Name: towards biomimicking wood: fabricated free-standing films of nanocellulose, lignin, and a synthetic polycation
Uploaded: 2014-06-17T22:45:00
Description: Watch this Scientific Journal Video about Towards Biomimicking Wood: Fabricated Free-standing Films of Nanocellulose, Lignin, and a Synthetic Polycation at JoVE.com

This work was supported primarily by the Doctoral Scholar&#8217;s program of the Institute for Critical Technology and Applied Science (ICTAS) at Virginia Tech, the Virginia Tech Graduate School for supporting the Sustainable Nanotechnology program, and also the United States Department of Agriculture, NIFA grant number 2010-65504-20429. The authors also thank the contributions of Rick Caudill, Stephen McCartney, and W. Travis Church to this work.

1. Nanofibrillated Cellulose Preparation55
<ol>
	<li>Setup a 3 L three-neck flask with 2 L of deionized water, an overhead stirrer, and pH probe.</li>
	<li>Add delignified kraft pulp, 88% brightness (20 g, 1% (w/v, dry weight basis)), 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) (0.313 g, 0.1 mmol/g cellulose), and sodium bromide (NaBr, 2.0 g, 1 mmol/g cellulose) to the flask.
	<ol>
		<li>Mix the pulp fiber with the overhead stirrer until the fiber is dispersed and no aggregates can be seen in the reaction.<...

Fabrication of Nanocellulose
For nanocellulose fabrication the successful oxidation of the pulp fiber is necessary for facile fibrillation. Oxidation is controlled by available sodium hypochlorite, which should be slowly added at known quantities based on the amount of cellulose. One reason for limited oxidation arises from the storage of the sodium hypochlorite solution for extended periods. This reduced oxidation efficiency can be noted during the reaction; the pulp slurry should turn a pale-ye...

There is great interest to derive additional chemicals and fuels from biomass, as carbon sequestered by plants during photosynthesis is part of the current CO2 cycle. The majority of sequestered carbon (42-44%) is in the form of cellulose, a polymer composed of&#160;&#946; 1-4-linked glucopyranose units; when hydrolyzed, glucose can be used as the primary reactant for fermentation into alcohol based fuels. However, cell wall architecture of woody plants has evolved for millennia creating a material that is resistant to degradation in the natural environment1. This stability carries over into the industrial processing of woody materials such as energy crops making cellulose difficult to access, isolate, and breakdown into glucose. A closer look at the ultrastructure of the secondary cell wall reveals that it is a polymer nanocomposite composed of layered paracrystalline cellulose microfibrils embedded in an amorphous matrix of lignin and hemicelluloses2-4. The longitudinally oriented cellulose microfibrils have a diameter of approximately 2-5 nm, which are aggregated together with other hetero-polysaccharides to form larger units of fibril bundles5. The fibril bundles are embedded in a lignin-hemicellulose complex composed of an amorphous polymer of phenylpropanol units with some linkages to other hetero-polysaccharides like glucoronoxylan4. Furthermore, this structure is further organized into layers, or lamellae, throughout the lignified secondary cell wall6-8. Enzymes, like cellulases, have a very difficult time accessing cellulose within the cell wall as it is found in its fibril form and embedded in lignin. The crux of truly making biobased fuels and renewable chemical platforms a reality is to develop processes that economically allow the saccharification of cellulose in its native form.
New chemical and imaging technologies are aiding in the study of the mechanisms involved in the saccharification of cellulose9,10. Much work has centered on Raman confocal imaging11 and atomic force microscopy12 to study the cell wall chemical composition and morphology. Being able to closely follow mechanisms of delignification and saccharification is a significant step forward, impacting the conversion of cellulose to glucose. Saccharification of model cellulose surfaces was analyzed by measuring enzyme kinetic rates with a quartz crystal microbalance with dissipation monitoring (QCM-D)13. However, native cell walls are highly complex as indicated above, and this creates ambiguity of how different conversion processes change the structure of the plant cell wall (polymer molecular weight, chemical linkages, porosity). Free-standing models of the cell wall substances with known structural composition would address this concern and allow the integration of samples into state-of-art chemical and imaging equipment.
There is a dearth of cell wall models and the few available can be categorized as blends of polymer materials and regenerated cellulose or bacterial cellulose14, enzymatically polymerized lignin-polysaccharide composites15-17, or model surfaces18-21. Some models that begin to resemble the cell wall are the samples that contain lignin precursors or analogs polymerized enzymatically in the presence of cellulose in its microfibrillar form. However, these materials suffer from the lack of organized layer architecture. A simple route for the creation of nanocomposite materials with organized architecture is the layer-by-layer (LbL) assembly technique, based on the sequential adsorption of polymers or nanoparticles with complementary charges or functional groups to form organized multilayered composite films22-25. Free-standing hybrid nanocomposites of high strength, made by LbL deposition of polymer and nanoparticles, have been reported by Kotov et al.26-30. Among many other applications, LbL films have also been investigated for their potential use in therapeutic delivery31, fuel cell membranes32,33, batteries34, and lignocellulosic fiber surface modification35-37. The recent interest in nanoscale cellulose based composite materials have led to the preparation and characterization of LbL multilayers of cellulose nanocrystals (CNC) prepared by sulfuric acid hydrolysis of cellulose fibers, and positively charged polyelectrolytes38-43. Similar studies have also been conducted with cellulose nanocrystals obtained from marine tunicin and cationic polyelectrolytes44, CNC and xyloglucan45, and CNC and chitosan46. LbL multilayer formation of carboxylated nanofibrillated celluloses (NFCs), obtained by high-pressure homogenization of pulp fibers with cationic polyelectrolytes has also been studied47-49. The preparation, properties, and application of CNCs and nanofibrillated cellulose have been reviewed in detail50-53.
The present study involves the examination of LbL technique as a potential way to assemble isolated lignocellulosic polymers (such as nanocellulose and lignin) in an ordered fashion as the first step towards a biomimetic lignocellulosic composite with lamellar structure. The LbL technique was selected for its benign processing conditions such as, ambient temperature, pressure, and water as the solvent, which are conditions for natural composite formation54. In this study we report on the multilayer build-up of constitutive wood components, namely cellulose microfibrils from the tetramethylpiperidine 1-oxyl (TEMPO) mediated oxidation of pulp and isolated lignin into free-standing lamellar films. Two different lignins are used from different extraction techniques, one a technical lignin from the organosolv pulping process, and the other a lignin isolated from ball-milling with less modification during isolation. These compounds are combined with a synthetic polyelectrolyte in this initial study to demonstrate the feasibility of making stable free-standing films with architecture similar to the native cell wall.

