Bio-Polyethylene and Polyethylene Biocomposites: An Alternative toward a Sustainable Future.

Polyethylene (PE), a highly prevalent non-biodegradable polymer in the field of plastics, presents a waste management issue. To alleviate this issue, bio-based PE (bio-PE), derived from renewable resources like corn and sugarcane, offers an environmentally friendly alternative. This review discusses various production methods of bio-PE, including fermentation, gasification, and catalytic conversion of biomass. Interestingly, the bio-PE production volumes and market are expanding due to the growing environmental concerns and regulatory pressures. Additionally, the production of PE and bio-PE biocomposites using agricultural waste as filler materials, highlights the growing demand for sustainable alternatives to conventional plastics. According to previous studies, addition of ≈50% defibrillated corn and abaca fibers into bio-PE matrix and a compatibilizer, results in the highest Young's modulus of 4.61 and 5.81 GPa, respectively. These biocomposites have potential applications in automotive, building construction, and furniture industries. Moreover, the advancement made in abiotic and biotic degradation of PE and PE biocomposites is elucidated to address their environmental impacts. Finally, the paper concludes with insights into the opportunities, challenges, and future perspectives in the sustainable production and utilization of PE and bio-PE biocomposites. In summary, production of PE and bio-PE biocomposites can contribute to a cleaner and sustainable future.

Mapping micrometer-scale wetting properties of superhydrophobic surfaces.

There is a huge interest in developing superrepellent surfaces for antifouling and heat-transfer applications. To characterize the wetting properties of such surfaces, the most common approach is to place a millimetric-sized droplet and measure its contact angles. The adhesion and friction forces can then be inferred indirectly using Furmidge's relation. While easy to implement, contact angle measurements are semiquantitative and cannot resolve wetting variations on a surface. Here, we attach a micrometric-sized droplet to an atomic force microscope cantilever to directly measure adhesion and friction forces with nanonewton force resolutions. We spatially map the micrometer-scale wetting properties of superhydrophobic surfaces and observe the time-resolved pinning-depinning dynamics as the droplet detaches from or moves across the surface.

Directional Excitation of Surface Plasmon Polaritons via Molecular Through-Bond Tunneling across Double-Barrier Tunnel Junctions.

Directional excitation of surface plasmon polaritons (SPPs) by electrical means is important for the integration of plasmonics with molecular electronics or steering signals toward other components. We report electrically driven SPP sources based on quantum mechanical tunneling across molecular double-barrier junctions, where the tunneling pathway is defined by the molecules' chemical structure as well as by their tilt angle with respect to the surface normal. Self-assembled monolayers of S(CH2)nBPh (BPh = biphenyl, n = 1-7) on Au, where the alkyl chain and the BPh units define two distinct tunnel barriers in series, were used to demonstrate and control the geometrical effects. The tilt angle of the BPh unit with respect to the surface normal depends on the value of n, and is 45° when n is even and 23° when n is odd. The tilt angle of the alkyl chain is fixed at 30° and independent of n. For values of n = 1-3, SPPs are directionally launched via directional tunneling through the BPh units. For values of n > 3, tunneling along the alkyl chain dominates the SPP excitation. Molecular level control of directionally launching SPPs is achieved without requiring additional on-chip optical elements, such as antennas, or external elements, such as light sources. Using the molecular tunneling junctions, we provide the first direct experimental demonstration of molecular double-barrier tunneling junctions.

Bright quantum-dot-sized single-chain conjugated polyelectrolyte nanoparticles: synthesis, characterization and application for specific extracellular labeling and imaging.

We report a simple method to fabricate quantum-dot-sized nanoparticles (NPs) from poly[9,9-bis((6-N,N,N-trimethylammonium)hexyl)fluorene-alt-co-2,1,3-benzo-xadiazole dibromide] (PFBD). The transmission electron microscope results reveal that the obtained NPs have a mean diameter of ≈4 nm, which is composed of a single PFBD chain. The NPs show bright fluorescence with an emission maximum at ≈636 nm and a quantum yield of ≈26% in water. The fluorescence properties of the NPs are characterized by steady fluorescence microscopy, fluorescence dynamic study and single nanoparticle microscopy, which show superior brightness over commercial quantum dots QD655. The NPs are further conjugated with streptavidin to yield PFBD-SA NPs, which serve as a specific extracellular labeling and imaging probe with high specificity and good photostability.

