Multiple Carbon Morphologies Derived from Polyion Complex-Based Double Hydrophilic Block Copolymers as Templates and Phenol as a Carbon Precursor.

This study demonstrates the multiple carbon morphology forming abilities of two dissimilar polyion complex (PIC)-based double hydrophilic block copolymers (DHBC) along with three different phenol concentrations when subjecting the blend in aqueous media via a hydrothermal-assisted carbonization strategy. The morphological transition from worm-like to spherical along with granular is found for the blend of oppositely charged poly(ethylene glycol) (PEG)-conjugated poly(amino acid) block copolymers, PEG-poly(l-lysine) (PEG-PLys) and PEG-poly(glutamic acid) (PEG-PGlu), along with three different concentrations of phenol. In contrast, after mixing the combination of PEG-PLys and PEG-poly(aspartic acid) (PEG-PAsp) separately with three different phenol contents, elliptical to irregular to spherical structural transition occurred. Fourier transform infrared and circular dichroism spectroscopic studies indicated that the formation of worm-like hybrid micellar structures is attributed to the presence of the ß-sheet structure, whereas spherical-shaped hybrid micellar structures are formed due to the existence of α-helix and random coil structures. We discuss the mechanism for the secondary structure-induced morphology formation based on the theory related to the packing parameter, which is commonly used for analyzing the shape of the micellar structures. Secondary structures of the PIC-based DHBC system are responsible for forming multiple carbon morphologies, whereas these structures are absent in the case of the amphiphilic block copolymer (ABC) system. Furthermore, ABC-based template methods require organic solvent, ultrasonication, and a prolonged solvent evaporation process to obtain multiple carbon morphologies. Scanning electron microscopy observations suggested there is no significant morphological change even after subjecting the hybrid micelles to carbonization at elevated temperatures. Raman scattering studies revealed that the degree of graphitization and the graphitic crystallite domain size of the carbonized sample depend on the phenol content. Carbon materials exhibited the highest specific surface area of 579 m2 g-1 along with a pore volume of 0.398 cc g-1, and this observation suggests that the prepared carbons are porous. Our findings illustrate the facile and effective strategy to fabricate the multiple carbon morphologies that can be used as potential candidates for energy storage applications.

Fabrication of High-κ Dielectric Metal Oxide Films on Topographically Patterned Substrates: Polymer Brush-Mediated Depositions.

Fabrication of ultrathin films of dielectric (with particular reference to materials with high dielectric constants) materials has significance in many advanced technological applications including hard protective coatings, sensors, and next-generation logic devices. Current state-of-the-art in microelectronics for fabricating these thin films is a combination of atomic layer deposition and photolithography. As feature size decreases and aspect ratios increase, conformality of the films becomes paramount. Here, we show a polymer brush template-assisted deposition of highly conformal, ultrathin (sub 5 nm) high-κ dielectric metal oxide films (hafnium oxide and zirconium oxide) on topographically patterned silicon nitride substrates. This technique, using hydroxyl terminated poly-4-vinyl pyridine (P4VP-OH) as the polymer brush, allows for conformal deposition with uniform thickness along the trenches and sidewalls of the substrate. Metal salts are infiltrated into the grafted monolayer polymer brush films via solution deposition. Tailoring specific polymer interfacial chemistries for ion infiltration combined with subsequent oxygen plasma treatment enabled the fabrication of high-quality sub 5 nm metal oxide films.

Room Temperature Fabrication of Macroporous Lignin Membranes for the Scalable Production of Black Silicon.

