Postoperatively Noninvasive Optogenetic Stimulation via Upconversion Nanoparticles Enhancing Sciatic Nerve Repair.

The efficacy of electrical stimulation facilitating peripheral nerve regeneration is evidenced extensively, while the associated secondary damage resulting from repeated electrode invasion and indiscriminate stimulation is inevitable. Here, we present an optogenetics strategy that utilizes upconversion nanoparticles (UCNPs) to convert deeply penetrating near-infrared excitation into blue emission, which activates an adeno-associated virus-encoding ChR2 photoresponsive ion channel on cell membranes. The induced Ca2+ flux, similar to the ion flux in the electrical stimulation approach, efficiently regulates viability and proliferation, secretion of nerve growth factor, and neural function of RSC96 cells. Furthermore, deep near-infrared excitation is harnessed to stimulate autologous Schwann cells in situ via a UCNP-composited scaffold, which enhances nerve sprouting and myelination, consequently promoting functional recovery, electrophysiological restoration, and reinnervation of damaged nerves. This developed postoperatively noninvasive optogenetics strategy presents a novel, minimally traumatic, and enduring therapeutic stimulus to effectively promote peripheral nerve repair.

Conformal sulfidation of HKUST-1 for constructing porous Cu2S/CuO octahedrons realizing highly sensitive non-enzymatic glucose detection.

Metal-organic frameworks (MOFs) are believed to be promising precursors for constructing novel and efficient catalysts for glucose sensing. Herein, HKUST-1 precursors are first fabricated using a one-pot hydrothermal approach, and then HKUST-1 is converted into porous Cu2S/CuO octahedrons through conformal sulfidation with the help of OH-ions. The as-obtained Cu2S/CuO composite can provide rich electrochemical active sites and promoted electric transfer kinetics. Benefiting from these combined merits, the as-fabricated Cu2S/CuO composite is confirmed to be a high-performance catalyst, with high sensitivities of 8269.45 and 4140.82µA mM-1cm-2in the corresponding ranges of 0.05 ∼ 0.6 mM and 0.6 ∼ 1.2 mM, respectively. Moreover, the as-prepared electrode materials possess good anti-interference ability, reproducibility and long-term stability. This work opens up new avenues for the design and preparation of transition metal sulfide composites.

Ratiometric fluorescence detection of dopamine based on copper nanoclusters and carbon dots.

Nanoclusters for fluorescence detection are generally comprised of rare and expensive noble metals, and the nanoclusters based on more affordable transition metal have attracted increasing attention. This study designed a ratiometric fluorescent probe to detect dopamine (DA), an important neurotransmitter. With carbon dots encapsulated within silica (CDs@SiO2) as the reference, the emitted reference signal was almost unchanged due to the protection of inert silicon shell. Meanwhile, copper nanoclusters modified with 3-aminophenyl boronic acid (APBA-GSH-CuNCs) provided the sensing signal, in which the phenylboric acid could specifically recognize the cis-diol structure of DA, and caused the fluorescence quenching by photoinduced electron transfer. This dual emission ratiometric fluorescent probe exhibited high sensitivity and anti-interference, and was able to selectively responded to DA with a linear range of 0-1.4 mM, the detection limit of 5.6 nM, and the sensitivity of 815 mM-1. Furthermore, the probe successfully detected DA in human serum samples, yielding recoveries ranging from 92.5% to 102.7%. Overall, this study highlights the promising potential of this ratiometric probe for detecting DA.

Dendritic Oligoethylenimine Decorated Liposome with Augmented Corneal Retention and Permeation for Efficient Topical Delivery of Antiglaucoma Drugs.

