the exosome contributes to many aspects of development and disease through intercellular communication between donor and recipient cells. However, the biological functions of exosomes secreted from cells have remained largely unexplored. Here, we report that the human hepatic progenitor cells (CdHs)-derived exosome (EXOhCdHs ) plays a crucial role in maintaining cell viability. The inhibition of exosome secretion treatment with GW4869 results in the acceleration of reactive oxygen species (ROS) production, thereby causing a decrease of cell viability. This event provokes inhibition of caspase dependent cell death signaling, leading to a ROS-dependent cell damage response and thus induces promotion of antioxidant gene expression or repair of cell death of hypoxia-exposed cells. Together, these findings show the effect of exosomes in regeneration of liver cells, and offer valuable new insights into liver regeneration.

Engineering oxygen nanobubbles for the effective reversal of hypoxia.

Hypoxia, which results from an inadequate supply of oxygen, is a major cause of concern in cancer therapy as it is associated with a reduction in the effectiveness of chemotherapy and radiotherapy in cancer treatment. Overexpression and stabilization of hypoxia-inducible factor 1α (HIF-1α) protein in tumours, due to hypoxia, results in poor prognosis and increased patient mortality. To increase oxygen tension in hypoxic areas, micro- and nanobubbles have been investigated by various researchers. In the present research, lipid-shelled oxygen nanobubbles (ONBs) were synthesized through a sonication method to reverse hypoxic conditions created in a custom-made hypoxic chamber. Release of oxygen gas from ONBs in deoxygenated water was evaluated by measuring dissolved oxygen. Hypoxic conditions were evaluated by performing in vitro experiments on MDA-MB231 breast cancer cells through the expression of HIF-1α and the fluorescence of image-iT™ hypoxia reagent. The results indicated the degradation of HIF-1α after the introduction of ONBs. We propose that ONBs are successful in reversing hypoxia, downregulating HIF-1α, and improving cellular conditions, leading to further medical applications.

Fabrication of highly luminescent and concentrated quantum dot/poly(methyl methacrylate) nanocomposites by matrix-free methods.

We present matrix-free methods for fabricating highly luminescent and transparent CdSe/ZnS quantum dot (QD)/polymer nanocomposites utilizing poly(methyl methacrylate) (PMMA)-grafted QDs with various molecular weights. We found that the QD-PMMA nanocomposites prepared by these matrix-free methods were superior to those prepared by a simple blending method in relation to their optical property, QD dispersion, and quantum efficiency (QE). In particular, a matrix-free nanocomposite containing PMMA with a molecular weight of 2000 had the highest QE (52.8%) and transmittance of all the samples studied even at a very high QD concentration (49 wt%). This finding was attributed to the enhanced passivation of the QD surface due to the higher grafting density of the PMMA ligands and reduced energy transfer due to more uniform dispersion of QDs. Finally, we applied the nanocomposites to LED devices, and found that the matrix-free nanocomposite exhibited a higher color conversion efficiency and smaller redshift in the peak emission wavelength than that prepared using a simple blending method.

Graphene Oxide Involved Air-Controlled Electrospray for Uniform, Fast, Instantly Dry, and Binder-Free Electrode Fabrication.

We report a facile air-controlled electrospray method to directly deposit binder-free active materials/graphene oxide (GO) onto current collectors. This method is inspired from an electrospinning process, and possesses all the advantages that electrospinning has such as low cost, easy scaling up, and simultaneous solvent evaporation during the spraying process. Moreover, the spray slurry is only a simple mixture of active materials and GO suspension in water, no binder polymer, organic solvent, and conductive carbon required. In our research, high-capacity Si nanoparticles (Si NP, 70-100 nm) and SiO microparticles (SiO MP, 3-10 µm) were selected to demonstrate the capability of this method to accommodate particles with different sizes. Their mixture with GO was sprayed onto a collector and then thermally annealed in an inert gas to obtain Si NP or SiO MP/reduced graphene oxide (RGO) binder-free electrodes. We are also able to directly deposit fairly large electrode sheets (e.g., 12 × 21 in.) upon the application requirement. To the best of our knowledge, this is the simplest approach to produce Si-related materials/RGO layered structures directly on current collector with controllable area and loading. Si and SiO MP/RGO are evaluated in both half and full lithium cells, showing good electrochemical performance. Prelithiation is also studied and gives a high first cycle Coulombic efficiency. In addition to Si-related materials, other materials with different shapes and sizes (e.g., MoO3 nanobelts, Sn/carbon nanofibers, and commercial sulfur particles) can also be sprayed. Beyond the preparation of battery electrodes, this approach can also be applied for other types of electrode preparation such as that of a supercapacitor, fuel cell, and solar cell.

Quantum efficiency of colloidal suspensions containing quantum dot/silica hybrid particles.