<table border="0" cellpadding="0" cellspacing="0" width="699">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">sulfate pulp</td>
			<td style="width:108px;">Weyerhaeuser&#160;</td>
			<td style="width:119px;">donated</td>
			<td style="width:215px;">brightness level of 88%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">organosolv lignin</td>
			<td style="width:108px;">Sigma Aldrich</td>
			<td style="width:119px;">371017</td>
			<td>discontinued</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:257px;">hardwood milled wood lignin</td>
			<td style="width:108px;">see reference in paper</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">polydiallyldimethylammonium chloride&#160;</td>
			<td style="width:108px;">Sigma Aldrich</td>
			<td style="width:119px;">409022</td>
			<td style="width:215px;">Mn = 7.2&#215;10^4, Mw=2.4&#215;10^5</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">2,2,6,6-Tetramethylpiperidine 1-oxyl (TEMPO)&#160;</td>
			<td style="width:108px;">Sigma Aldrich</td>
			<td style="width:119px;">214000</td>
			<td>catalytic oxidation of primary alcohols to aldehydes with a purity of 98%, molecular weight is 156.25g/mol</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">sodium bromide</td>
			<td style="width:108px;">Sigma Aldrich</td>
			<td style="width:119px;">S4547</td>
			<td>purity &#8805;99.0%, molecular weight 102.89</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">sodium hypochlorite</td>
			<td style="width:108px;">Sigma Aldrich</td>
			<td style="width:119px;">425044</td>
			<td>reagent grade, available chlorine 10~15%, molecular weight 74.44g/mol</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">sodium hydroxide</td>
			<td style="width:108px;">VWR</td>
			<td style="width:119px;">BDH7221-4</td>
			<td>0.5N aqueous solution, density 1.02g/ml, molecular weight 40 g/mol</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">sodium hydroxide</td>
			<td style="width:108px;">Acros Organics</td>
			<td style="width:119px;">AC12419-0010</td>
			<td>0.1N aquesous solution, specific gravity 1.0 g/ml, molecular weight 40 g/mol</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">ammonium hydroxide</td>
			<td style="width:108px;">Acros Organics</td>
			<td style="width:119px;">AC39003-0025</td>
			<td>25% solution in water, pH 13.6, density 0.89, molecular weight 35.04 g/mol</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">hydrogen peroxide</td>
			<td style="width:108px;">Fisher Scientific</td>
			<td style="width:119px;">H325-100</td>
			<td>30.0~32.0% certified ACS, pH 3.3, density 1.11</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">Mica sheets</td>
			<td style="width:108px;">TED Pella</td>
			<td style="width:119px;">NC9655733</td>
			<td>Pelco, grade V5, 10&#215;40mm, 23mm T, minimum air and bubbles, very clean</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">sulfuric acid</td>
			<td style="width:108px;">Fisher Scientific</td>
			<td style="width:119px;">A300-212</td>
			<td>95.0~98.0 w/w%, certified ACS plus, molecular weight 98.08 g/mol</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">cellulose acetate</td>
			<td style="width:108px;">McMaster Carr</td>
			<td style="width:119px;">8564K44</td>
			<td>degree of substitution 2.5</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:257px;">ethanol</td>
			<td style="width:108px;">Decon Laboratories</td>
			<td style="width:119px;">04-355-223</td>
			<td>200 proof (100%), USP</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">acetone</td>
			<td style="width:108px;">Fisher Scientific</td>
			<td style="width:119px;">A18-4</td>
			<td>purity &#8805;99.5%, certified ACS reagent grade, density 0.79 g/ml, molecular weight 58.08 g/mol</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:257px;">syringy pump</td>
			<td style="width:108px;">Harvard Apparatus</td>
			<td style="width:119px;">552226</td>
			<td>pump 22 infusion/withdraw with standard syringe holder, flow rate 0.002 ul/h~55.1ml/min</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">Mill-Q water purification system</td>
			<td style="width:108px;">EMD Millipore</td>
			<td style="width:119px;">D3-UV</td>
			<td>Direct-Q, UV, water conductivity 18.5 M&#937; cm with 20 liter reservair</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">pH meter</td>
			<td style="width:108px;">Mettler Toledo</td>
			<td style="width:119px;"></td>
			<td style="width:215px;">SeverMulti</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">balance</td>
			<td style="width:108px;">Mettler Toledo</td>
			<td style="width:119px;">AB135-S</td>
			<td>accuracy 0.1mg</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:257px;">atomic force microscope</td>
			<td style="width:108px;">Asylum Research</td>
			<td style="width:119px;"></td>
			<td>MFP-3D, Olympic fluorescent microscope stage</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:257px;">ellipsometer</td>
			<td style="width:108px;">Beaglehole Instruments</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">fiber centrifuge</td>
			<td style="width:108px;">unknown</td>
			<td style="width:119px;"></td>
			<td>basket style centrifuge</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">Warring blender</td>
			<td style="width:108px;">Warring</td>
			<td style="width:119px;"></td>
			<td>Commercial</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">ultrasonic processor</td>
			<td style="width:108px;">Sonics</td>
			<td style="width:119px;"></td>
			<td>Sonics 750W, sound enclosure</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:257px;">Quartz crystal microbalance with dissipation monitoring (QCM-D)</td>
			<td style="width:108px;">Q-Sense Inc.&#160;</td>
			<td style="width:119px;">E4</td>
			<td>measure fundamental frequency of 5MHz, and monitor odd number overtones/harmonics from 3~13, use gold-coated piezoelectric quartz crystals</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:257px;">automatted dipper arm</td>
			<td style="width:108px;">Lynxmotion</td>
			<td style="width:119px;"></td>
			<td></td>
		</tr>
	</tbody>
</table>

