Photo-degradable and recyclable starch/Fe3O4/TiO2 nanocomposites: feasibility of an approach to reduce the recycling labor cost in plastic waste management.

In this research, a biodegradable starch/Fe3O4/TiO2 bio-nanocomposites (SFT) were produced using different nano Fe3O4/TiO2 (FT) (3, 5, and 10 (wt% dry based)) contents. Mechanical properties, visual properties, moisture-sensitive parameters, magnetic properties, and physical properties of the film specimens were investigated. Photodegradability of film specimens was also evaluated under UV-A irradiation. The FT content increased the hydrophobicity of the film specimens. Tensile strength (TS) of SFT films was increased by increasing FT up to 3%. Elongation at break (EB) and tensile energy to break (TEB) were decreased by adding FT content up to 3% simultaneously. The film specimens' water vapor permeability (WVP) was decreased with increasing FT content. The intrinsic viscosity of SFT was decreased by increasing FT content. It confirms the enhancement of photodegradability of the specimens by increasing FT content. It seems the compatibility of FT with biopolymer has had great effects on these properties. Use of FT-based nanocomposites is an appropriate approach to developing magnetic-recyclable and photodegradable packaging materials.

TiO2/carbonaceous nanocomposite from titanium-alginate coordination compound.

TiO2-based materials have been developing rapidly as eco-friendly photocatalysts, but the inherent defects limited their application, such as rapid recombination of photogenerated electrons and wide bandgap. To obtain high-efficient TiO2/carbonaceous photocatalysts (TiO2/C), we prepared the nanocomposite by carbonizing titanium alginate coordination compound and studied their photocatalytic performance against methylene blue (MB) under simulated sunlight irradiation. The resultant nanocomposites were characterized by FT-IR, XPS, XRD, SEM-EDS, TG-DTG, UV-DRS, and N2 adsorption-desorption analysis. The carbon mainly existed in the outer layer of TiO2/C composites, contributing to the optical sensibilization. As a result, the degradation efficiency of sample TiO2/C-20 to MB could reach 97.47% within 15 min under simulated sunlight. The samples also possessed high stability, proved by the 0.72% reduction in photodegradation ratio after five cyclic tests. The present study proved the feasibility of preparing photocatalyst from titanium-alginate coordination compound and provided an extensible approach for preparing high-efficiency photocatalysts from a polysaccharide-based coordination compound.

Covalent RGD-graphene-phthalocyanine nanocomposite for fluorescence imaging-guided dual active/passive tumor-targeted combinatorial phototherapy.

Poor tumor selectivity, low stability and quenched fluorescence are the main challenges to be overcome for nanomedicine, and are mainly caused by the dissociation of the nanostructure and aggregation of chromophores in the biological environment. Herein, covalently connected nanoparticles RGD-graphene-phthalocyanine (RGD-GO-SiPc) were constructed based on RGD peptide, silicon phthalocyanine (SiPc) and graphene oxide (GO) via a conjugation reaction for fluorescence imaging-guided cancer-targeted combinatorial phototherapy. The prepared RGD-GO-SiPc exhibited supreme biological stability, high-contrast fluorescence imaging, significantly enhanced NIR absorption, high photothermal conversion efficiency (25.6%), greatly improved cancer-targeting capability, and synergistic photodynamic (PDT) and photothermal therapy (PTT) efficacy along with low toxicity. Both in vitro and in vivo biological studies showed that RGD-GO-SiPc is a kind of promising multifunctional nanomedicine for fluorescence imaging-guided combined photothermal and photodynamic therapy with dual active/passive tumor-targeting properties.

3D-Printed Multifunctional Polyetheretherketone Bone Scaffold for Multimodal Treatment of Osteosarcoma and Osteomyelitis.

In this work, we developed the first 3D-printed polyetheretherketone (PEEK)-based bone scaffold with multi-functions targeting challenging bone diseases such as osteosarcoma and osteomyelitis. A 3D-printed PEEK/graphene nanocomposite scaffold was deposited with a drug-laden (antibiotics and/or anti-cancer drugs) hydroxyapatite coating. The graphene nanosheets within the scaffold served as effective photothermal agents that endowed the scaffold with on-demand photothermal conversion function under near-infrared laser irradiation. The bioactive hydroxyapatite coating significantly boosted the stem cell proliferation in vitro and promoted new bone growth in vivo. The presence of antibiotics and anti-cancer drugs enabled eradication of drug-resistant bacteria and ablation of osteosarcoma cancer cells, the treatment efficacy of which can be further enhanced by on-demand laser-induced heating. The promising results demonstrate the strong potential of our multi-functional scaffold in applications such as bone defect repair and multimodal treatment of osteosarcoma and osteomyelitis.