We have investigated the fluorescence properties of colloidal suspensions conntaining quantum dot (QD)/silica hybrid particles. First, we synthesized QD/silica hybrid particles with silica-QD-silica (SQS) core-shell-shell geometry, and monitored the quantum efficiencies of their suspensions at various particle concentrations. We found that the quantum efficiency (QE) of SQS particles in deionized (DI) water was much lower than that of the QDs even at low particle concentration, mainly due to the light scattering of emitted photons at the silica/water interface, followed by reabsorption by QDs. As the concentration of SQS particles was increased, both light scattering and reabsorption by QDs became more important, which further reduced the QE. Refractive index-matched solvent, however, reduced light scattering, yielding greater QE than DI water. Next, we induced aggregation of SQS particles, and found that QE increased as particles aggregated in DI water because of reduced light scattering and reabsorption, whereas it remained almost constant in the refractive index-matched solvent. Finally, we studied aggregation of highly concentrated silica particle suspensions containing a low concentration of SQS particles, and found that QE increased with aggregation because light scattering and reabsorption were reduced.

Columnar liquid crystals in cylindrical nanoconfinement.

Axial orientation of discotic columnar liquid crystals in nanopores of inorganic templates, with the columns parallel to the axis of the nanochannels, is considered desirable for applications such as production of molecular wires. Here, we evaluate experimentally the role of the rigidity of the LC columns in achieving such orientation in nanopores where the planar anchoring (i.e., columns parallel to wall surface) is enforced. We studied the columnar phase of several discotic compounds with increasing column rigidity in the following order: dendronized carbazole, hexakis(hexyloxy)triphenylene (HAT6), a 1:1 HAT6-trinitrofluorenone (TNF) complex, and a helicene derivative. Using 2-D X-ray diffraction, AFM, grazing incidence diffraction, and polarized microscopy, we observed that the orientation of the columns changes from circular concentric to axial with increasing column rigidity. Additionally, when the rigidity is borderline, increasing pore diameter can change the configuration from axial back to circular. We derive expressions for distortion free energy that suggest that the orientation is determined by the competition between, on the one hand, the distortion energy of the 2-d lattice and the mismatch of its crystallographic facets with the curved pore wall in the axial orientation and, on the other hand, the bend energy of the columns in the circular configuration. Furthermore, the highly detailed AFM images of the core of the disclinations of strength +1 and +1/2 in the center of the pore reveal that the columns spiral down to the very center of the disclination and that there is no amorphous or misaligned region at the core, as suggested previously.

Estimating the solubility of amorphous ibuprofen using nanoporous anodic aluminum oxide as a solidification template.

Amorphous phases of active pharmaceutical ingredients (APIs) generally possess greater solubility than the crystalline counterparts. This presents them as attractive candidates for enhancing the bioavailability of the sparingly soluble drugs, while the unstable nature of them makes it challenging to reliably evaluate their potential improvement in solubility and utilize them in drug formulations. We have investigated the anodic aluminum oxide (AAO) substrates with nanopores to establish a simple system to examine the solubility increase accompanied by the decrease of the API crystallinity, using ibuprofen (IBU) as a model compound. The fabricated AAO substrates had the average pore diameters: 25, 55, and 370 nm. The AAO substrates with nanopores allowed the solidification of IBU with lower crystallinity. Also, the release behavior directly from the AAO substrates made it possible to estimate the accompanying solubility increase. The amorphous IBU in the 25-nm pores possessed solubility about 6 times higher than the bulk crystalline phase. The present study demonstrated that the nanoporous AAO substrates could be utilized as a straightforward tool to investigate the solubility and stability of the amorphous phases of APIs.

Influence of surface property on the crystallization of hentetracontane under nanoscopic cylindrical confinement.

The crystallization behavior and the orientation of linear alkane hentetracontane (C41) confined in cylindrical nanoporous alumina templates with different surface energies were investigated by nonisothermal crystallization and X-ray diffraction. The surface of pristine nanoporous alumina was modified to have low surface energy by grafting with polydimethylsiloxane. In the pristine nanoporous alumina, C41 crystallized at two crystallization temperature ranges, lower than bulk, and exhibited the decreased Avrami exponents. C41 in the surface-modified nanoporous alumina showed the inhibition of crystallization at higher temperature range among the two crystallization temperature ranges but the enhancement of crystallization at much lower temperature ranges than in the pristine nanoporous alumina. It was clearly shown that those variations of crystallization behavior imply the surface effect on crystallization. The crystal orientation was also affected by surface-modification of the alumina template. The a-axis of orthorhombic C41 crystals in the pristine nanoporous alumina was preferentially oriented parallel to the pore axis, while b- and c-axes were perpendicular to the pore axis. C41 crystals in the surface-modified nanoporous alumina showed two types of orientation. One was identical to that in the pristine nanoporous alumina, and the other was the orientation that the crystals were tilted with respect to the c-axis as the (110) plane parallel to the pore axis.

Efficiency improvement of organic solar cells by tuning hole transport layer with germanium oxide.

Improving optical property is critical for optimizing the power conversion efficiency of organic solar cells. In the present research, we show that modification of poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) layer with GeO2 leads to 15% improvement of power conversion efficiency in a polymer solar cells through enhancement of short circuit currents. Modified PEDOT:PSS layer with optimized concentration of GeO2 assists active layer absorbing much light by playing a role of optical spacer. Using AFM and grazing incidence X-ray diffraction (GIXD) data, we also present the evidence that an addition of GeO2 does not affect crystallinity of active layer.