Rising global demand for biodegradable materials and green sources of energy has brought attention to lignin. Herein, we report a method for manufacturing standalone lignin membranes without additives for the first time to date. We demonstrate a scalable method for macroporous (∼100 to 200 nm pores) lignin membrane production using four different organosolv lignin materials under a humid environment (>50% relative humidity) at ambient temperatures (∼20 °C). A range of different thicknesses is reported with densely porous films observed to form if the membrane thickness is below 100 nm. The fabricated membranes were readily used as a template for Ni2+ incorporation to produce a nickel oxide membrane after UV/ozone treatment. The resultant mask was etched via an inductively coupled plasma reactive ion etch process, forming a silicon membrane and as a result yielding black silicon (BSi) with a pore depth of >1 µm after 3 min with reflectance <3% in the visible light region. We anticipate that our lignin membrane methodology can be readily applied to various processes ranging from catalysis to sensing and adapted to large-scale manufacturing.

Comparison Study of an Optimized Ultrasound-Based Method versus an Optimized Conventional Method for Agar Extraction, and Protein Co-Extraction, from Gelidium sesquipedale.

Agar is a hydrocolloid found in red seaweeds, which has been of industrial interest over the last century due to its multiple applications in the food, cosmetic, and medical fields. This polysaccharide, extracted by boiling for several hours, is released from the cell wall of red seaweeds. However, the environmental impact coming from the long processing time and the energy required to reach the targeted processing temperature needs to be reduced. In this study, a response surface methodology was employed to optimize both conventional extraction and ultrasound-assisted extractions. Two different models were successfully obtained (R2 = 0.8773 and R2 = 0.7436, respectively). Additionally, a further re-extraction confirmed that more agar could be extracted. Protein was also successfully co-extracted in the seaweed residues. Optimized conditions were obtained for both the extractions and the re-extraction of the two methods (CE: 6 h, 100 °C; and UAE: 1 h, 100% power). Finally, FT-IR characterization demonstrated that the extracts had a similar spectrum to the commercial agar. Compared to commercial samples, the low gel strength of the agar extracts shows that these extracts might have novel and different potential applications.

Fabrication of Graphoepitaxial Gate-All-Around Si Circuitry Patterned Nanowire Arrays Using Block Copolymer Assisted Hard Mask Approach.

We demonstrate the fabrication of sub-20 nm gate-all-around silicon (Si) nanowire field effect transistor structures using self-assembly. To create nanopatterned Si feature arrays, a block-copolymer-assisted hard mask approach was utilized using a topographically patterned substrate with well-defined Si3N4 features for graphoepitaxially alignment of the self-assembled patterns. Microphase-separated long-range ordered polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block-copolymer-derived dot and line nanopatterns were achieved by a thermo-solvent approach within the substrate topographically defined channels of various widths and lengths. Solvent annealing parameters (temperature, annealing time, etc.) were varied to achieve the desired patterns. The BCP structures were modified by anhydrous ethanol to facilitate insertion of iron oxide features within the graphoepitaxial trenches that maintained the parent BCP arrangements. Vertical and horizontal ordered Si nanowire structures within trenches were fabricated using the iron oxide features as hard masks in an inductively coupled plasma (ICP) etch process. Cross-sectional micrographs depict wires of persistent width and flat sidewalls indicating the effectiveness of the mask. The aspect ratios could be varied by varying etch times. The sharp boundaries between the transistor components was also examined through the elemental mapping.

Biodegradation of Poly (Butylene Succinate) (PBS)/Stearate Modified Magnesium-Aluminium Layered Double Hydroxide Composites under Marine Conditions Prepared via Melt Compounding.

In the present work, polybutylene succinate (PBS)/stearate modified magnesium-aluminium layered double hydroxide (St-Mg-Al LDH) composites were prepared via melt processing and the effect of different loadings of St-Mg-Al LDH on the degradation behaviour of PBS under marine conditions was investigated. The morphological, mechanical and thermal characteristics of the composites were studied using different characterisation techniques. Optical imaging and scanning electron microscopy revealed that the incorporation of St-Mg-Al LDH accelerates the degradation of PBS along with the activity of microorganisms adhered to the composite films. PBS/St-Mg-Al LDH composites are found to have lower thermal degradation temperatures than those of pure PBS. The decrease in thermal stability is correlated with the degradation of PBS due to the catalytic action Mg and Al present in LDH. Tensile and DMA analysis revealed that the addition of St-Mg-Al LDH did not have a significant impact on the mechanical properties of PBS.