Photomechanical Polymer Nanocomposites for Drug Delivery Devices.

We demonstrate a novel structure based on smart carbon nanocomposites intended for fabricating laser-triggered drug delivery devices (DDDs). The performance of the devices relies on nanocomposites' photothermal effects that are based on polydimethylsiloxane (PDMS) with carbon nanoparticles (CNPs). Upon evaluating the main features of the nanocomposites through physicochemical and photomechanical characterizations, we identified the main photomechanical features to be considered for selecting a nanocomposite for the DDDs. The capabilities of the PDMS/CNPs prototypes for drug delivery were tested using rhodamine-B (Rh-B) as a marker solution, allowing for visualizing and quantifying the release of the marker contained within the device. Our results showed that the DDDs readily expel the Rh-B from the reservoir upon laser irradiation and the amount of released Rh-B depends on the exposure time. Additionally, we identified two main Rh-B release mechanisms, the first one is based on the device elastic deformation and the second one is based on bubble generation and its expansion into the device. Both mechanisms were further elucidated through numerical simulations and compared with the experimental results. These promising results demonstrate that an inexpensive nanocomposite such as PDMS/CNPs can serve as a foundation for novel DDDs with spatial and temporal release control through laser irradiation.

Synergistic Multimodal Cancer Therapy Using Glucose Oxidase@CuS Nanocomposites.

Multimodal nanotherapeutic cancer treatments are widely studied but are often limited by their costly and complex syntheses that are not easily scaled up. Herein, a simple formulation of glucose-oxidase-coated CuS nanoparticles was demonstrated to be highly effective for melanoma treatment, acting through a synergistic combination of glucose starvation, photothermal therapy, and synergistic advanced chemodynamic therapy enabled by near-infrared irradiation coupled with Fenton-like reactions that were enhanced by endogenous chloride.

Fluorescent detection of microRNA-21 in MCF-7 cells based on multifunctional gold nanorods and the integration of chemotherapy and phototherapy.

MicroRNA-21 is an important biomarker of tumor early prediction and metastasis, and its accurate detection is of great significance for tumor diagnosis and treatment. It will be a meaningful work to combine the detection of RNA with chemotherapy and photothermal therapy on the same composite material. Herein, we designed a multifunctional nanocomposite based on gold nanorods (AuNRs), making use of microRNA-triggered drug release and near-infrared photothermal effect, which has been developed for cancer therapy and microRNA-21detection. Firstly, the AuNRs with photothermal effect were synthesized as carriers for drug delivery. Then the surface of gold nanorods was modified by functional DNA chains to provide an efficient site for doxorubicin (DOX) loading. Finally, folic acid was introduced to achieve the targeted treatment of MCF-7 cells. The microRNA competed with the double-stranded DNA, resulting in the release of DOX and the recovery of fluorescence signal located at 595 nm with an excitation of 488 nm effectively. The nano-biosensor could not only achieve dual-function of diagnosis and treatment of cancer cells, but also accomplish the detection of microRNA in tumor cells. It showed a high selectivity for microRNA-21 determination with a limit of detection (LOD) of 2.1 nM from the linear relationship from 1.0 × 10-5 M to 5.0 × 10-7 M. This scheme provides an outstanding strategy for cell imaging, treatment, and detection, which serves as a promising candidate in the field of biomedical research.

Near-Infrared Radiation-Assisted Drug Delivery Nanoplatform to Realize Blood-Brain Barrier Crossing and Protection for Parkinsonian Therapy.