Hydrolytic degradation and biodegradation of polylactic acid electrospun fibers.

Increased use of bioplastics, such as polylactic acid (PLA), helps in reducing greenhouse gas emissions, decreases energy consumption and lowers pollution, but its degradation efficiency has much room for improvement. The degradation rate of electrospun PLA fibers of varying diameters ranging from 0.15 to 1.33 µm is measured during hydrolytic degradation under different pH from 5.5 to 10, and during aerobic biodegradation in seawater supplemented with activated sewage sludge. In hydrolytic conditions, varying PLA fiber diameter had significant influence over percentage weight loss (W%L), where faster degradation was achieved for PLA fibers with smaller diameter. W%L was greatest for PLA-5 > PLA-12 > PLA-16 > PLA-20, with average W%L at 30.7%, 27.8%, 17.2% and 14.3% respectively. While different pH environment does not have a significant influence on PLA degradation, with W%L only slightly higher for basic environments. Similarly biodegradation displayed faster degradation for small diameter fibers with PLA-5 attaining the highest degree of biodegradation at 22.8% after 90 days. Hydrolytic degradation resulted in no significant structural change, while biodegradation resulted in significant hydroxyl end capping products on the PLA surface. Scanning electron microscopy (SEM) imaging of degraded PLA fibers showed a deteriorated morphology of PLA-5 and PLA-12 fibers with increased adhesion structures and irregularly shaped fibers, while a largely unmodified morphology for PLA-16 and PLA-20.

A bioinspired silica nanocomposite for enhanced multidrug-resistant bacteria treatment and wash-free imaging.

Bacterial infections have posed significant threats to public health due to the emergence of antibiotic resistance. In this work, a novel antibacterial composite nanomaterial based on spiky mesoporous silica spheres loaded with poly(ionic liquid)s and aggregation-induced emission luminogens (AIEgens) was designed for efficient multidrug-resistant (MDR) bacteria treatment and imaging. The nanocomposite exhibited excellent and long-term antibacterial activity towards both Gram-negative and Gram-positive bacteria. Meanwhile, fluorescent AIEgens facilitate real-time bacterial imaging. Our study provides a multifunctional platform and a promising alternative to antibiotics for combating pathogenic MDR bacteria.

AFM Manipulation of EGaIn Microdroplets to Generate Controlled, On-Demand Contacts on Molecular Self-Assembled Monolayers.

Liquid metal droplets, such as eutectic gallium-indium (EGaIn), are important in many research areas, such as soft electronics, catalysis, and energy storage. Droplet contact on solid surfaces is typically achieved without control over the applied force and without optimizing the wetting properties in different environments (e.g., in air or liquid), resulting in poorly defined contact areas. In this work, we demonstrate the direct manipulation of EGaIn microdroplets using an atomic force microscope (AFM) to generate repeated, on-demand making and breaking of contact on self-assembled monolayers (SAMs) of alkanethiols. The nanoscale positional control and feedback loop in an AFM allow us to control the contact force at the nanonewton level and, consequently, tune the droplet contact areas at the micrometer length scale in both air and ethanol. When submerged in ethanol, the droplets are highly nonwetting, resulting in hysteresis-free contact forces and minimal adhesion; as a result, we are able to create reproducible geometric contact areas of 0.8-4.5 µm2 with the alkanethiolate SAMs in ethanol. In contrast, there is a larger hysteresis in the contact forces and larger adhesion for the same EGaIn droplet in air, which reduced the control over the contact area (4-12 µm2). We demonstrate the usefulness of the technique and of the gained insights in EGaIn contact mechanics by making well-defined molecular tunneling junctions based on alkanethiolate SAMs with small geometric contact areas of between 4 and 12 µm2 in air, 1 to 2 orders of magnitude smaller than previously achieved.