The topically administered glaucoma medications usually encounter serious precorneal drug loss and low corneal penetration, leading to a low bioavailability. In addition, due to the complexity of glaucoma etiology, a single medication is often insufficient. In this work, we report a novel dendritic oligoethylenimine decorated liposome for codelivery of two antiglaucoma drugs, latanoprost and timolol. The liposome showed a uniform nanoscopic particle size, positive surface charge, and excellent dual-drug loading capacity. A prolonged precorneal retention is observed by using this liposomal delivery system. This liposomal delivery system presents increased cellular uptake and tight junctions opening capacity, contributing respectively to the transcellular and paracellular permeation, thereby enhancing the trans-corneal transportation. Following topical administration of one eye drop in brown Norway rats, the dual-drug-loaded liposome formulation resulted in a sustained and effective intraocular pressure reduction as long as 5 days, without inducing ocular inflammation, discomfort, and tissue damage.

Quasi-aligned Cu2S/Cu(OH)2nanorod arrays anchored on Cu foam as self-supported electrode for non-enzymatic glucose detection.

Self-supported Cu2S/Cu(OH)2composite nanorods for highly sensitive non-enzymatic glucose sensing werein situgrown on Cu foam by simple hydrothermal treatment of aligned Cu(OH)2nanorods. The physicochemical and electrochemical properties of the as-fabricated Cu2S/Cu(OH)2composite nanorods were characterized by scanning electron microscopy, transmission electron microscopy, x-ray diffraction, Raman spectroscope, x-ray photoelectron spectroscope, cyclic voltammetry, electrochemical impedance spectroscopy, amperometrici-tmeasurements. The mechanism of the composite nanorods produced on conductive substrates was also explored. The electrode exhibits a sensitivity of 9626.88µA mM-1cm-2towards glucose with good anti-interference ability, indicating it a promising electrode material for the enhanced non-enzymatic glucose detection.

Reversing the immunosuppressive microenvironment with reduced redox level by microwave-chemo-immunostimulant Ce-Mn MOF for improved immunotherapy.

BACKGROUNDS: Reversing the immunosuppressive tumor microenvironment (TME) in the tumor is widely deemed to be an effective strategy to improve immune therapy. In particular, the redox balance in TME needs to be well controlled due to its critical role in mediating the functions of various cells, including cancer cells and immune-suppressive cells. RESULTS: Here, we propose an efficient strategy to reshape the redox homeostasis to reverse immunosuppressive TME. Specifically, we developed a microwave-chemo-immunostimulant CMMCP to promote the infiltration of the tumor-T cells by simultaneously reducing the reactive oxygen species (ROS) and glutathione (GSH) and improving the oxygen (O2) levels in TME. The CMMCP was designed by loading chemotherapy drugs cisplatin into the bimetallic Ce-Mn MOF nanoparticles coated with polydopamine. The Ce-Mn MOF nanoparticles can effectively improve the catalytic decomposition of ROS into O2 under microwave irradiation, resulting in overcoming hypoxia and limited ROS generation. Besides, the activity of intracellular GSH in TME was reduced by the redox reaction with Ce-Mn MOF nanoparticles. The reprogrammed TME not only boosts the immunogenic cell death (ICD) induced by cisplatin and microwave hyperthermia but also gives rise to the polarization of pro-tumor M2-type macrophages to the anti-tumor M1-type ones. CONCLUSION: Our in vivo experimental results demonstrate that the microwave-chemo-immunostimulant CMMCP significantly enhances the T cell infiltration and thus improves the antitumor effect. This study presents an easy, safe, and effective strategy for a whole-body antitumor effect after local treatment.

Fluorescent hollow ZrO2@CdTe nanoparticles-based lateral flow assay for simultaneous detection of C-reactive protein and troponin T.