Simple fabrication of asymmetric high-aspect-ratio polymer nanopillars by reusable AAO templates.

We present a simple method of utilizing anodized aluminum oxide (AAO) as a reproducible template for fabricating high-aspect-ratio uniformly bent polymeric nanopillars that can be used as a physical adhesive. It is shown how to achieve straight high-aspect-ratio nanopillars with concepts of the work of adhesion and lateral collapse between polymer pillars without serious damage to the master template. With the support of manufacturing polymeric nanopillars from the reusable AAO, a simple route to asymmetric dry adhesive nanopillars bent by residual stresses was demonstrated.

Fabrication of antireflection and antifogging polymer sheet by partial photopolymerization and dry etching.

We present a simple method to fabricate a polymer optical sheet with antireflection and antifogging properties. The method consists of two consecutive steps: photocross-linking of UV-curable polyurethane acrylate (PUA) resin and reactive ion etching (RIE). During photopolymerization, the cured PUA film is divided into two domains of randomly distributed macromers and oligomers due to a relatively short exposure time of 20 s at ambient conditions. Using the macromer domain as an etch-mask, dry etching was subsequently carried out to remove the oligomer domain, leaving behind a nanoturf surface with tunable roughness. UV-vis spectroscopy measurements demonstrate that transmittance of a nanoturf surface is enhanced up to 92.5% as compared to a flat PUA surface (89.5%). In addition, measurements of contact angle (CA) reveal that the etched surface shows superhydrophilicity with a CA as small as 5 degrees. To seek potential applications, I-V characteristics of a thin film organic solar cell were measured under various testing conditions. It is shown that the efficiency can be increased to 2.9% when a nanoturf film with the surface roughness of 34.73 nm is attached to indium tin oxide (ITO) glass. More importantly, the performance is maintained even in the presence of water owing to superhydrophilic nature of the film.

Enhanced mobility of confined polymers.

Non-classical behaviour, brought about by a confinement that imposes spatial constraints on molecules, is opening avenues to novel applications. For example, carbon nanotubes, which show rapid and selective transport of small molecules across the nanotubes, have significant potential as biological or chemical separation materials for organic solvents or gaseous molecules. With polymers, when the dimensions of a confining volume are much less than the radius of gyration, a quantitative understanding of perturbations to chain dynamics due to geometric constraints remains a challenge and, with the development of nanofabrication processes, the dynamics of confined polymers have significant technological implications. Here, we describe a weak molecular-weight-dependent mobility of polymers confined within nanoscopic cylindrical pores having diameters smaller than the dimension of the chains in the bulk. On the basis of the chain configuration along the pore axis, the measured mobility of polymers in the confined geometry is much higher than the mobility of the unconfined chain. With the emergence of nanofabrication processes based on polymer flow, the unexpected enhancement in flow and reduction in intermolecular entanglements are of significant importance in the design and execution of processing strategies.

A simple fabrication route to a highly transparent super-hydrophobic surface with a poly(dimethylsiloxane) coated flexible mold.

A super-hydrophobic and highly transparent nanostructured film was fabricated via imprinting and conformally uniform chemical anchoring of poly(dimethylsiloxane) on a controlled nanoscopic dimension.

From homogeneous to heterogeneous nucleation of chain molecules under nanoscopic cylindrical confinement.

The crystallization of monodisperse linear polyethylene confined in nanoporous alumina is investigated with the calorimetric measurements. We observe a drastic change in crystallization behavior, specifically nucleation, with a decrease in the pore diameter. Crystallization in relatively larger pores with the diameters of 62 and 110 nm occurs at lower temperatures within a very narrow range, whereas crystallization in smaller pores with diameters of 15-48 nm occurs at a higher and broad range of temperatures. Nucleation and crystallization kinetics in nanopores is discussed based on classical nucleation theory as well as the Avrami theory.

Capillary filling of anodized alumina nanopore arrays.

The filling behavior of a room temperature solvent, perfluoromethylcyclohexane, in approximately 20 nm nanoporous alumina membranes was investigated in situ with small angle x-ray scattering. Adsorption in the pores was controlled reversibly by varying the chemical potential between the sample and a liquid reservoir via a thermal offset, DeltaT. The system exhibited a pronounced hysteretic capillary filling transition as liquid was condensed into the nanopores. These results are compared with Kelvin-Cohan theory, with a modified Derjaguin approximation, as well as with predictions by Cole and Saam.

Synthesis of gold nanoparticles from gold(I)-alkanethiolate complexes with supramolecular structures through electron beam irradiation in TEM.

Monodisperse gold nanoparticles were prepared via electron beam irradiation of Au(I)-SR (R = -CnH2n+1) polymers with highly ordered supramolecular structures in transmission electron microscopy. The Au(I)-SR polymers were synthesized simply by mixing LiAuCl4 and an excess amount of alkanethiol in tetrahydrofuran. The sizes of the gold nanoparticles were controlled by changing the length of the alkyl group or by adjusting the energy of the electron beam.