Defect Engineering of Graphene for Dynamic Reliability.

The interface between two-dimensional (2D) materials and soft, stretchable polymeric substrates is a governing criterion in proposed 2D materials-based flexible devices. This interface is dominated by weak van der Waals forces and there is a large mismatch in elastic constants between the contact materials. Under dynamic loading, slippage, and decoupling of the 2D material is observed, which then leads to extensive damage propagation in the 2D lattice. Herein, graphene is functionalized through mild and controlled defect engineering for a fivefold increase in adhesion at the graphene-polymer interface. Adhesion is characterized experimentally using buckling-based metrology, while molecular dynamics simulations reveal the role of individual defects in the context of adhesion. Under in situ cyclic loading, the increased adhesion inhibits damage initiation and interfacial fatigue propagation within graphene. This work offers insight into achieving dynamically reliable and robust 2D material-polymer contacts, which can facilitate the development of 2D materials-based flexible devices.

Dipole Engineering through the Orientation of Interface Molecules for Efficient InP Quantum Dot Light-Emitting Diodes.

InP-based quantum dot (QD) light-emitting diodes (QLEDs) provide a heavy-metal-free route to size-tuned LEDs having high efficiency. The stability of QLEDs may be enhanced by replacing organic hole-injection layers (HILs) with inorganic layers. However, inorganic HILs reported to date suffer from inefficient hole injection, the result of their shallow work functions. Here, we investigate the tuning of the work function of nickel oxide (NiOx) HILs using self-assembled molecules (SAMs). Density functional theory simulations and near-edge X-ray absorption fine structure put a particular focus onto the molecular orientation of the SAMs in tuning the work function of the NiOx HIL. We find that orientation plays an even stronger role than does the underlying molecular dipole itself: SAMs having the strongest electron-withdrawing nitro group (NO2), despite having a high intrinsic dipole, show limited work function tuning, something we assign to their orientation parallel to the NiOx surface. We further find that the NO2 group─which delocalizes electrons over the molecule by resonance─induces a deep lowest unoccupied molecular orbital level that accepts electrons from QDs, producing luminescence quenching. In contrast, SAMs containing a trifluoromethyl group exhibit an angled orientation relative to the NiOx surface, better activating hole injection into the active layer without inducing luminescence quenching. We report an external quantum efficiency (EQE) of 18.8%─the highest EQE among inorganic HIL-based QLEDs (including Cd-based QDs)─in InP QLEDs employing inorganic HILs.

A Carbon-Based Biosensing Platform for Simultaneously Measuring the Contraction and Electrophysiology of iPSC-Cardiomyocyte Monolayers.

Heart beating is triggered by the generation and propagation of action potentials through the myocardium, resulting in the synchronous contraction of cardiomyocytes. This process highlights the importance of electrical and mechanical coordination in organ function. Investigating the pathogenesis of heart diseases and potential therapeutic actions in vitro requires biosensing technologies which allow for long-term and simultaneous measurement of the contractility and electrophysiology of cardiomyocytes. However, the adoption of current biosensing approaches for functional measurement of in vitro cardiac models is hampered by low sensitivity, difficulties in achieving multifunctional detection, and costly manufacturing processes. Leveraging carbon-based nanomaterials, we developed a biosensing platform that is capable of performing on-chip and simultaneous measurement of contractility and electrophysiology of human induced pluripotent stem-cell-derived cardiomyocyte (iPSC-CM) monolayers. This platform integrates with a flexible thin-film cantilever embedded with a carbon black (CB)-PDMS strain sensor for high-sensitivity contraction measurement and four pure carbon nanotube (CNT) electrodes for the detection of extracellular field potentials with low electrode impedance. Cardiac functional properties including contractile stress, beating rate, beating rhythm, and extracellular field potential were evaluated to quantify iPSC-CM responses to common cardiotropic agents. In addition, an in vitro model of drug-induced cardiac arrhythmia was established to further validate the platform for disease modeling and drug testing.

Purification, structural characterization, and anticoagulant activity evaluation of chondroitin sulfate from codfish (Gadus macrocephalus) bones.