towards biomimicking wood: fabricated free-standing films of nanocellulose, lignin, and a synthetic polycation

Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and lignin. Layer-by-layer (LbL) assembly process which relies on the assembly of oppositely charged molecules from aqueous solutions was used to build a freestanding composite film of isolated wood polymers of lignin and oxidized nanofibril cellulose (NFC). To facilitate the assembly of these negatively charged polymers, a positively charged polyelectrolyte, poly(diallyldimethylammomium chloride) (PDDA), was used as a linking layer to create this simplified model cell wall. The layered adsorption process was studied quantitatively using quartz crystal microbalance with dissipation monitoring (QCM-D) and ellipsometry. The results showed that layer mass/thickness per adsorbed layer increased as a function of total number of layers. The surface coverage of the adsorbed layers was studied with atomic force microscopy (AFM). Complete coverage of the surface with lignin in all the deposition cycles was found for the system, however, surface coverage by NFC increased with the number of layers. The adsorption process was carried out for 250 cycles (500 bilayers) on a cellulose acetate (CA) substrate. Transparent free-standing LBL assembled nanocomposite films were obtained when the CA substrate was later dissolved in acetone. Scanning electron microscopy (SEM) of the fractured cross-sections showed a lamellar structure, and the thickness per adsorption cycle (PDDA-Lignin-PDDA-NC) was estimated to be 17 nm for two different lignin types used in the study. The data indicates a film with highly controlled architecture where nanocellulose and lignin are spatially deposited on the nanoscale (a polymer-polymer nanocomposites), similar to what is observed in the native cell wall.