Mitochondrial dysfunction, which is directly involved in Parkinson's disease (PD), is characterized by the production of reactive oxygen species (ROS) and aberrant energy metabolism. Thus, regulating mitochondrial function might be an effective strategy to treat PD. However, the blood-brain barrier (BBB) presents a significant challenge for the intracerebral delivery of drugs. Here, we synthesized a zeolitic imidazolate framework 8-coated Prussian blue nanocomposite (ZIF-8@PB), which was encapsulated with quercetin (QCT), a natural antioxidant, to treat PD. ZIF-8@PB-QCT exhibited superior near-infrared radiation (NIR) response and penetrated through the BBB to the site of mitochondrial damage guided by the photothermal effect. In the mice model of PD, the QCT released from ZIF-8@PB-QCT significantly increased the adenosine triphosphate levels, reduced the oxidative stress levels, and reversed dopaminergic neuronal damage as well as PD-related behavioral deficits without any damage to the normal tissues. Furthermore, we explored the underlying neuroprotective mechanism of ZIF-8@PB-QCT that was mediated by activating the PI3K/Akt signaling pathway. Thus, combined with noninvasive NIR radiation, the biocompatible ZIF-8@PB-QCT nanocomposite could be used to treat neurodegenerative diseases.

Triformyl cholic acid and folic acid functionalized magnetic graphene oxide nanocomposites: Multiple-targeted dual-modal synergistic chemotherapy/photothermal therapy for liver cancer.

Photo-chemotherapy (PCT) reveals great potential in hepatocellular carcinoma (HCC) treatment, therefore the construct of smart PCT nano-agents with high photothermal conversion efficiency and accurate drug delivery is of great significant. Herein, a novel hybrid nanomaterial MGO-TCA-FA has been designed and constructed by grafting the triformyl cholic acid (TCA) and folic acid (FA) on the surface of Fe3O4 modified graphene oxide (MGO). The doxorubicin hydrochloride (DOX) as a model drug could be effectively loaded on the MGO-TCA-FA via hydrogen bonding and π-π stacking (the drug loading amount was 1040 mg/g). The formed MGO-TCA-FA@DOX has been developed to be an effective PCT nanoplatform with the advantages of multiple-targeted drug delivery, near-infrared light (NIR) and pH triggered drug release, and photothermal conversion efficiency. In vitro experiments showed that compared with other cancer cells and normal liver cells, MGO-TCA-FA@DOX could specifically target liver cancer cells and presented significant killing ability to liver cancer cells. More importantly, in vivo experiments indicated that PCT synergistic therapy (MGO-TCA-FA@DOX) revealed the best tumor inhibition (the tumor inhibition rate was about 85%) compared with chemotherapy and photothermal therapy alone. Thus, this study supplied a viable multiple-targeted PCT nano-agent for chemo-photothermal combination therapy of liver cancer.

Van der Waals enhanced interfacial interaction in cellulose/zinc oxide nanocomposite coupled by graphitic carbon nitride.

In-depth understanding of interfacial property is the key to guiding the synthesis of biomass composites with desired performance. However, the exploration is of great challenge due to limitations of experimental techniques in locating hydrogen, requiring large/good crystals and detecting a weak interaction like van der Waals (vdW). Herein, we experimentally and computationally investigated the composite cellulose/zinc oxide/g-C3N4. Hydrothermal synthesis afforded cellulose/ZnO, and then fabricated the ternary composite by adding g-C3N4 under ultrasonic condition. Three components are found to co-exist in the composite, and the ZnO nanoparticle is attaching to cellulose and coupling with g-C3N4. These experimental findings were corroborated by relativistic DFT calculations. The interfacial coupling is elaborated as contributions of dative bonds, hydrogen bonds and vdW interaction. The vdW is increased by a factor of 4.23 in the ZnO/g-C3N4 interface. This improves electron-hole separation and offers prospective application of the composite in photocatalysis, antibacteria and gas sensing.

Synergistic Photodynamic and Photothermal Antibacterial Activity of In Situ Grown Bacterial Cellulose/MoS2-Chitosan Nanocomposite Materials with Visible Light Illumination.