Highly fluorescent hollow ZrO2@CdTe nanoparticles (NPs) were synthesized efficiently via the hydrothermal method. By changing the hydrothermal time of ZrO2@CdTe NP, the peaks of fluorescence spectra measured at fluorescent excitation of 330 nm were at 540 nm, 590 nm, and 640 nm, respectively. Hollow ZrO2 NPs have a uniform core-shell structure with the size of 178 ± 10 nm and shell of 19 ± 4 nm. The as-prepared yellow-ZrO2@CdTe NPs were used to develop lateral flow assay (LFA) for the sensitive and qualitative detection of C-reactive protein (CRP). The visual limit of detection of the LFA for the CRP antigen was 1 µg/L within 20 min, which is 1000-fold lower than that of colloidal gold-based LFA. In addition, a multiplex lateral flow assay (mLFA) was developed using the as-prepared green and red-ZrO2@CdTe NPs for the simultaneous, specific, sensitive, and qualitative detection of CRP and troponin T (cTnT). The visual limits of detection of CRP and cTnT in mLFA were 10 µg/L and 0.1 mg/L, respectively. The excellent performance of ZrO2@CdTe NPs should facilitate their application in point-of-care technology for the detection of other biomarkers.

Hierarchically porous CuO spindle-like nanosheets grown on a carbon cloth for sensitive non-enzymatic glucose sensoring.

Herein, porous CuO spindle-like nanosheets were fabricated on a carbon cloth using a facile hydrothermal method, and surface morphology, microstructure, and glucose sensing performance were studied. The porous spindle-like nanosheets are constructed by nanoparticles and slit-like pores, exhibiting a hierarchical structure. When used for non-enzymatic glucose sensoring, the obtained CuO nanosheet electrode exhibits a wide linear range from 0.05 to 3.30 mM, a high sensitivity of 785.2 µA mM-1 cm-2 and a low detection limit of 0.22 µM (S/N = 3). Besides, good selectivity, stability, and reproducibility for glucose detection indicate a promising application of CuO nanosheet electrodes as non-enzymatic glucose sensors.

Co(OH)2 nanosheets decorated Cu(OH)2 nanorods for highly sensitive nonenzymatic detection of glucose.

Co(OH)2 nanosheets/Cu(OH)2 nanorods composite electrodes for non-enzymatic glucose detection were fabricated by electrodepositing Co(OH)2 nanosheets on Cu(OH)2 nanorods substrate grown directly on the copper sheet via a simple one-step reaction. The Co(OH)2 nanosheets/Cu(OH)2 nanorods composite electrode was characterized by scanning electron microscopy, energy dispersive x-ray spectroscopy, x-ray diffraction and x-ray photoelectron spectroscopy. The glucose sensing performance of the composite electrode was investigated by cyclic voltammetry and chronoamperometry. The composite electrode shows high sensitivity of 2366 µA mM-1 cm-2 up to 2 mM with a lower detection limit of 0.17 mM (S/N = 3). The composite electrode is highly selective to glucose in the presence of various substances that always co-exist with glucose in real blood samples. The response of the composite towards human blood serum was in good agreement with that of commercially available glucose sensors, suggesting that a promising electrode material for highly sensitive and selective non enzymatic detection of glucose can be envisioned.

Method of calculating porosity based on M44 element images of the Mueller matrix.

As a drug carrier, the porosity of porous electrospun fiber can greatly affect its drug loading ability and stability. In this work, a method to calculate the porosity of porous electrospun fiber with a polarization micrograph is described. Different porosities of porous electrospun fibers were measured by scanning electron microscope images and transmission Mueller matrix M44 element images, respectively. Mueller matrix M44 element images were obtained after polarization micrograph and normalization. The pore areas of M44 images were extracted by region growing, and the contour parts were obtained by performing morphological operation on pore areas. The porosity calculated by the polarization microscope image is in good consistency with that measured by the scanning electron microscope. Our results will promote practical application of electrospun porous fibers in the early stage of screening a large number of porous materials in the biomedicine field.

The sp2 character of new two-dimensional AsB with tunable electronic properties predicted by theoretical studies.