Streptomyces sp. BV410 isolate from chamomile rhizosphere soil efficiently produces staurosporine with antifungal and antiangiogenic properties.

Applying a bioactivity-guided isolation approach, staurosporine was separated and identified as the active principle in the culture extract of the new isolate Streptomyces sp. BV410 collected from the chamomile rhizosphere. The biotechnological production of staurosporine by strain BV410 was optimized to yield 56 mg/L after 14 days of incubation in soy flour-glucose-starch-mannitol-based fermentation medium (JS). The addition of FeSO4 significantly improved the staurosporine yield by 30%, while the addition of ZnSO4 significantly reduced staurosporine yield by 62% in comparison with the starting conditions. Although staurosporine was first isolated in 1977 from Lentzea albida (now Streptomyces staurosporeus) and its potent kinase inhibitory effect has been established, here, the biological activity of this natural product was assessed in depth in vivo using a selection of transgenic zebrafish (Danio rerio) models, including Tg(fli1:EGFP) with green fluorescent protein-labeled endothelial cells allowing visualization and monitoring of blood vessels. This confirmed a remarkable antiangiogenic activity of the compound at doses of 1 ng/ml (2.14 nmol/L) which is below doses inducing toxic effects (45 ng/ml; 75 nmol/L). A new, efficient producing strain of commercially significant staurosporine has been described along with optimized fermentation conditions, which may lead to optimization of the staurosporine scaffold and its wider applicability.

Development of an efficient biocatalytic system based on bacterial laccase for the oxidation of selected 1,4-dihydropyridines.

Biocatalytic oxidations mediated by laccases are gaining importance due to their versatility and beneficial environmental effects. In this study, the oxidation of 1,4-dihydropyridines has been performed using three different types of bacterial laccase-based catalysts: purified laccase from Bacillus licheniformis ATCC 9945a (BliLacc), Escherichia coli whole cells expressing this laccase, and bacterial nanocellulose (BNC) supported BliLacc catalysts. The catalysts based on bacterial laccase were compared to the commercially available Trametes versicolor laccase (TvLacc). The oxidation product of 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate was obtained within 7-24 h with good yields (70-99%) with all three biocatalysts. The substrate scope was examined with five additional 1,4-dihydropyridines, one of which was oxidized in high yield. Whole-cell biocatalyst was stable when stored for up to 1-month at 4 °C. In addition, evidence has been provided that multicopper oxidase CueO from the E. coli expression host contributed to the oxidation efficiency of the whole-cell biocatalyst. The immobilized whole-cell biocatalyst showed satisfactory activity and retained 37% of its original activity after three biotransformation cycles.

Production of bacterial nanocellulose (BNC) and its application as a solid support in transition metal catalysed cross-coupling reactions.

Bacterial nanocellulose (BNC) emerged as an attractive advanced biomaterial that provides desirable properties such as high strength, lightweight, tailorable surface chemistry, hydrophilicity, and biodegradability. BNC was successfully obtained from a wide range of carbon sources including sugars derived from grass biomass using Komagataeibacter medellinensis ID13488 strain with yields up to 6 g L-1 in static fermentation. Produced BNC was utilized in straightforward catalyst preparation as a solid support for two different transition metals, palladium and copper with metal loading of 20 and 3 wt%, respectively. Sustainable catalysts were applied in the synthesis of valuable fine chemicals, such as biphenyl-4-amine and 4'-fluorobiphenyl-4-amine, used in drug discovery, perfumes and dye industries with excellent product yields of up to 99%. Pd/BNC catalyst was reused 4 times and applied in two consecutive reactions, Suzuki-Miyaura cross-coupling reaction followed by hydrogenation of nitro to amino group while Cu/BNC catalyst was examined in Chan-Lam coupling reaction. Overall, the environmentally benign process of obtaining nanocellulose from biomass, followed by its utilisation as a solid support in metal-catalysed reactions and its recovery has been described. These findings reveal that BNC is a good support material, and it can be used as a support for different catalytic systems.