QCM-D Analysis of Structured Woody Polymer Film Fabrication
The LbL adsorption of lignin, NFC and PDDA was monitored in real-time with QCM-D in two different experiments involving two types of lignins. This analysis method is very sensitive to detect changes in frequency when molecules adsorb to the surface of the quartz crystal. Figure 1 contains a detailed description of the QCM-D response in one deposition cycle, which involves two bilayers (PDDA:HMWL and PDDA:NC). The data re...

Watch this Scientific Journal Video about Towards Biomimicking Wood: Fabricated Free-standing Films of Nanocellulose, Lignin, and a Synthetic Polycation at JoVE.com

Towards Biomimicking Wood: Fabricated Free-standing Films of Nanocellulose, Lignin, and a Synthetic Polycation

The objective of this research was to form synthetic plant cell wall tissue using layer-by-layer assembly of nanocellulose fibrils and isolated lignin assembled from dilute aqueous suspensions.&#160; Surface measurement techniques of quartz crystal microbalance and atomic force microscopy were used to monitor the formation of the polymer-polymer nanocomposite material.

Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and ...

towards-biomimicking-wood-fabricated-free-standing-films

Research

JoVE Journal

Chemistry

A Technique to Functionalize and Self-assemble Macroscopic Nanoparticle-ligand Monolayer Films onto Template-free Substrates

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface. This drives the ligand-capped nanoparticles to form monolayer domains at the air-fluid interface.&#160; The use of water-miscible organic solvents is important as it enables the transport of the nanoparticles from the interface onto template-free substrates.&#160; The flow is mediated by a surface tension gradient3,4 and creates macroscopic, high-density, monolayer nanoparticle-ligand films.&#160; This self-assembly technique may be generalized to include the use of particles of different compositions, size, and shape and may lead to an efficient assembly method to produce low-cost, macroscopic, high-density, monolayer nanoparticle films for wide-spread applications.

A simple, robust and scalable technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates is described in this protocol.

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and ...

Atomically Defined Templates for Epitaxial Growth of Complex Oxide Thin Films

Atomically defined substrate surfaces are prerequisite for the epitaxial growth of complex oxide thin films. In this protocol, two approaches to obtain such surfaces are described. The first approach is the preparation of single terminated perovskite SrTiO3 (001) and DyScO3 (110) substrates. Wet etching was used to selectively remove one of the two possible surface terminations, while an annealing step was used to increase the smoothness of the surface. The resulting single terminated surfaces allow for the heteroepitaxial growth of perovskite oxide thin films with high crystalline quality and well-defined interfaces between substrate and film. In the second approach, seed layers for epitaxial film growth on arbitrary substrates were created by Langmuir-Blodgett (LB) deposition of nanosheets. As model system Ca2Nb3O10- nanosheets were used, prepared by delamination of their layered parent compound HCa2Nb3O10. A key advantage of creating seed layers with nanosheets is that relatively expensive and size-limited single crystalline substrates can be replaced by virtually any substrate material.

Various procedures are outlined to prepare atomically defined templates for epitaxial growth of complex oxide thin films. Chemical treatments of single crystalline SrTiO3 (001) and DyScO3 (110) substrates were performed to obtain atomically smooth, single terminated surfaces. Ca2 Nb3 O10- nanosheets were used to create atomically defined templates on arbitrary substrates.

Atomically defined substrate surfaces are prerequisite for the epitaxial growth of complex oxide thin films. In this protocol, two approaches to obtain ...

Fabrication of Large-area Free-standing Ultrathin Polymer Films

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films. Typically, ultrathin films are prepared using either sacrificial layers, which may damage the film or affect its mechanical properties, or they are made on freshly cleaved mica, a substrate that is difficult to scale. Further, the size of ultrathin film is typically limited to a few square millimeters. In this method, we modify a surface with a polyelectrolyte that alters the strength of adhesion between polymer and deposition substrate. The polyelectrolyte can be shown to remain on the wafer using spectroscopy, and a treated wafer can be used to produce multiple films, indicating that at best minimal amounts of the polyelectrolyte are added to the film. The process has thus far been shown to be limited in scalability only by the size of the coating equipment, and is expected to be readily scalable to industrial processes. In this study, the protocol for making the solutions, preparing the deposition surface, and producing the films is described.