Influence of the length and grafting density of PNIPAM chains on the colloidal and optical properties of quantum dot/PNIPAM assemblies.

Structural and optical characterization of water soluble, thermo-responsive quantum dot/poly(N-isopropyl acrylamide) (QD/PNIPAM) hybrid particles using fluorescence correlation spectroscopy (FCS) and time-correlated single photon counting (TCSPC) measurements performed at temperatures below and above the lower critical solution temperature (LCST) of PNIPAM is reported. By increasing the temperature above the LCST, the signature of the PNIPAM chain collapse covering the QDs is revealed by FCS measurements. Despite the significant structural change, the TCSPC measurements show that the fluorescence lifetimes remain of the same order of magnitude at T > LCST. Such QD/PNIPAM hybrid particles with water solubility and robust thermo-responsive behavior at physiologically relevant temperatures are potentially useful for (bio)molecular sensing and separation applications.

Visualizing resonance energy transfer in supramolecular surface patterns of ß-CD-functionalized quantum dot hosts and organic dye guests by fluorescence lifetime imaging.

Detection of an analyte via supramolecular host-guest binding and quantum dot (QD)-based fluorescence resonance energy transfer (FRET) signal transduction mechanism is demonstrated. Surface patterns consisting of CdSe/ZnS QDs functionalized at their periphery with ß-cyclodextrin (ß-CD) were obtained by immobilization of the QDs from solution onto glass substrates patterned with adamantyl-terminated poly(propylene imine) dendrimeric "glue." Subsequent formation of host-guest complexes between vacant ß-CD on the QD surface and an adamantyl-functionalized lissamine rhodamine resulting in FRET was confirmed by fluorescence microscopy, spectroscopy, and fluorescence lifetime imaging microscopy (FLIM).

Ferrocene-coated CdSe/ZnS quantum dots as electroactive nanoparticles hybrids.

Electrochemical properties of core-shell CdSe/ZnS quantum dots (QDs) in a non-aqueous solution are presented. Cathodic reduction and anodic oxidation processes involving the QD HOMO and LUMO levels as well as defect states were identified by cyclic voltammetry. The electrochemical bandgap was estimated from the anodic and cathodic redox peaks and found to match well with the optical bandgap estimated from the absorption spectrum. The trioctylphosphine oxide ligands on the surface of the QDs were exchanged to electroactive ferrocenyl thiols and the resulting material was characterized by NMR and optical spectroscopy. Cyclic voltammetry showed that the redox potentials of the QDs are modified due to the presence of ferrocene on the surface of the QD. The QD oxidation peak decreased and the reduction peak shifted to more negative potentials. The concurrent shift of the ferrocene redox peaks indicates that the system displays features of a 'molecular hybrid', where both the QD and the ligand influence each other.

Quantifying Surface Wetting Properties Using Droplet Probe Atomic Force Microscopy.

The functional properties of a surface, such as its anti-fogging or anti-fouling performance, are influenced by its wettability. To quantify surface wettability, the most common approach is to measure the contact angles of a liquid droplet on the surface. While well established and relatively easy to perform, contact angle measurements were developed to describe macroscopic wetting properties and are difficult to perform for submillimetric droplets. Moreover, they cannot spatially resolve surface heterogeneities that can contribute to surface fouling. To address these shortcomings, we report on using an atomic force microscopy technique to quantitatively measure the interaction forces between a microdroplet and a surface with piconewton force resolution. We show how our technique can be used to spatially map topographical and chemical heterogeneities with micron resolution.

Temperature-modulated quenching of quantum dots covalently coupled to chain ends of poly(N-isopropyl acrylamide) brushes on gold.

