Nanocellulose-Based Materials for Water Treatment: Adsorption, Photocatalytic Degradation, Disinfection, Antifouling, and Nanofiltration.

Nanocelluloses are promising bio-nano-materials for use as water treatment materials in environmental protection and remediation. Over the past decades, they have been integrated via novel nanoengineering approaches for water treatment processes. This review aims at giving an overview of nanocellulose requirements concerning emerging nanotechnologies of waster treatments and purification, i.e., adsorption, absorption, flocculation, photocatalytic degradation, disinfection, antifouling, ultrafiltration, nanofiltration, and reverse osmosis. Firstly, the nanocellulose synthesis methods (mechanical, physical, chemical, and biological), unique properties (sizes, geometries, and surface chemistry) were presented and their use for capturing and removal of wastewater pollutants was explained. Secondly, different chemical modification approaches surface functionalization (with functional groups, polymers, and nanoparticles) for enhancing the surface chemistry of the nanocellulose for enabling the effective removal of specific pollutants (suspended particles, microorganisms, hazardous metals ions, organic dyes, drugs, pesticides fertilizers, and oils) were highlighted. Thirdly, new fabrication approaches (solution casting, thermal treatment, electrospinning, 3D printing) that integrated nanocelluloses (spherical nanoparticles, nanowhiskers, nanofibers) to produce water treatment materials (individual composite nanoparticles, hydrogels, aerogels, sponges, membranes, and nanopapers) were covered. Finally, the major challenges and future perspectives concerning the applications of nanocellulose based materials in water treatment and purification were highlighted.

Molecularly engineered truncated tissue factor with therapeutic aptamers for tumor-targeted delivery and vascular infarction.

Selective occlusion of tumor vasculature has proven to be an effective strategy for cancer therapy. Among vascular coagulation agents, the extracellular domain of coagulation-inducing protein tissue factor, truncated tissue factor (tTF), is the most widely used. Since the truncated protein exhibits no coagulation activity and is rapidly cleared in the circulation, free tTF cannot be used for cancer treatment on its own but must be combined with other moieties. We here developed a novel, tumor-specific tTF delivery system through coupling tTF with the DNA aptamer, AS1411, which selectively binds to nucleolin receptors overexpressing on the surface of tumor vascular endothelial cells and is specifically cytotoxic to target cells. Systemic administration of the tTF-AS1411 conjugates into tumor-bearing animals induced intravascular thrombosis solely in tumors, thus reducing tumor blood supply and inducing tumor necrosis without apparent side effects. This conjugate represents a uniquely attractive candidate for the clinical translation of vessel occlusion agent for cancer therapy.

Paraffin-enabled graphene transfer.

The performance and reliability of large-area graphene grown by chemical vapor deposition are often limited by the presence of wrinkles and the transfer-process-induced polymer residue. Here, we report a transfer approach using paraffin as a support layer, whose thermal properties, low chemical reactivity and non-covalent affinity to graphene enable transfer of wrinkle-reduced and clean large-area graphene. The paraffin-transferred graphene has smooth morphology and high electrical reliability with uniform sheet resistance with ~1% deviation over a centimeter-scale area. Electronic devices fabricated on such smooth graphene exhibit electrical performance approaching that of intrinsic graphene with small Dirac points and high carrier mobility (hole mobility = 14,215 cm2 V-1 s-1; electron mobility = 7438 cm2 V-1 s-1), without the need of further annealing treatment. The paraffin-enabled transfer process could open realms for the development of high-performance ubiquitous electronics based on large-area two-dimensional materials.

Synthetic Lateral Metal-Semiconductor Heterostructures of Transition Metal Disulfides.