Chondroitin sulfate (CCS) was purified from discarded codfish (Gadus macrocephalus) bones, and its chemical structure and anticoagulant activity were assessed. CCS was obtained via enzymatic lysis and ion-exchange column chromatography, with a yield of approximately 0.15%. High-performance gel performance chromatography revealed CCS to be a largely homogeneous polysaccharide with a relatively low molecular weight of 12.3 kDa. FT-IR spectroscopy, NMR spectroscopy, and SAX-HPLC indicated that CCS was composed of monosulfated disaccharides (ΔDi4S 73.85% and ΔDi6S 19.06%) and nonsulfated disaccharides (ΔDi0S 7.09%). In vitro anticoagulation analyses revealed that CCS was able to significantly prolong activated partial thromboplastin time (APTT) and thrombin time (TT) (p < 0.05). At a CCS concentration of 5 µg/mL and 25 µg/mL, APTT and TT were approximately 1.08 and 1.12 times higher, respectively, compared to the negative control group. The results indicated that CCS might offer value as a dietary fiber supplement with the potential to prevent the incidence of coagulation-related thrombosis.

Friction of magnetene, a non-van der Waals 2D material.

Two-dimensional (2D) materials are known to have low-friction interfaces by reducing the energy dissipated by sliding contacts. While this is often attributed to van der Waals (vdW) bonding of 2D materials, nanoscale and quantum confinement effects can also act to modify the atomic interactions of a 2D material, producing unique interfacial properties. Here, we demonstrate the low-friction behavior of magnetene, a non-vdW 2D material obtained via the exfoliation of magnetite, showing statistically similar friction to benchmark vdW 2D materials. We find that this low friction is due to 2D confinement effects of minimized potential energy surface corrugation, lowered valence states reducing surface adsorbates, and forbidden low-damping phonon modes, all of which contribute to producing a low-friction 2D material.

Multication perovskite 2D/3D interfaces form via progressive dimensional reduction.

Many of the best-performing perovskite photovoltaic devices make use of 2D/3D interfaces, which improve efficiency and stability - but it remains unclear how the conversion of 3D-to-2D perovskite occurs and how these interfaces are assembled. Here, we use in situ Grazing-Incidence Wide-Angle X-Ray Scattering to resolve 2D/3D interface formation during spin-coating. We observe progressive dimensional reduction from 3D to n = 3 → 2 → 1 when we expose (MAPbBr3)0.05(FAPbI3)0.95 perovskites to vinylbenzylammonium ligand cations. Density functional theory simulations suggest ligands incorporate sequentially into the 3D lattice, driven by phenyl ring stacking, progressively bisecting the 3D perovskite into lower-dimensional fragments to form stable interfaces. Slowing the 2D/3D transformation with higher concentrations of antisolvent yields thinner 2D layers formed conformally onto 3D grains, improving carrier extraction and device efficiency (20% 3D-only, 22% 2D/3D). Controlling this progressive dimensional reduction has potential to further improve the performance of 2D/3D perovskite photovoltaics.

Protein corona-guided tumor targeting therapy via the surface modulation of low molecular weight PEG.

The discovery of protein corona (PC) formed on the surface of nanomaterials has promoted research on PC regulation to guide the biological behavior of nanomaterials in vivo. Different from changing the size, shape, and surface charge of nanoparticles, we propose to control the nature of PC by adjusting the molecular weight of low molecular weight polyethylene glycol (LMW PEG, not more than 1000 Da) on the surface of the particles. After excluding the influence of physicochemical factors of PEGylated gold nanoparticles (GNPs), different proteins on the surface of PEGylated GNPs were separated and identified after incubation with human plasma. It is noted that GNP-550 bearing PEG chains of 550 Da absorbed more transferrin responsible for tumor targeting than the other two particles, i.e., GNP-350 and GNP-1000. To validate our speculation, doxorubicin (Dox) was inserted between GNPs and PEGs to explore the cellular and animal studies of Dox-conjugated GNPs. Interestingly, Dox-containing Conj-550 also showed the highest intracellular uptake, cytotoxicity, and apoptosis against HepG2 cells, as well as the best tumor targeting effect and antitumor efficacy in Heps-bearing mice. This protein corona-guided tumor targeting therapy by transferrin provides a new perspective on the function modulation of nanomedicine via LMW PEGs.