A thermo-responsive polymer/quantum dot platform based on poly(N-isopropyl acrylamide) (PNIPAM) brushes 'grafted from' a gold substrate and quantum dots (QDs) covalently attached to the PNIPAM layer is presented. The PNIPAM brushes are grafted from the gold surface using an iniferter-initiated controlled radical polymerization. The PNIPAM chain ends are functionalized with amine groups for coupling to water-dispersible COOH-functionalized QDs. Upon increasing the temperature above the lower critical solution temperature (LCST) of PNIPAM the QD luminescence is quenched. The luminescence was observed to recover upon decreasing the temperature below the LCTS. The data obtained are consistent with temperature-modulated thickness changes of the PNIPAM layer and quenching of the QDs by the gold surface via nonradiative energy transfer.

In Operando Characterization and Control over Intermittent Light Emission from Molecular Tunnel Junctions via Molecular Backbone Rigidity.

In principle, excitation of surface plasmons by molecular tunnel junctions can be controlled at the molecular level. Stable electrical excitation sources of surface plasmons are therefore desirable. Herein, molecular junctions are reported where tunneling charge carriers excite surface plasmons in the gold bottom electrodes via inelastic tunneling and it is shown that the intermittent light emission (blinking) originates from conformational dynamics of the molecules. The blinking rates, in turn, are controlled by changing the rigidity of the molecular backbone. Power spectral density analysis shows that molecular junctions with flexible aliphatic molecules blink, while junctions with rigid aromatic molecules do not.

Probing the morphology and nanoscale mechanics of single poly(N-isopropylacrylamide) microgels across the lower-critical-solution temperature by atomic force microscopy.

Submicrometer-sized particles of poly(N-isopropylacrylamide) (PNIPAM) are synthesized by surfactant-free radical polymerization. The morphology and nanomechanical properties of individual, isolated PNIPAM microgel particles at the silicon/air and silicon/water interfaces, below and above the PNIPAM volume-phase-transition temperature (VPTT), are probed by atomic force microscopy. In air, and in water below the VPTT, the PNIPAM spheres are flattened and adopt a pancakelike shape. Interestingly, above the VPTT the microgels adopt a more spherical form with increased height and decreased width, which is attributed to reduced interactions of the particles with the substrate. The elastic modulus calculated from force-indentation curves obtained for individual microgel spheres reveals that the stiffness of the particle's surface decreases by two orders of magnitude upon swelling in water. Additionally, the modulus of the PNIPAM spheres in water increases by one order of magnitude when crossing the VPTT from the swollen to the collapsed states, indicating a more compact chain packing at the particle surface.

Organic nanoparticles with ultrahigh quantum yield and aggregation-induced emission characteristics for cellular imaging and real-time two-photon lung vasculature imaging.

Fluorescent organic nanoparticles based on small molecules have emerged as an attractive class of fluorescent agents for bioimaging in recent years. Herein, we report orange light-emitting BTPEBD based organic nanoparticles (BTPEBD NPs) with a large Stokes shift (>135 nm), ultrahigh quantum yield (>90% in water) and aggregation-induced emission characteristics. Single nanoparticle analysis studied by wide field microscopy imaging further proves that the BTPEBD NPs exhibit high brightness and good photostability. Both in vitro and in vivo experiments reveal that the BTPEBD NPs are promising fluorescent agents for cellular imaging and real-time two-photon lung vasculature imaging.

Protein Nanocage as a pH-Switchable Pickering Emulsifier.

Encapsulation of active compounds in Pickering emulsions using bioderived protein-based stabilizers holds potential for the development of novel formulations in the fields of foods and cosmetics. We employ a dodecahedron hollow protein nanocage as a pH-switchable Pickering emulsifier. E2 protein nanocages are derived from pyruvate dehydrogenase multienzyme complex from Geobacillus stearothermophilus which adsorb at the oil/water interface at neutral and basic pH's and stabilize the Pickering emulsions, while in the acidic range, at pH ∼4, the emulsion separates into emulsion and serum phases due to flocculation. The observed process is reversible for at least five cycles. Optimal formulation of a Pickering emulsion composed of rosemary oil, an essential oil, and water has been achieved by ultrasonication and results in droplets of approximately 300 nm in diameter with an oil/water ratio of 0.11 (v/v) and 0.30-0.35% (wt %). Ionic stabilization is observed for concentrations up to 250 mM NaCl and pH values from 7 to 11. The emulsions are stable for at least 10 days when stored at different temperatures up to 50 °C. The resulting Pickering emulsions of different compositions also form a gel-like structure and show shear thinning behavior under shear stress at a higher oil/water ratio.