Nanopatterning via Self-Assembly of a Lamellar-Forming Polystyrene-block-Poly(dimethylsiloxane) Diblock Copolymer on Topographical Substrates Fabricated by Nanoimprint Lithography.

The self-assembly of a lamellar-forming polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS) diblock copolymer (DBCP) was studied herein for surface nanopatterning. The DBCP was synthesized by sequential living anionic polymerization of styrene and hexamethylcyclotrisiloxane (D3). The number average molecular weight (Mn), polydispersity index (Mw/Mn) and PS volume fraction (φps) of the DBCP were MnPS = 23.0 kg mol-1, MnPDMS = 15.0 kg mol-1, Mw/Mn = 1.06 and φps = 0.6. Thin films of the DBCP were cast and solvent annealed on topographically patterned polyhedral oligomeric silsesquioxane (POSS) substrates. The lamellae repeat distance or pitch (λL) and the width of the PDMS features (dL) are ~35 nm and ~17 nm, respectively, as determined by SEM. The chemistry of the POSS substrates was tuned, and the effects on the self-assembly of the DBCP noted. The PDMS nanopatterns were used as etching mask in order to transfer the DBCP pattern to underlying silicon substrate by a complex plasma etch process yielding sub-15 nm silicon features.

Large Block Copolymer Self-Assembly for Fabrication of Subwavelength Nanostructures for Applications in Optics.

Nanostructured surfaces are common in nature and exhibit properties such as antireflectivity (moth eyes), self-cleaning (lotus leaf), iridescent colors (butterfly wings), and water harvesting (desert beetles). We now understand such properties and can mimic some of these natural structures in the laboratory. However, these synthetic structures are limited since they are not easily mass produced over large areas due to the limited scalability of current technologies such as UV-lithography, the high cost of infrastructure, and the difficulty in nonplanar surfaces. Here, we report a solution process based on block copolymer (BCP) self-assembly to fabricate subwavelength structures on large areas of optical and curved surfaces with feature sizes and spacings designed to efficiently scatter visible light. Si nanopillars (SiNPs) with diameters of ∼115 ± 19 nm, periodicity of 180 ± 18 nm, and aspect ratio of 2-15 show a reduction in reflectivity by a factor of 100, <0.16% between 400 and 900 nm at an angle of incidence of 30°. Significantly, the reflectivity remains below 1.75% up to incident angles of 75°. Modeling the efficiency of a SiNP PV suggests a 24.6% increase in efficiency, representing a 3.52% (absolute) or 16.7% (relative) increase in electrical energy output from the PV system compared to AR-coated device.

Self-Assembled Nanofeatures in Complex Three-Dimensional Topographies via Nanoimprint and Block Copolymer Lithography Methods.

Achieving ultrasmall dimensions of materials and retaining high throughput are critical fabrication considerations for nanotechnology use. This article demonstrates an integrated approach for developing isolated sub-20 nm silicon oxide features through combined "top-down" and "bottom-up" methods: nanoimprint lithography (NIL) and block copolymer (BCP) lithography. Although techniques like those demonstrated here have been developed for nanolithographic application in the microelectronics processing industry, similar approaches could be utilized for sensor, fluidic, and optical-based devices. Thus, this article centers on looking at the possibility of generating isolated silica structures on substrates. NIL was used to create intriguing three-dimensional (3-D) polyhedral oligomeric silsesquioxane (POSS) topographical arrays that guided and confined polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS) BCP nanofeatures in isolated regions. A cylinder forming PS-b-PDMS BCP system was successfully etched using a one-step etching process to create line-space arrays with a period of 35 nm in confined POSS arrays. We highlight large-area (>6 µm) coverage of line-space arrays in 3-D topographies that could potentially be utilized, for example, in nanofluidic systems. Aligned features for directed self-assembly application are also demonstrated. The high-density, confined silicon oxide nanofeatures in soft lithographic templates over macroscopic areas illustrate the advantages of integrating distinct lithographic methods for attaining discrete features in the deep nanoscale regime.