As a competitive candidate for replacing graphene that possesses an appropriate fundamental bandgap, structural stability and tunable electronic properties, the recently synthesized honeycomb arsenene has rekindled much enthusiasm in the area of two-dimensional materials. By using first-principles calculations and acoustic phonon limited deformation potential theory, we identify a compelling two-dimensional electronic material, single-layer AsB, which is a direct-gap semiconductor with a bandgap (Eg) of 1.18 eV, almost the same as that of bulk silicon. The orbital projected band structure and electron density as well as partial density of states demonstrate that the frontier state of the planar atomic structural AsB is sp2 orbital hybridization, which is distinct from that of buckled arsenene monolayers. Layer thickness, stacking order and strain are effective ways to tune the frontier states, and thus the band structure and bandgap of AsB. Moreover, thicker AsB exhibits one-layer localized states in the AB-stacking structure, which is in sharp contrast to other layered materials such as MoS2 and phosphorene. Benefiting from the non-localized pz orbital and larger elastic modulus, the carrier mobility of AsB is in the range of 103-104 cm2 V-1 s-1, which is much higher than that of pristine arsenene and some other analogues. Our work provides an effective way to tailor the electronic properties of 2D arsenene, which may open up new avenues for applying it in future nano-optoelectronics and electronics.

Superconductivity in an organometallic compound.

Organometallic compounds constitute a very large group of substances that contain at least one metal-to-carbon bond in which the carbon is part of an organic group. They have played a major role in the development of the science of chemistry. These compounds are used to a large extent as catalysts (substances that increase the rate of reactions without themselves being consumed) and as intermediates in the laboratory and in industry. Recently, novel quantum phenomena such as topological insulators and superconductors were also suggested in these materials. However, there has been no report on the experimental exploration of the topological state. Evidence for superconductivity from the zero-resistivity state in any organometallic compound has not been achieved yet, though much effort has been made. Here we report the experimental realization of superconductivity with a critical temperature of 3.6 K in a potassium-doped organometallic compound, i.e. tri-o-tolylbismuthine, with evidence of both the Meissner effect and the zero-resistivity state through dc and ac magnetic susceptibility measurements. The obtained superconducting parameters classify this compound as a type-II superconductor. The benzene ring is identified to be the essential superconducting unit in such a phenyl organometallic compound. The superconducting phase and its composition are determined by combined studies of X-ray diffraction and theoretical calculations as well as Raman spectroscopy measurements. These findings enrich the applications of organometallic compounds in superconductivity and add a new electron-acceptor family of organic superconductors. This work also points to a large pool for finding superconductors from organometallic compounds.

Charge transfer effect on Raman shifts of aromatic hydrocarbons with three phenyl rings from ab initio study.

To clarify the charge transfer effect on Raman spectra of aromatic hydrocarbons, we investigate the Raman shifts of phenanthrene, p-terphenyl, and anthracene and their negatively charged counterparts by using density functional theory. For the three molecules, upon charge increasing, the computed Raman peaks generally shift down with the exception of a few shifting up. The characteristic Raman modes in the 0-1000 cm-1 region persist up, while some high-frequency ones change dramatically with three charges transferred. The calculated Raman shifts for one- and two-electron transfer are in agreement with the measured Raman spectra, and in accordance to the stoichiometric ratios 1:1 and 2:1 of the metal atom and aromatic hydrocarbon molecule in recent experimental and theoretical studies. Our theoretical results provide the fundamental information to elucidate the Raman shifts and the stoichiometric ratios for alkali-metal-doped aromatic hydrocarbons.

Superconductivity at 3.5 K and/or 7.2 K in potassium-doped triphenylbismuth.

We develop a two-step synthesis method-ultrasound treatment and low temperature annealing to explore superconductivity in potassium-doped triphenylbismuth, which is composed of one bismuth atom and three phenyl rings. The combination of dc and ac magnetic measurements reveals that one hundred percent of synthesized samples exhibit superconductivity at 3.5 K and/or 7.2 K at ambient pressure. The magnetization hysteresis loops provide a strong piece of evidence of type-II superconductors. It is found that the doped materials crystallize into the triclinic P1 structure, with a mole ratio of 4:1 between potassium and triphenylbismuth. Both the calculated electronic structure and measured Raman spectra indicate that superconductivity is realized by transferring electrons from the K-4s to C-2p orbital. Our study opens an encouraging window for the search of organic superconductors in organometallic molecules.