Lateral heterostructures with planar integrity form the basis of two-dimensional (2D) electronics and optoelectronics. Here we report that, through a two-step chemical vapor deposition (CVD) process, high-quality lateral heterostructures can be constructed between metallic and semiconducting transition metal disulfide (TMD) layers. Instead of edge epitaxy, polycrystalline monolayer MoS2 in such junctions was revealed to nucleate from the vertices of multilayered VS2 crystals, creating one-dimensional junctions with ultralow contact resistance (0.5 kΩ·µm). This lateral contact contributes to 6-fold improved field-effect mobility for monolayer MoS2, compared to the conventional on-top nickel contacts. The all-CVD strategy presented here hence opens up a new avenue for all-2D-based synthetic electronics.

In Situ-Generated Volatile Precursor for CVD Growth of a Semimetallic 2D Dichalcogenide.

Semimetallic-layered transition-metal dichalcogenides, such as TiS2, can serve as a platform material for exploring novel physics modulated by dimensionality, as well as for developing versatile applications in electronics and thermoelectrics. However, controlled synthesis of ultrathin TiS2 in a dry-chemistry way has yet to be realized because of the high oxophilicity of active Ti precursors. Here, we report the ambient pressure chemical vapor deposition (CVD) method to grow large-size, highly crystalline two-dimensional (2D) TiS2 nanosheets through in situ generating titanium chloride as the gaseous precursor. The addition of NH4Cl promoter can react with Ti powders and switch the solid-phase sulfurization reaction into a CVD process, thus enabling the controllability over the size, shape, and thickness of the TiS2 nanosheets via tuning the synthesis conditions. Interestingly, this semimetallic 2D material exhibits near-infrared surface plasmon resonance absorption and a memristor-like electrical behavior, both holding promise for further application developments. Our method hence opens a new avenue for the CVD growth of 2D metal dichalcogenides directly from metal powders and pave the way for exploring their intriguing properties and applications.

Efficient and tumor-specific knockdown of MTDH gene attenuates paclitaxel resistance of breast cancer cells both in vivo and in vitro.

BACKGROUND: Drug resistance of paclitaxel (TAX), the first-line chemotherapy drug for breast cancer, was reported to develop in 90% of patients with breast cancer, especially metastatic breast cancer. Investigating the mechanism of TAX resistance of breast cancer cells and developing the strategy improving its therapeutic efficiency are crucial to breast cancer cure. METHODS AND RESULTS: We here report an elegant nanoparticle (NP)-based technique that realizes efficient breast cancer treatment of TAX. Using lentiviral vector-mediated gene knockdown, we first demonstrated that TAX therapeutic efficiency was closely correlated with metadherin (MTDH) gene expression in breast cancer cell lines. This finding was also supported by efficacy of TAX treatment in breast cancer patients from our clinical studies. Specifically, TAX treatment became more effective when MTDH expression was decreased in MCF-7 cancer cells by the blocking nuclear factor-kappa B (NF-κB) pathway. Based on these findings, we subsequently synthesized a polymeric NP that could co-deliver MTDH-small interfering RNA (MTDH-siRNA) and TAX into the breast cancer tumors in tumor-bearing mice. The NPs were composed of a cationic copolymer, which wrapped TAX in the inside and adsorbed the negatively charged siRNA on their surface with high drug-loading efficiency and good stability. CONCLUSIONS: NP-based co-delivery approach can effectively knock down the MTDH gene both in vitro and in vivo, which dramatically inhibits breast tumor growth, achieving effective TAX chemotherapy treatment without overt side effects. This study provides a potential therapeutic strategy for the treatment of a wide range of solid tumors highly expressing MTDH.

Low-Temperature Copper Bonding Strategy with Graphene Interlayer.

The reliability of lead-free Cu bonding technology is often limited by high bonding temperature and perpetual growth of intermetallic compounds between Sn solder and Cu substrate. Here, we report a low-bonding-temperature and highly reliable Cu bonding strategy with the use of graphene as an interlayer. By integrating a nanoscale graphene/Cu composite on the Cu substrate prior to thermocompression bonding, we observe a macroscale phenomenon where reliable Sn-Cu joints can be fabricated at a bonding temperature as low as 150 °C. During the bonding process, nanoscale features are replicated in the Sn solder by the Cu nanocone array morphology. Compared to microscale Sn, nanoscale Sn is mechanically weaker and thus can distribute on the Cu substrate at a much lower temperature. Furthermore, insertion of a graphene interlayer, which is one atom thick, can successfully retard the intermetallic compounds' growth and preserve a high bonding yield, following 96 h of aging, as confirmed through SEM and shear strength analyses. Our graphene-based Cu bonding strategy demonstrated in this work is highly reliable, cost-effective, and environmentally friendly, representing a much closer step toward industrial applications.