Owing to the rise in prevalence of multidrug-resistant pathogens attributed to the overuse of antibiotics, infectious diseases caused by the transmission of microbes from contaminated surfaces to new hosts are an ever-increasing threat to public health. Thus, novel materials that can stem this crisis, while also functioning via multiple antimicrobial mechanisms so that pathogens are unable to develop resistance to them, are in urgent need. Toward this goal, in this work, we developed in situ grown bacterial cellulose/MoS2-chitosan nanocomposite materials (termed BC/MoS2-CS) that utilize synergistic membrane disruption and photodynamic and photothermal antibacterial activities to achieve more efficient bactericidal activity. The BC/MoS2-CS nanocomposite exhibited excellent antibacterial efficacy, achieving 99.998% (4.7 log units) and 99.988% (3.9 log units) photoinactivation of Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus, respectively, under visible-light illumination (xenon lamp, 500 W, λ ≥ 420 nm, and 30 min). Mechanistic studies revealed that the use of cationic chitosan likely facilitated bacterial membrane disruption and/or permeability, with hyperthermia (photothermal) and reactive oxygen species (photodynamic) leading to synergistic pathogen inactivation upon visible-light illumination. No mammalian cell cytotoxicity was observed for the BC/MoS2-CS membrane, suggesting that such composite nanomaterials are attractive as functional materials for infection control applications.

Albumin-Templated Bi2Se3-MnO2 Nanocomposites with Promoted Catalase-Like Activity for Enhanced Radiotherapy of Cancer.

Novel and effective radiosensitizers that can enhance radiosensitivity of tumor tissues and increase the local radiation dose are highly desirable. In this work, templated by bovine serum albumin (BSA), Bi2Se3-MnO2 nanocomposites (Bi2Se3-MnO2@BSA) were fabricated via biomineralization, while Bi2Se3 nanodots act as radiosensitizers to increase the local radiation dosage because of their strong X-ray attenuation ability, and MnO2 with catalase-like activity can increase the oxygen concentration in tumors by triggering the decomposition of tumor endogenous H2O2 so as to improve the hypoxia-associated radioresistance of tumors. Owing to the interaction of the two components in the interface, Bi2Se3-MnO2@BSA showed promoted catalytic activity compared to MnO2@BSA, favoring tumor radiotherapy (RT) sensitization. BSA templating enabled the nanocomposites with high colloidal stability and biocompatibility as well as satisfactory tumor targeting both in vitro and in vivo; thus, an enhanced RT efficacy was obtained. Moreover, the proposed Bi2Se3-MnO2@BSA exhibited excellent performances in computerized tomography and magnetic resonance imaging. Thus, this work provides a tumor microenvironment-responsive multifunctional theranostic nanoagent with an improved performance for imaging-guided tumor RT sensitization.

Cellulose nanocrystals reinforced highly stretchable thermal-sensitive hydrogel with ultra-high drug loading.

Hydrogels often have poor mechanical properties which limit their application in load-bearing tissues such as muscle and cartilage. In this work, a near-infrared light-triggered stretchable thermal-sensitive hydrogel with ultra-high drug loading was developed by a combination of natural polymeric nanocrystals, a network of synthetic thermo-responsive polymer, and magnetic Fe3O4 nanoparticles. The hydrogels comprise cellulose nanocrystals (CNCs) decorated with Fe3O4 nanoparticles (Fe3O4/CNCs) dispersed homogeneously in poly(N-isopropylacrylamide) (PNIPAm) networks. The composite hydrogels exhibit an extensibility of 2200%. Drug loading of vancomycin (VCM) reached a high value of 10.18 g g-1 due to the dispersion of Fe3O4/CNCs and the interactions between the CNCs and the PNIPAm network. Importantly, the hydrogels demonstrated a thermo-response triggered by NIR, with the temperature increasing from 26 to 41 °C within 60 s. The hydrogels have high biocompatibility evidenced by cell proliferation tests, illustrating that these hydrogels are promising as dressings for wound closure, and wound healing.

FRET Modulated Signaling: A Versatile Strategy to Construct Photoelectrochemical Microsensors for In Vivo Analysis.

Microelectrode-based electrochemical (EC) and photoelectrochemical (PEC) sensors are promising candidates for in vivo analysis of biologically important chemicals. However, limited selectivity in complicated biological systems and poor adaptability to electrochemically non-active species restrained their applications. Herein, we propose the concept of modulating the PEC output by a fluorescence resonance energy transfer (FRET) process. The emission of energy donor was dependent on the concentration of target SO2 , which in turn served as the modulator of the photocurrent signal of the photoactive material. The employment of optical modulation circumvented the problem of selectivity, and the as-fabricated PEC microelectrode showed good stability and reproducibility in vivo. It can monitor fluctuations of SO2 levels in brains of rat models of cerebral ischemia-reperfusion and febrile seizure. More significantly, such a FRET modulated signaling strategy can be extended to diverse analytes.