One-pot synthesis of γ-MnS/reduced graphene oxide with enhanced performance for aqueous asymmetric supercapacitors.

In this work, γ-MnS/reduced graphene oxide composites (γ-MnS/rGO) were prepared using a facile one-pot hydrothermal method. As an electrode material for supercapacitors, the γ-MnS/rGO-60 composite obtained under dosages of graphene oxide  was 60 mg and exhibited an enhanced specific capacitance of 547.6 F g-1 at a current density of 1 A g-1, and outstanding rate capability (65% capacitance retention at 20 A g-1), with superior cycling stability and electrochemical reversibility. An asymmetric supercapacitor assembled from γ-MnS/rGO-60 composite and rGO (γ-MnS/rGO-60//rGO) showed a voltage window of 0-1.6 V and delivered a high energy density of 23.1 W h kg-1 at a power density of 798.8 W kg-1, and 15.9 W h kg-1 at 4.5 kW kg-1. Moreover, two such 1.0 × 1.0 cm2 devices connected together in series easily light up a group of LED lights, showing its potential practical application as an attractive energy storage device.

Room temperature multiferroicity in hydrogenated triapentafulvalene and pentaheptafulvalene oligomers.

To search for new organic multiferroics, we perform a systematic study on the magnetic and ferroelectric properties of fused triapentafulvalene and pentaheptafulvalene oligomers (n = 2-6), by using the density functional theory and quantum Monte Carlo method. It is found that the oligomers without hydrogenation always lie in the spin singlet (nonmagnetic) state, while a selective hydrogenation of carbon atoms at the ends of oligomers can result in the spin triplet (ferromagnetic) state, which is tens to hundreds meV lower than the nonmagnetic state. The formation of ferromagnetism can be attributed to the hydrogenation-induced near degeneracy between the highest occupied and lowest unoccupied molecular orbitals. Simultaneously, there exists a finite dipole moment in the ferromagnetic state, due to the breaking of the inversion symmetry of oligomers. Our results imply that the hydrogenated triapentafulvalene and pentaheptafulvalene oligomers could be promising candidates in the development of room temperature organic multiferroics.

Directional water collection on wetted spider silk.

Many biological surfaces in both the plant and animal kingdom possess unusual structural features at the micro- and nanometre-scale that control their interaction with water and hence wettability. An intriguing example is provided by desert beetles, which use micrometre-sized patterns of hydrophobic and hydrophilic regions on their backs to capture water from humid air. As anyone who has admired spider webs adorned with dew drops will appreciate, spider silk is also capable of efficiently collecting water from air. Here we show that the water-collecting ability of the capture silk of the cribellate spider Uloborus walckenaerius is the result of a unique fibre structure that forms after wetting, with the 'wet-rebuilt' fibres characterized by periodic spindle-knots made of random nanofibrils and separated by joints made of aligned nanofibrils. These structural features result in a surface energy gradient between the spindle-knots and the joints and also in a difference in Laplace pressure, with both factors acting together to achieve continuous condensation and directional collection of water drops around spindle-knots. Submillimetre-sized liquid drops have been driven by surface energy gradients or a difference in Laplace pressure, but until now neither force on its own has been used to overcome the larger hysteresis effects that make the movement of micrometre-sized drops more difficult. By tapping into both driving forces, spider silk achieves this task. Inspired by this finding, we designed artificial fibres that mimic the structural features of silk and exhibit its directional water-collecting ability.

Fabrication and Protein Conjugation of Aligned Polypyrrole-Poly(L-lactic acid) Fibers Film with the Conductivity and Stability.