Suppression of Tumor Energy Supply by Liposomal Nanoparticle-Mediated Inhibition of Aerobic Glycolysis.

Aerobic glycolysis enables cancer cells to rapidly take up nutrients (e.g., nucleotides, amino acids, and lipids) and incorporate them into the biomass needed to produce a new cell. In contrast to existing chemotherapy/radiotherapy strategies, inhibiting aerobic glycolysis to limit the adenosine 5'-triphosphate (ATP) yield is a highly efficient approach for suppressing tumor cell proliferation. However, most, if not all, current inhibitors of aerobic glycolysis cause significant adverse effects because of their nonspecific delivery and distribution to nondiseased organs, low bioavailability, and a narrow therapeutic window. New strategies to enhance the biosafety and efficacy of these inhibitors are needed for moving them into clinical applications. To address this need, we developed a liposomal nanocarrier functionalized with a well-validated tumor-targeting peptide to specifically deliver the aerobic glycolysis inhibitor 3-bromopyruvate (3-BP) into the tumor tissue. The nanoparticles effectively targeted tumors after systemic administration into tumor-bearing mice and suppressed tumor growth by locally releasing 3-BP to inhibit the ATP production of the tumor cells. No overt side effects were observed in the major organs. This report demonstrates the potential utility of the nanoparticle-enabled delivery of an aerobic glycolysis inhibitor as an anticancer therapeutic agent.

Electrical Homogeneity of Large-Area Chemical Vapor Deposited Multilayer Hexagonal Boron Nitride Sheets.

Large-area hexagonal boron nitride (h-BN) can be grown on polycrystalline metallic substrates via chemical vapor deposition (CVD), but the impact of local inhomogeneities on the electrical properties of the h-BN and their effect in electronic devices is unknown. Conductive atomic force microscopy (CAFM) and probe station characterization show that the tunneling current across the h-BN stack fluctuates up to 3 orders of magnitude from one substrate (Pt) grain to another. Interestingly, the variability in the tunneling current across the h-BN within the same substrate grain is very low, which may enable the use of CVD-grown h-BN in ultra scaled technologies.

Origin of Contact Resistance at Ferromagnetic Metal-Graphene Interfaces.

Edge contact geometries are thought to yield ultralow contact resistances in most nonferromagnetic metal-graphene interfaces, owing to their large metal-graphene coupling strengths. Here, we examine the contact resistance of edge- versus surface-contacted ferromagnetic metal-graphene interfaces (i.e., nickel- and cobalt-graphene interfaces) using both single-layer and few-layer graphene. Good qualitative agreement is obtained between theory and experiment. In particular, in both theory and experiment, we observe that the contact resistance of edge-contacted ferromagnetic metal-graphene interfaces is much lower than that of surface-contacted ones, for all devices studied and especially for the single-layer graphene systems. We show that this difference in resistance is not due to differences in the metal-graphene coupling strength, which we quantify using Hamiltonian matrix elements. Instead, the larger contact resistance in surface contacts results from spin filtering at the interface, in contrast to the edge-contacted case where both spins are transmitted. Temperature-dependent resistance measurements beyond the Curie temperature TC show that the spin degree of freedom is indeed important for the experimentally measured contact resistance. These results show that it is possible to induce a large change in contact resistance by changing the temperature in the vicinity of TC.

Tuning the threshold voltage of MoS2 field-effect transistors via surface treatment.