A Highly Efficient Sensor Platform Using Simply Manufactured Nanodot Patterned Substrates.

Block copolymer (BCP) self-assembly is a low-cost means to nanopattern surfaces. Here, we use these nanopatterns to directly print arrays of nanodots onto a conducting substrate (Indium Tin Oxide (ITO) coated glass) for application as an electrochemical sensor for ethanol (EtOH) and hydrogen peroxide (H2O2) detection. The work demonstrates that BCP systems can be used as a highly efficient, flexible methodology for creating functional surfaces of materials. Highly dense iron oxide nanodots arrays that mimicked the original BCP pattern were prepared by an 'insitu' BCP inclusion methodology using poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO). The electrochemical behaviour of these densely packed arrays of iron oxide nanodots fabricated by two different molecular weight PS-b-PEO systems was studied. The dual detection of EtOH and H2O2 was clearly observed. The as-prepared nanodots have good long term thermal and chemical stability at the substrate and demonstrate promising electrocatalytic performance.

Fabrication of 3-D nanodimensioned electric double layer capacitor structures using block copolymer templates.

The need for materials for high energy storage has led to very significant research in supercapacitor systems. These can exhibit electrical double layer phenomena and capacitances up to hundreds of F/g. Here, we demonstrate a new supercapacitor fabrication methodology based around the microphase separation of PS-b-PMMA which has been used to prepare copper nanoelectrodes of dimension -13 nm. These structures provide excellent capacitive performance with a maximum specific capacitance of -836 F/g for a current density of 8.06 A/g at a discharge current as high as 75 mA. The excellent performance is due to a high surface area: volume ratio. We suggest that this highly novel, easily fabricated structure might have a number of important applications.

Fabrication of ordered, large scale, horizontally-aligned si nanowire arrays based on an in situ hard mask block copolymer approach.

A simple technique is demonstrated to fabricate horizontal, uniform, and hexagonally arranged Sinanowire arrays with controlled orientation and density at spatially well defined locations on a substrate based on an in situ hard-mask pattern-formation approach by microphase-separated block-copolymer thin films. The technique may have significant application in the manufacture of transistor circuitry.

Size and space controlled hexagonal arrays of superparamagnetic iron oxide nanodots: magnetic studies and application.

Highly dense hexagonally arranged iron oxide nanodots array were fabricated using PS-b-PEO self-assembled patterns. The copolymer molecular weight, composition and choice of annealing solvent/s allows dimensional and structural control of the nanopatterns at large scale. A mechanism is proposed to create scaffolds through degradation and/or modification of cylindrical domains. A methodology based on selective metal ion inclusion and subsequent processing was used to create iron oxide nanodots array. The nanodots have uniform size and shape and their placement mimics the original self-assembled nanopatterns. For the first time these precisely defined and size selective systems of ordered nanodots allow careful investigation of magnetic properties in dimensions from 50 nm to 10 nm, which delineate the nanodots are superparamagnetic, well-isolated and size monodispersed. This diameter/spacing controlled iron oxide nanodots systems were demonstrated as a resistant mask over silicon to fabricate densely packed, identical ordered, high aspect ratio silicon nanopillars and nanowire features.

Swift nanopattern formation of PS-b-PMMA and PS-b-PDMS block copolymer films using a microwave assisted technique.