Polyaniline@Au organic-inorganic nanohybrids with thermometer readout for photothermal immunoassay of tumor marker.

A photothermal immunoassay using a thermometer as readout based on polyaniline@Au organic-inorganic nanohybrids was built. Temperature output is acquired due to the photothermal effect of the photothermal nanomaterial. Polyaniline@Au organic-inorganic nanohybrids were synthesized by interfacial reactions with high photothermal conversion efficiency. A sandwich structure of the immunocomplex was prepared on a microplate for determination of carcinoembryonic antigen (CEA) by polyaniline@Au organic-inorganic nanohybrids as nanolabel. The released heat based on light-to-heat conversion from the photothermal nanolabel under NIR irradiation is detectable using the thermometer. The increased temperature is directly proportional to CEA concentration. The linear range of the photothermal immunoassay is 0.20 to 25 ng mL-1 with determination limit of 0.17 ng mL-1. Polyaniline@Au organic-inorganic nanohybrids with high photothermal conversion efficiency was synthesized as labels to construct photothermal immunosensor. The sandwich-type immunoassay was built on 96 hole plate based on specific binding of antigen and antibody. Carcinoembryonic antigen in sample was detected quantitatively by thermometer readout.

NIR-Driven Intracellular Photocatalytic O2 Evolution on Z-Scheme Ni3S2/Cu1.8S@HA for Hypoxic Tumor Therapy.

Hypoxia in a tumor microenvironment (TME) has inhibited the photodynamic therapy (PDT) efficacy. Here, Ni3S2/Cu1.8S nanoheterostructures were synthesized as a new photosensitizer, which also realizes the intracellular photocatalytic O2 evolution to relieve hypoxia in TME and enhance PDT as well. With the narrow band gap (below 1.5 eV), the near infrared (NIR) (808 nm) can stimulate their separation of the electron-hole. The novel Z-scheme nanoheterostructures, testified by experimental data and density functional theory (DFT) calculation, possess a higher redox ability, endowing the photoexited holes with sufficient potential to oxide H2O into O2, directly. Meanwhile, the photostimulated electrons can capture the dissolved O2 to form a toxic reactive oxygen species (ROS). Moreover, Ni3S2/Cu1.8S nanocomposites also possess the catalase-/peroxidase-like activity to convert the endogenous H2O2 into ·OH and O2, which not only cause chemodynamic therapy (CDT) but also alleviate hypoxia to assist the PDT as well. In addition, owing to the narrow band gap, they possess a high NIR harvest and great photothermal conversion efficiency (49.5%). It is noted that the nanocomposites also exhibit novel biodegradation and can be metabolized and eliminated via feces and urine within 2 weeks. The present single electrons in Ni/Cu ions induce the magnetic resonance imaging (MRI) ability for Ni3S2/Cu1.8S. To make sure that the cancer cells were specifically targeted, hyaluronic acid (HA) was grafted outside and Ni3S2/Cu1.8S@HA integrated photodynamic therapy (PDT), chemodynamic therapy (CDT), and photothermal therapy (PTT) to exhibit the great anticancer efficiency for hypoxic tumor elimination.

Novel Core-Sheath Cu/Cu2O-ZnO-Fe3O4 Nanocomposites with High-Efficiency Chlorine-Resistant Bacteria Sterilization and Trichloroacetic Acid Degradation Performance.

In order to solve two issues of chlorine-resistant bacteria (CRB) and disinfection byproducts (DBPs) in tap water after the chlorine-containing treatment process, an innovative core-sheath nanostructured Cu/Cu2O-ZnO-Fe3O4 was designed and synthesized. The fabrication mechanism of the materials was then systematically analyzed to determine the component and valence state. The properties of CRB inactivation together with trichloroacetic acid (TCAA) photodegradation by Cu/Cu2O-ZnO-Fe3O4 were investigated in detail. It was found that Cu/Cu2O-ZnO-Fe3O4 displayed excellent antibacterial activity with a relatively low cytotoxicity concentration due to its synergism of nanowire structure, ion release, and reactive oxygen species generation. Furthermore, the Cu/Cu2O-ZnO-Fe3O4 nanocomposite also exhibited outstanding photocatalytic degradation activity on TCAA under simulated sunlight irradiation, which was verified to be dominated by the surface reaction through kinetic analysis. More interestingly, the cell growth rate of Cu/Cu2O-ZnO-Fe3O4 was determined to be 50% and 10% higher than those of Cu/Cu2O and Cu/Cu2O-ZnO after 10 h incubation, respectively, manifesting a weaker cytotoxicity. Therefore, the designed Cu/Cu2O-ZnO-Fe3O4 could be a promising agent for tap water treatment.