Fracture and Fatigue of Al2O3-Graphene Nanolayers.

Al2O3-graphene nanolayers are widely used within integrated micro/nanoelectronic systems; however, their lifetimes are largely limited by fracture both statically and dynamically. Here, we present a static and fatigue study of thin (1-11 nm) free-standing Al2O3-graphene nanolayers. A remarkable fatigue life of greater than one billion cycles was obtained for films <2.2 nm thick under large mean stress levels, which was up to 3 orders of magnitude longer than that of its thicker (11 nm) counterpart. A similar thickness dependency was also identified for the elastic and static fracture behavior, where the enhancement effect of graphene is prominent only within a thickness of ∼3.3 nm. Moreover, plastic deformation, manifested by viscous creep, was observed and appeared to be more substantial for thicker films. This study provides mechanistic insights on both the static and dynamic reliability of Al2O3-graphene nanolayers and can potentially guide the design of graphene-based devices.

Graphene fatigue through van der Waals interactions.

Graphene is often in contact with other materials through weak van der Waals (vdW) interactions. Of particular interest is the graphene-polymer interface, which is constantly subjected to dynamic loading in applications, including flexible electronics and multifunctional coatings. Through in situ cyclic loading, we directly observed interfacial fatigue propagation at the graphene-polymer interface, which was revealed to satisfy a modified Paris' law. Furthermore, cyclic loading through vdW contact was able to cause fatigue fracture of even pristine graphene through a combined in-plane shear and out-of-plane tear mechanism. Shear fracture was found to mainly initiate at the fold junctions induced by cyclic loading and propagate parallel to the loading direction. Fracture mechanics analysis was conducted to explain the kinetics of an exotic self-tearing behavior of graphene during cyclic loading. This work offers mechanistic insights into the dynamic reliability of graphene and graphene-polymer interface, which could facilitate the durable design of graphene-based structures.

Enhanced sensitivity of nanoscale subsurface imaging by photothermal excitation in atomic force microscopy.

Photothermal excitation of the cantilever for use in subsurface imaging with atomic force microscopy was compared against traditional piezoelectric excitation. Photothermal excitation alleviates issues commonly found in traditional piezoelectrics such as spurious resonances by producing clean resonance peaks through direct cantilever excitation. A calibration specimen consisting of a 3 × 3 array of holes ranging from 200 to 30 nm etched into silicon and covered by graphite was used to compare these two drive mechanisms. Photothermal excitation exhibited a signal-to-noise ratio as high as four times when compared to piezoelectric excitation, utilizing higher eigenmodes for subsurface imaging. The cleaner and sharper resonance peaks obtained using photothermal excitation revealed all subsurface holes down to 30 nm through 135 nm of graphite. In addition, we demonstrated the ability of using photothermal excitation to detect the contact quality variation and evolution at graphite-polymer interfaces, which is critical in graphene-based nanocomposites, flexible electronics, and functional coatings.

Fatigue of graphene.

Materials can suffer mechanical fatigue when subjected to cyclic loading at stress levels much lower than the ultimate tensile strength, and understanding this behaviour is critical to evaluating long-term dynamic reliability. The fatigue life and damage mechanisms of two-dimensional (2D) materials, of interest for mechanical and electronic applications, are currently unknown. Here, we present a fatigue study of freestanding 2D materials, specifically graphene and graphene oxide (GO). Using atomic force microscopy, monolayer and few-layer graphene were found to exhibit a fatigue life of more than 109 cycles at a mean stress of 71 GPa and a stress range of 5.6 GPa, higher than any material reported so far. Fatigue failure in monolayer graphene is global and catastrophic without progressive damage, while molecular dynamics simulations reveal this is preceded by stress-mediated bond reconfigurations near defective sites. Conversely, functional groups in GO impart a local and progressive fatigue damage mechanism. This study not only provides fundamental insights into the fatigue enhancement behaviour of graphene-embedded nanocomposites, but also serves as a starting point for the dynamic reliability evaluation of other 2D materials.