Microphase separation of block copolymer (BCPs) thin films has high potential as a surface patterning technique. However, the process times (during thermal or solvent anneal) can be inordinately long, and for it to be introduced into manufacturing, there is a need to reduce these times from hours to minutes. We report here BCP self-assembly on two different systems, polystyrene-b-polymethylmethacrylate (PS-b-PMMA) (lamellar- and cylinder-forming) and polystyrene-b-polydimethylsiloxane (PS-b-PDMS) (cylinder-forming) by microwave irradiation to achieve ordering in short times. Unlike previous reports of microwave assisted microphase segregation, the microwave annealing method reported here was undertaken without addition of solvents. Factors such as the anneal time and temperature, BCP film thickness, substrate surface type, etc. were investigated for their effect of the ordering behavior. The microwave technique was found to be compatible with graphoepitaxy, and in the case of the PS-b-PDMS system, long-range translational alignment of the BCP domains was observed within the topographic patterns. To demonstrate the usefulness of the method, the BCP nanopatterns were turned into an 'on-chip' resist by an initial plasma etch and these were used to transfer the pattern into the substrate.

Tuning PDMS brush chemistry by UV-O3 exposure for PS-b-PDMS microphase separation and directed self-assembly.

The directed self-assembly (DSA) of block copolymer (BCP) thin films could enable a scalable, bottom-up alternative to photolithography for the generation of substrate features. The PS-b-PDMS (polystyrene-b-polydimethylsiloxane) system is attractive as it can be extended toward very small feature sizes as well as having two blocks that can be readily differentiated during pattern transfer. However, PS-b-PDMS offers a considerable challenge because of the chemical differences in the blocks which lead to poor surface-wetting, poor pattern orientation control, and structural instabilities. These challenges can be mitigated by careful definition of the interface chemistry between the substrate and the BCP. Here, we report controlled pattern formation in cylinder forming PS-b-PDMS system by use of a carefully controlled PDMS brush. Control of the brush was achieved using exposure to UV-O3 for varying time. It is demonstrated that this treatment enhances surface wetting and coverage of the BCP. The modified brushes also enable DSA of the BCP on topographically patterned substrates. UV-O3 exposure was also used to reveal the BCP structure and provide an in situ "hard mask" for pattern transfer to the substrate.

The sensitivity of random polymer brush-lamellar polystyrene-b-polymethylmethacrylate block copolymer systems to process conditions.

The use of random copolymer brushes (polystyrene-r-polymethylmethacrylate--PS-r-PMMA) to 'neutralise' substrate surfaces and ordain perpendicular orientation of the microphase separated lamellae in symmetric polystyrene-b-polymethylmethacrylate (PS-b-PMMA) block copolymers (BCPs) is well known. However, less well known is how the brushes interact with both the substrate and the BCP, and how this might change during thermal processing. A detailed study of changes in these films for different brush and diblock PS-b-PMMA molecular weights is reported here. In general, self-assembly and pattern formation is altered little, and a range of brush molecular weights are seen to be effective. However, on extended anneal times, the microphase separated films can undergo dimension changes and loss of order. This process is not related to any complex microphase separation dynamics but rather a degradation of methacrylate components in the film. The data suggest that care must be taken in interpretation of structural changes in these systems as being due to BCP only effects.

Orientation and alignment control of microphase-separated PS-b-PDMS substrate patterns via polymer brush chemistry.

Block copolymer (BCP) microphase separation at substrate surfaces might enable the generation of substrate features in a scalable, bottom-up fashion, provided that the pattern structure, orientation, and alignment can be strictly controlled. The PS-b-PDMS (polystyrene-b-polydimethylsiloxane) system is attractive because it can form small features and the two blocks can be readily differentiated during pattern transfer. However, PS-b-PDMS offers a considerable challenge, because of the chemical differences in the blocks, which leads to poor surface wetting, poor pattern orientation control, and structural instabilities. These challenges are considerably greater when line patterns must be created, and this is the focus of the current work. Here, we report controlled pattern formation in cylinder-forming PS-b-PDMS by anchoring different types of hydroxyl-terminated homopolymer and random copolymer brushes on planar and topographically patterned silicon substrates for the fabrication of nanoscale templates. It is demonstrated that non-PDMS-OH-containing brushes may be used, which offers an advantage for substrate feature formation. To demonstrate the three-dimensional (3-D) film structure and show the potential of this system toward applications such as structure generation, the PDMS patterns were transferred to the underlying substrate to fabricate nanoscale features with a feature size of ~14 nm.