Controlling the threshold voltage (Vth) of a field-effect transistor is important for realizing robust logic circuits. Here, we report a facile approach to achieve bidirectional Vth tuning of molybdenum disulfide (MoS2) field-effect transistors. By increasing and decreasing the amount of sulfur vacancies in the MoS2 surface, the Vth of MoS2 transistors can be left- and right-shifted, respectively. Transistors fabricated on perfect MoS2 flakes are found to exhibit a two-fold enhancement in mobility and a very positive Vth (18.5 ± 7.5 V). More importantly, our elegant hydrogen treatment is able to tune the large Vth to a small value (∼0 V) without any performance degradation simply by reducing the atomic ratio of S : Mo slightly; in other words, it creates a certain amount of sulfur vacancies in the MoS2 surface, which generate defect states in the band gap of MoS2 that mediates conduction of a MoS2 transistor in the subthreshold regime. First-principles calculations further indicate that the defect band's edge and width can be tuned according to the vacancy density. This work not only demonstrates for the first time the ease of tuning the Vth of MoS2 transistors, but also offers a process technology solution that is critical for further development of MoS2 as a mainstream electronic material.

Low resistance metal contacts to MoS2 devices with nickel-etched-graphene electrodes.

We report an approach to achieve low-resistance contacts to MoS2 transistors with the intrinsic performance of the MoS2 channel preserved. Through a dry transfer technique and a metal-catalyzed graphene treatment process, nickel-etched-graphene electrodes were fabricated on MoS2 that yield contact resistance as low as 200 Ω · µm. The substantial contact enhancement (∼ 2 orders of magnitude), as compared to pure nickel electrodes, is attributed to the much smaller work function of nickel-graphene electrodes, together with the fact that presence of zigzag edges in the treated graphene surface enhances tunneling between nickel and graphene. To this end, the successful fabrication of a clean graphene-MoS2 interface and a low resistance nickel-graphene interface is critical for the experimentally measured low contact resistance. The potential of using graphene as an electrode interlayer demonstrated in this work paves the way toward achieving high performance next-generation transistors.

What does annealing do to metal-graphene contacts?

Annealing is a postprocessing treatment commonly used to improve metal-graphene contacts with the assumption that resist residues sandwiched at the metal-graphene contacts are removed during annealing. Here, we examine this assumption by undertaking a systematic study to understand mechanisms that lead to the contact enhancement brought about by annealing. Using a soft shadow-mask, we fabricated residue-free metal-graphene contacts with the same dimensions as lithographically defined metal-graphene contacts on the same graphene flake. Both cases show comparable contact enhancement for nickel-graphene contacts after annealing treatment signifying that removal of resist residues is not the main factor for contact enhancement. It is found instead that carbon dissolves from graphene into the metal at chemisorbed Ni- and Co-graphene interfaces and leads to many end-contacts being formed between the metal and the dangling carbon bonds in the graphene, which contributes to much smaller contact resistance.

Low-contact-resistance graphene devices with nickel-etched-graphene contacts.

The performance of graphene-based transistors is often limited by the large electrical resistance across the metal-graphene contact. We report an approach to achieve ultralow resistance metal contacts to graphene transistors. Through a process of metal-catalyzed etching in hydrogen, multiple nanosized pits with zigzag edges are created in the graphene portions under source/drain metal contacts while the graphene channel remains intact. The porous graphene source/drain portions with pure zigzag-termination form strong chemical bonds with the deposited nickel metallization without the need for further annealing. This facile contact treatment prior to electrode metallization results in contact resistance as low as 100 Ω·µm in single-layer graphene field-effect transistors, and 11 Ω·µm in bilayer graphene transistors. Besides 96% reduction in contact resistance, the contact-treated graphene transistors exhibit 1.5-fold improvement in mobility. More importantly, the metal-catalyzed etching contact treatment is compatible with complementary metal-oxide-semiconductor (CMOS) fabrication processes, and holds great promise to meet the contact performance required for the integration of graphene in future integrated circuits.