Pure Graphene Oxide Vertical p-n Junction with Remarkable Rectification Effect.

Graphene p-n junctions have important applications in the fields of optical interconnection and low-power integrated circuits. Most current research is based on the lateral p-n junction prepared by chemical doping and other methods. Here, we report a new type of pure graphene oxide (pGO) vertical p-n junctions which do not dope any other elements but only controls the oxygen content of GO. The I-V curve of the pGO vertical p-n junction demonstrates a remarkable rectification effect. In addition, the pGO vertical p-n junction shows stability of its rectification characteristic over long-term storage for six months when sealed and stored in a PE bag. Moreover, the pGO vertical p-n junctions have obvious photoelectric response and various rectification effects with different thicknesses and an oxygen content of GO, humidity, and temperature. Hall effect test results show that rGO is an n-type semiconductor; theoretical calculations and research show that GO is generally a p-type semiconductor with a bandgap, thereby forming a p-n junction. Our work provides a method for preparing undoped GO vertical p-n junctions with advantages such as simplicity, convenience, and large-scale industrial preparation. Our work demonstrates great potential for application in electronics and highly sensitive sensors.

Fullerene-intercalated graphene nanocontainers for gas storage and sustained release.

Molecular dynamics simulations are performed to investigate the storage capacity and sustained release of nitrogen (N2) in the graphene-based nanocontainers. Sandwiched graphene-fullerene composites (SGFC) composed of two parallel graphene sheets and intercalated fullerenes are constructed. The simulation results show that the mass density of N2 at the first layer is extremely high, due to the strong adsorption ability of graphene sheets. And N2 molecules at this adsorbed layer are thermodynamically stable. Furthermore, we analyze the storage efficiency of SGFC. In general, the gravimetric and volumetric capacities decrease with the increasing number of intercalated fullerenes. On the contrary, the stability of SGFC is enhanced by more intercalated fullerenes. We therefore make a compromise and propose that 1 fullerene per 5 nm2 graphene to build a SGFC, which is much effective to storage N2. We also verify the reversibility that N2 can sustainably release from the SGFC. Our results may provide insights into the design of graphene-based nanocomposites for gas storage and sustained release with excellent structural stability and high storage capacity. Graphical abstract.

Fabrication of Biodegradable Poly(caprolactone) Spherical-Microcarriers for Arterial Embolization.

This study aimed to develop emulsification assisted with ultrasonic atomization (EUA) to make embolic biodegradable poly(caprolactone) (PCL) spherical-microcarriers with uniform particle size for mass production which was used to cure hepatocellular carcinoma, because this kind of embolic drugs is expensive at the current market due to their complex manufacturing process. The embolic spherical-microcarriers with sustained-releasing therapeutic agents can shrink an unresectable tumor into a respectable size. Through high frequency vibrating surface on the ultrasonic atomizer nozzle, the thin liquid film for PCL oil-phase solution was broken into the uniform PCL microdroplets (particle sizes are from 20 to 55 µm) with less medicine loss. To determine the optimal parameters to make PCL microcarriers, the ultrasonic module parameters including the concentration of PCL solution, vibrating amplitude of atomizer, feeding rate of PCL oil-phase solution and collection distance on the particle size of microdroplets were analyzed. Besides, a vertical circulation flow field of aqueous-phase poly(vinyl alcohol) (PVA) solution was created to enhance the separation of the microdroplets and increase the production of the PCL microcarriers, and about 8~11 wt% of PVA solution with high stable dispersion property was used to effectively improve the yield rate of PCL spherical-microcarriers (89.8~98.2 wt%). The final particle size of PCL microcarriers was ca. 5-18 µm, indicating an about 25-50% volume shrinkage from microdroplets to solid spherical-microcarriers.

Molecular insights into the dispersion stability of graphene oxide in mixed solvents: Theoretical simulations and experimental verification.

HYPOTHESIS: Improving the dispersion stability of graphene oxide (GO) suspensions is of great importance in many potential applications of GO, such as GO-based laminated membranes used for separation, printable electronics, and aqueous liquid crystals. EXPERIMENTS: Molecular dynamics (MD) simulations and quantum chemistry (QC) calculations along with complementary experiments were performed to study the dispersion stability of GO in the mixtures of water and polar organic solvents (dimethyl sulfoxide (DMSO), ethanol, and acetone). FINDINGS: GO exhibits better dispersion stability in a solvent mixture than in pure water. The MD simulations uncover the underlying mechanism that mixed solvent layers are formed steadily on the surface of GO sheets and screen the interactions between them. QC calculations reveal that both DMSO and water form hydrogen bonds with the oxidized regions of GO. X-ray diffraction experiments confirm that the GO sheets are intercalated by DMSO and water molecules. Furthermore, the optimal ratio of the organic solvent to water is determined to achieve the best dispersion stability of GO through MD simulations. And such ratio is also verified by ultraviolet absorption spectral experiments. Thus, our findings provide a facile method to prepare GO suspensions with high dispersion stability.