Nanomechanical elasticity and fracture studies of lithium phosphate (LPO) and lithium tantalate (LTO) solid-state electrolytes.

All-solid-state batteries (ASSBs) have attracted much attention due to their enhanced energy density and safety as compared to traditional liquid-based batteries. However, cyclic performance depreciates due to microcrack formation and propagation at the interface of the solid-state electrolytes (SSEs) and electrodes. Herein, we studied the elastic and fracture behavior of atomic layer deposition (ALD) synthesized glassy lithium phosphate (LPO) and lithium tantalate (LTO) thin films as promising candidates for SSEs. The mechanical behavior of ALD prepared SSE thin films with a thickness range of 5 nm to 30 nm over suspended single-layer graphene was studied using an atomic force microscope (AFM) film deflection technique. Scanning transmission electron microscopy (STEM) coupled with AFM was used for microstructural analysis. LTO films exhibited higher stiffness and higher fracture forces as compared to LPO films. Fracture in LTO films occurred directly under the indenter in a brittle fashion, while LPO films failed by a more complex fracture mechanism including significant plastic deformation prior to the onset of complete fracture. The results and methodology described in this work open a new window to identify the potential influence of SSEs mechanical performance on their operation in flexible ASSBs.

Investigating the detection limit of subsurface holes under graphite with atomic force acoustic microscopy.

The subsurface imaging capabilities of atomic force acoustic microscopy (AFAM) was investigated by imaging graphite flakes suspended over holes in a silicon dioxide substrate. The graphite thickness and the hole size were varied to determine the detection limit on the maximum graphite thickness and the smallest detectable hole size. Parameters including operating frequency, eigenmode, contact force, and cantilever stiffness were investigated for their influence of defect detection. AFAM was reliably able to detect 2.5 µm diameter holes through a maximum graphite thickness of 570 nm and sub 100 nm holes through 140 nm of graphite. The smallest detectable defect size was a 50 nm hole covered by an 80 nm thick graphite flake. Increasing the graphite thickness and decreasing the hole size both resulted in a decrease in subsurface contrast. However, the non-linear trend observed from increasing the graphite thickness indicates thickness has a greater effect on subsurface defect detection than variations in defect size. Through investigating various parameters, we have found certain cases to increase the observed contrast of the embedded subsurface holes, however the smallest detectable defect size remained the same. This technique's ability to reveal sub 100 nm defects buried under graphite has previously only been demonstrated in much softer polymer systems.

Electrochemical Detection for Uric Acid Based on ß-Lactoglobulin-Functionalized Multiwall Carbon Nanotubes Synthesis with PtNPs Nanocomposite.

In this work, a simple and highly selective electrochemical biosensor for determination of uric acid (UA) is synthesized by using ß-lactoglobulin (BLG)-functionalized multiwall carbon nanotubes (MWCNTs) and a platinum nanoparticles (PtNPs) nanocomposite. Urate oxidase (UOx) can oxidize uric acid to hydrogen peroxide and allantoin, which provides a good opportunity for electrochemical detection for UA. Under the optimized conditions, the current changes by the UOx/Bull Serum Albumin (BSA)/BLG-MWCNTs-PtNPs/Glassy Carbon (GC) electrode with the electrochemical method was proportional to the concentration of UA. According to experiments, we obtained a linear response with a concentration range from 0.02 to 0.5 mM and achieved a high sensitivity of 31.131 µA mM-1 and a low detection limit (0.8 µΜ). Meanwhile, nanoparticles improved the performance of the biosensor and combined with BLG not only prevented the accumulation of composite nanomaterials, but also provided immobilization of uricase through electrostatic adsorption. This improves the stability and gives the constructed electrode sensing interface superior performance in UA detection.

A novel group of avian Avastrovirus in domestic geese, China.