A novel ternary heterogeneous TiO2/BiVO4/NaY-Zeolite nanocomposite for photocatalytic degradation of microcystin-leucine arginine (MC-LR) under visible light.

Microcystin-leucine arginine (MC-LR) is a carcinogenic toxin, produced by cyanobacteria. The release of this toxin into drinking water sources can threaten public health and environmental safety. Therefore, effective MC-LR removal from water resources is necessary. In the present study, the hydrothermal method was used to synthesize a novel ternary BiVO4/TiO2/NaY-Zeolite (B/T/N-Z) nanocomposite for MC-LR degradation under visible light. FESEM, FTIR, XRD, and DRS were performed for characterizing the nanocomposite structure. Also, the Response Surface Methodology (RSM) was applied to determine the impact of catalyst dosage, pH, and contact time on the MC-LR removal. High-performance liquid chromatography was performed to measure the MC-LR concentration. Based on the results, independent parameters, including contact time, catalyst dosage, and pH, significantly affected the MC-LR removal (P < 0.05). In other words, increasing the contact time, catalyst dosage, and acidic pH had positive effects on MC-LR removal. Among these variables, the catalyst dosage, with the mean square and F-value of 1041.37 and 162.84, respectively, had the greatest effect on the MC-LR removal efficiency. Apart from the interaction between the catalyst dosage and contact time, the interaction effects of other parameters were not significant. Also, the maximum MC-LR removal efficiency was 99.88% under optimal conditions (contact time = 120 min, catalyst dosage = 1 g/L, and pH = 5). According to the results, the B/T/N-Z nanocomposite, as a novel and effective photocatalyst could be used to degrade MC-LR from polluted water.

Antibacterial Activity of Porous Gold Nanocomposites via NIR Light-Triggered Photothermal and Photodynamic Effects.

Phototherapeutic approaches, including photothermal therapy (PTT) and photodynamic therapy (PDT), have become a promising strategy to combat microbial pathogens and tackle the crisis brought about by antibiotic-resistant strains. Herein, porous gold nanoparticles (AuPNs) were synthesized as photothermal agents and loaded with indocyanine green (ICG), a common photosensitizer for PDT, to fabricate a nanosystem presenting near-infrared (NIR) light-triggered synchronous PTT and PDT effects. The AuPNs can not only convert NIR light into heat with a high photothermal conversion efficiency (50.6-68.5%), but also provide a porous structure to facilely load ICG molecules. The adsorption of ICG onto AuPNs was mainly driven by electrostatic and hydrophobic interactions with the surfactant layer of AuPNs, and the aggregate state of ICG significantly enhanced its generation of reactive oxygen species. Moreover, taking advantage of its synergistic PTT and PDT effect, the hybrid nanocomposites displayed a remarkable antibacterial effect to the gram-positive pathogen Staphylococcus aureus (S. aureus) upon 808 nm laser irradiation.

Use of gamma irradiation technology for modification of bacterial cellulose nanocrystals/chitosan nanocomposite film.

The objective of this work was to investigate the influence of different gamma ray dosages (5, 10, and 10 kGy) on the structural, mechanical, surface and barrier properties of chitosan (Ch) based nanocomposite film. The results showed gamma irradiation caused an increase in the surface hydrophobicity, water vapor permeability and sensitivity of films to water and also, yellowness and opacity of films increased, simultaneously. By increasing the irradiation doses up to 10 kGy, the mechanical properties of Ch/BCNC film was significantly enhanced. As observed by FTIR spectra, no change occurred in the chemical functional groups of the films during irradiation. XRD studies confirmed that crystallinity of films was increased after irradiation. The nanocomposite film irradiated by 10 kGy had the highest thermal stability. In conclusion, gamma radiation can be considered as a safe method for sterilization of foods and modification of Ch/BCNC film properties.