Molecular dynamics simulations of loading and unloading of drug molecule bortezomib on graphene nanosheets.

Graphene has been regarded as one of the most hopeful candidates for transporting drugs to target cells because of its huge surface area and high cellular uptake. In this work, we performed molecular dynamics simulations to investigate the potential application of graphene as a substrate to carry and deliver drug molecules. Bortezomib (BOR) was selected as a model drug, as its atomic structure and polarity are suitable to be adsorbed on pristine graphene (PG) and graphene oxide (GO). First, BOR molecules are loaded on graphene surface to form graphene-BOR complexes, then these complexes readily enter the lipid bilayer and finally BOR releases from graphene surface into the membrane. The entry of graphene-BOR complexes into the membrane is mainly driven by the hydrophobic interactions between lipid tails and the basal plane of nanosheets, while the electrostatic interaction between the polar groups of BOR and lipid headgroups contributes to the release of BOR from graphene into the membrane. Different from PG, BOR molecules are hard to remove from GO surface after the complex enters the lipid bilayer. The electrostatic attraction from the oxygen-containing groups enhances the binding of BOR on GO. Potential of mean force calculations confirm that BOR on GO has lower free energy than it adsorbed on PG surface. The results indicate that the adsorption intensity and release rate of graphene nanosheets can be tuned by oxidation and electrification, and graphene served as substrate to transport and release particular drug molecules is feasible.

Molecular simulations of conformation change and aggregation of HIV-1 Vpr13-33 on graphene oxide.

Recent experiments have reported that the fragment of viral protein R (Vpr), Vpr13-33, can assemble and change its conformation after adsorbed on graphene oxide (GO) and then reduce its cytotoxicity. This discovery is of great importance, since the mutation of Vpr13-33 can decrease the viral replication, viral load and delay the disease progression. However, the interactions between Vpr13-33 and GO at atomic level are still unclear. In this study, we performed molecular dynamics simulation to investigate the dynamic process of the adsorption of Vpr13-33 onto GO and the conformation change after aggregating on GO surface. We found that Vpr13-33 was adsorbed on GO surface very quickly and lost its secondary structure. The conformation of peptides-GO complex was highly stable because of π-π stacking and electrostatic interactions. When two peptides aggregated on GO, they did not dimerize, since the interactions between the two peptides were much weaker than those between each peptide and GO.

Exploring the Effects on Lipid Bilayer Induced by Noble Gases via Molecular Dynamics Simulations.

Noble gases seem to have no significant effect on the anesthetic targets due to their simple, spherical shape. However, xenon has strong narcotic efficacy and can be used clinically, while other noble gases cannot. The mechanism remains unclear. Here, we performed molecular dynamics simulations on phospholipid bilayers with four kinds of noble gases to elucidate the difference of their effects on the membrane. Our results showed that the sequence of effects on membrane exerted by noble gases from weak to strong was Ne, Ar, Kr and Xe, the same order as their relative narcotic potencies as well as their lipid/water partition percentages. Compared with the other three kinds of noble gases, more xenon molecules were distributed between the lipid tails and headgroups, resulting in membrane's lateral expansion and lipid tail disorder. It may contribute to xenon's strong anesthetic potency. The results are well consistent with the membrane mediated mechanism of general anesthesia.

Nonlinear adaptive PID control for greenhouse environment based on RBF network.

This paper presents a hybrid control strategy, combining Radial Basis Function (RBF) network with conventional proportional, integral, and derivative (PID) controllers, for the greenhouse climate control. A model of nonlinear conservation laws of enthalpy and matter between numerous system variables affecting the greenhouse climate is formulated. RBF network is used to tune and identify all PID gain parameters online and adaptively. The presented Neuro-PID control scheme is validated through simulations of set-point tracking and disturbance rejection. We compare the proposed adaptive online tuning method with the offline tuning scheme that employs Genetic Algorithm (GA) to search the optimal gain parameters. The results show that the proposed strategy has good adaptability, strong robustness and real-time performance while achieving satisfactory control performance for the complex and nonlinear greenhouse climate control system, and it may provide a valuable reference to formulate environmental control strategies for actual application in greenhouse production.