The conducting composite scaffold, including fiber-cores of aligned poly(L-lactic acid) (PLLA) and shell-layer of polypyrrole (PPy), was fabricated, and then bovine serum albumin (BSA) was conjugated on the PPy shell-layer. Aligned PLLA fibers (about 300 nm diameter) were obtained by electrospinning and rotating drum collection, and then coated by PPy nanoparticles (NPs, about 50 nm diameter) via chemical oxidation. The surface resistivity of PPy-PLLA fibers film were 0.971, 0.874 kΩ. cm at the fiber's vertical and parallel directions, respectively. The results of PPy-PLLA fibers film immersed in phosphate buffer saline for 8 d indicated that the fibers morphology and the film conductivity were not significantly changed, and the fluorescent images showed that FITC-labeled BSA (FITC-BSA) were successfully conjugated in the fibers film with carbodiimide chemistry, and the largest amount of FITC-BSA conjugated in the fibers film from 100 µg/mL proteins solution was 31.31 µg/cm2 due to lots of poly(glutamic acid) in surface-nanogrooves of the fibers surface. Under electrical stimulation of 100 mV, the fibers film was accompanied the release of all conjugated FITC-BSA with the detachment of some PPy NPs. These results suggested that PPy-PLLA fibers film would be potentially applied in the construction of degradable tissue engineering scaffold with protein factors, especially neurotrophic factors for nerve tissue repair.

Preparation of Polypyrrole-Protein Composite Films and the Electrochemically Controlled Release of Proteins.

It is fabricated that an electrically controlled release system based on the (poly-L-lactic acid)-mixed polypyrrole (PLLA-PPy) films through casting film of PPy and PLLA mixed solution on the glass plate, in which polyglutamic acid (PGlu)-doped PPy nanoparticles (NPs) with -50 nm diameter are synthesized via chemical oxidation. Surface conductivity of the composite film is (3.33 ± 2.01) x 10(-3) S/cm. Bovine serum albumin (BSA), as a model protein drug, is chemically linked onto the composite film via carbodiimide chemistry due to the good surface nano-structure of PLLA-PPy film. The releases of BSA from PLLA-PPy film under constant current and constant voltage can be achieved using the two-electrode electrochemical system. 6 h accumulative releases of BSA are 276 µg/cm2 and 176 µg/cm2 under 3 mA and 1 V electrical stimulation, respectively, accompanied with de-doping of PGlu and separation of a part of PPy NPs from the composite film. The results of cell experiment indicate that PGlu-doped PPy NPs in the prepared composite film have good cyto-compatibility. These results suggest that PPy-PLLA composite film would be able to be applied in the construction of degradable protein-drug-loaded scaffold for nerve tissue repair.

Tumor-targeted paclitaxel-loaded folate conjugated poly(ethylene glycol)-poly(L-lactide) microparticles produced by supercritical fluid technology.

The new biodegradable diblock copolymers poly(ethylene glycol)-poly(L-lactide) (PEG-PLLA) were synthesized and were chemically conjugated with folate (FA) in the PEG terminal ends to form FA-PEG-PLLA. Then the hydrophobic drug paclitaxel (PTX) loaded microparticles (PTX/FA-PEG-PLLA) were produced via solution enhanced dispersion by supercritical fluids (SEDS). These microparticles exhibited sphere-like shape by scanning electron microscopy observation and showed narrow hydrodynamic size distributions by dynamic light scattering measurement. Drug loading of PTX loaded microparticles was about 7-9% and the encapsulation efficiency of PTX loaded microparticles was about 18-23%. Flow cytometry and confocal laser scanning microscope analyses revealed that fluorescein isothiocyanate labeled FA conjugated microparticles presented significantly higher cellular uptake than FA-free group due to the FA-receptor-mediated endocytosis. In vitro cytotoxicity evaluation indicated that FA-PEG-PLLA expressed negligible cytotoxicity to mouse fibroblasts L929 cells. Moreover, PTX/FA-PEG-PLLA microparticles exhibited much higher anti-cancer efficacy than PTX/PEG-PLLA microparticles against human ovarian cancer SKOV3 cells. Nude mice xenografted with SKOV3 cells were used in biodistribution studies, the results indicated that an increased amount of PTX was accumulated in the tumor tissue deal with PTX/FA-PEG-PLLA microparticles. These results collectively suggested that PTX/FA-PEG-PLLA microparticles prepared by SEDS would have potential in anti-tumor applications as a tumor-targeted drug delivery formulation.