Ultrasmall Conjugated Polymer Nanoparticles with High Specificity for Targeted Cancer Cell Imaging.

Fluorescent and biocompatible organic nanoparticles have attracted great interest in cancer detection and imaging, but the nonspecific cellular uptake has limited the detection specificity and sensitivity. Herein, the authors report the ultrasmall conjugated polymer nanoparticles (CPNs) with bright far-red/near-infrared emission for targeted cancer imaging with high specificity. The sizes of the ultrasmall CPNs are around 6 nm (CPN6), while large CPNs show sizes around 30 nm (CPN30). Moreover, CPN6 exhibits largely improved fluorescence quantum yield (η) of 41% than CPN30 (25%). Benefiting from the ultrasmall size, bare CPN6 shows largely suppressed nonspecific cellular uptake as compared to CPN30, while cyclic arginine-glycine-aspartic acid (cRGD) functionalized CPN6 (cRGD-CPN6) possesses excellent selectivity toward αvß3 integrin overexpressed MDA-MB-231 cells over other cells in cell mixtures. The faster body clearance of CPN6 over CPN30 indicates its greater potentials as a noninvasive nanoprobe for in vivo and practical applications.

Specific Internalisation of Gold Nanoparticles into Engineered Porous Protein Cages via Affinity Binding.

Porous protein cages are supramolecular protein self-assemblies presenting pores that allow the access of surrounding molecules and ions into their core in order to store and transport them in biological environments. Protein cages' pores are attractive channels for the internalisation of inorganic nanoparticles and an alternative for the preparation of hybrid bioinspired nanoparticles. However, strategies based on nanoparticle transport through the pores are largely unexplored, due to the difficulty of tailoring nanoparticles that have diameters commensurate with the pores size and simultaneously displaying specific affinity to the cages' core and low non-specific binding to the cages' outer surface. We evaluated the specific internalisation of single small gold nanoparticles, 3.9 nm in diameter, into porous protein cages via affinity binding. The E2 protein cage derived from the Geobacillus stearothermophilus presents 12 pores, 6 nm in diameter, and an empty core of 13 nm in diameter. We engineered the E2 protein by site-directed mutagenesis with oligohistidine sequences exposing them into the cage's core. Dynamic light scattering and electron microscopy analysis show that the structures of E2 protein cages mutated with bis- or penta-histidine sequences are well conserved. The surface of the gold nanoparticles was passivated with a self-assembled monolayer made of a mixture of short peptidols and thiolated alkane ethylene glycol ligands. Such monolayers are found to provide thin coatings preventing non-specific binding to proteins. Further functionalisation of the peptide coated gold nanoparticles with Ni2+ nitrilotriacetic moieties enabled the specific binding to oligohistidine tagged cages. The internalisation via affinity binding was evaluated by electron microscopy analysis. From the various mutations tested, only the penta-histidine mutated E2 protein cage showed repeatable and stable internalisation. The present work overcomes the limitations of currently available approaches and provides a new route to design tailored and well-controlled hybrid nanoparticles.

A multifunctional probe with aggregation-induced emission characteristics for selective fluorescence imaging and photodynamic killing of bacteria over mammalian cells.

A multifunctional probe aggregation-induced emission-Zinc(II)-dipicolylamine (AIE-ZnDPA) is developed for selective targeting, fluorescence imaging, and photodynamic killing of both Gram-positive and Gram-negative bacteria over mammalian cells. The probe has significant advantages in simple probe design, enhanced fluorescence upon bacteria binding, excellent photostability, and broad-spectrum antibacterial activity with almost no harm to mammalian cells.