Using an ORF1b-based astrovirus-specfic reverse transcription (RT)-PCR assay, a novel astrovirus-like was detected from domestic geese in China. Pairwise comparisons and phylogenetic analyzes suggested that a novel group of goose astrovirus, different with previously known astroviruses in the genus Avastrovirus, was found circulating in geese. This study has expanded our understanding about the role of domestic waterfowls as reservoirs for diverse astroviruses.

Performance of Doxorubicin-Conjugated Gold Nanoparticles: Regulation of Drug Location.

Drug-conjugated gold nanoparticles (GNPs), which are generally constructed with many molecules of thiol-terminated polyethylene glycol (PEG)-drug decorated on their surfaces via a thiol-Au covalent bond, are promising and efficient nanoprodrugs. However, because of the exposure of the hydrophobic drug molecules on the surface of the conjugate, in vivo stability, opsonization, and subsequent inefficient therapy become the main issues of this system. To solve these problems without complicating the structures of gold conjugates, herein we propose a method to change the relative position of PEG and the drug. A novel gold conjugate (GNP-NHN═Dox-mPEG) with doxorubicin (Dox) shielded by PEGylation on the surface of GNPs is designed. It demonstrates improved solubility, stability, and dispersion and achieves a two-step stimulus-responsive drug release in response to an acidic environment in lysosomes and then esterase in the cytoplasm. This unique manner of release enables the cytoplasm to act as a reservoir for sustained drug delivery into the nucleus to improve antitumor efficacy in vivo. The intratumoral drug concentrations of the conjugate reach 14.4 ± 1.4 µg/g at 8 h, a two-fold increase in the drug concentration compared with that of the doxorubicin hydrochloride group. This molecular design and regulation approach is facile but important in modulating the in vivo performance of nanovehicles and demonstrates its vital potential in developing effective nanoparticle-based drug delivery agents.

Development of a restriction length polymorphism combined with direct PCR technique to differentiate goose and Muscovy duck parvoviruses.

A restriction fragment length polymorphism combined with direct PCR technique to differentiate goose and Muscovy duck parvoviruses (GPV and MDPV) was developed based on comparison of the NS gene of GPV and MDPV. Both GPV and MDPV genomic DNA can be amplified with 641 bp using the specific PCR primers. The PCR fragments can be cut into 463 bp and 178 bp only in the case of MDPV-derived PCR products, whereas the GPV-derived PCR products cannot. The method established in this study can be used to differentiate GPV and MDPV with high specificity and precision, by using a direct PCR kit and QuickCut enzyme, as quickly as conventional PCR.

[Polymer-modified gold nanoparticles for cancer therapy].

Polymer-modified gold nanoparticles, which are more stable, less toxic to human body and have improved biocompatibility, have received intensive attention in biomedical applications, which can be used as or construct various therapy agents or carriers in cancer treatment. This review summarizes the current investigation of polymer-modified gold nanoparticles on their cancer treatment applications.

[High output of a Trametes laccase in Pichia pastoris and characterization of recombinant enzymes].

A laccase gene (lacD) from the basidiomycete Trametes sp. 420 was heterologously expressed in Pichia pastoris in two ways, resulting in two recombinant enzymes of rLacDx with native N-terminus and rLacDe with eight additional amino acid residues at N-terminus. The yields of rLacDx and rLacDe in shaken-flask cultures after an 18-day growth were 1.21 x 10(5) u/L and 7.38 x 10(4) u/L, respectively, as determined with 2,2'-azinobis(3-ethylbenzothia-zoline- 6-sulfonic acid) (ABTS) as substrate. The yield of rLacDx was further increased to 2.39 x 10(5) u/L under high-density fermentation while the production process was decreased to 7.5 days. In addition, rLacDx and rLacDe exhibited similar enzymatic characters in oxidizing substrate guaiacol, and were stable at 50 degrees C and at a pH range from 3 to 10. However, the specific activity of rLacDx (1761 u/mg) for ABTS was higher than that of rLacDe (1122 u/mg), and the apparent Km value of rLacDx (427 microM) was less than that of rLacDe (604 microM).