We describe a method for the fabrication of large-area (up to 13 cm diameter) and ultrathin (as thin as 8 nm) polymer films. Instead of using a sacrificial interlayer to delaminate the film from its substrate, we use a self-limiting surface treatment suitable for arbitrarily large areas.

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films.  Typically, ultrathin films are prepared ...

From Constructs to Crystals &#8211; Towards Structure Determination of &#946;-barrel Outer Membrane Proteins

Membrane proteins serve important functions in cells such as nutrient transport, motility, signaling, survival and virulence, yet constitute only ~1% percent of known structures. There are two types of membrane proteins, &#945;-helical and &#946;-barrel. While &#945;-helical membrane proteins can be found in nearly all cellular membranes, &#946;-barrel membrane proteins can only be found in the outer membranes of mitochondria, chloroplasts, and Gram-negative bacteria. One common bottleneck in structural studies of membrane proteins in general is getting enough pure sample for analysis. In hopes of assisting those interested in solving the structure of their favorite &#946;-barrel outer membrane protein (OMP), general protocols are presented for the production of target &#946;-barrel OMPs at levels useful for structure determination by either X-ray crystallography and/or NMR spectroscopy. Here, we outline construct design for both native expression and for expression into inclusion bodies, purification using an affinity tag, and crystallization using detergent screening, bicelle, and lipidic cubic phase techniques. These protocols have been tested and found to work for most OMPs from Gram-negative bacteria; however, there are some targets, particularly for mitochondria and chloroplasts that may require other methods for expression and purification. As such, the methods here should be applicable for most projects that involve OMPs from Gram-negative bacteria, yet the expression levels and amount of purified sample will vary depending on the target OMP.

From Constructs to Crystals &amp;#8211; Towards Structure Determination of &amp;#946;-barrel Outer Membrane Proteins

&#946;-barrel outer membrane proteins (OMPs) serve many functions within the outer membranes of Gram-negative bacteria, mitochondria, and chloroplasts. Here, we hope to alleviate a known bottleneck in structural studies by presenting protocols for the production of &#946;-barrel OMPs in sufficient quantities for structure determination by X-ray crystallography or NMR spectroscopy.

Membrane proteins serve important functions in cells such as nutrient transport, motility, signaling, survival and virulence, yet constitute only ~1% ...

Highly Stable, Functional Hairy Nanoparticles and Biopolymers from Wood Fibers: Towards Sustainable Nanotechnology

Nanoparticles, as one of the key materials in nanotechnology and nanomedicine, have gained significant importance during the past decade. While metal-based nanoparticles are associated with synthetic and environmental hassles, cellulose introduces a green, sustainable alternative for nanoparticle synthesis. Here, we present the chemical synthesis and separation procedures to produce new classes of hairy nanoparticles (bearing both amorphous and crystalline regions) and biopolymers based on wood fibers. Through periodate oxidation of soft wood pulp, the glucose ring of cellulose is opened at the C2-C3 bond to form 2,3-dialdehyde groups. Further heating of the partially oxidized fibers (e.g., T = 80 &#176;C) results in three products, namely fibrous oxidized cellulose, sterically stabilized nanocrystalline cellulose (SNCC), and dissolved dialdehyde modified cellulose (DAMC), which are well separated by intermittent centrifugation and co-solvent addition. The partially oxidized fibers (without heating) were used as a highly reactive intermediate to react with chlorite for converting almost all aldehyde to carboxyl groups. Co-solvent precipitation and centrifugation resulted in electrosterically stabilized nanocrystalline cellulose (ENCC) and dicarboxylated cellulose (DCC). The aldehyde content of SNCC and consequently surface charge of ENCC (carboxyl content) were precisely controlled by controlling the periodate oxidation reaction time, resulting in highly stable nanoparticles bearing more than 7 mmol functional groups per gram of nanoparticles (e.g., as compared to conventional NCC bearing &#60;&#60; 1 mmol functional group/g). Atomic force microscopy (AFM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) attested to the rod-like morphology. Conductometric titration, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), dynamic light scattering (DLS), electrokinetic-sonic-amplitude (ESA) and acoustic attenuation spectroscopy shed light on the superior properties of these nanomaterials.

Synthesis schemes to prepare highly stable wood fiber-based hairy nanoparticles and functional cellulose-based biopolymers have been detailed.

Nanoparticles, as one of the key materials in nanotechnology and nanomedicine, have gained significant importance during the past decade. While ...

Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

We demonstrate a method of conformally coating conjugated polymers on arbitrary substrates using a custom-designed, low-pressure reaction chamber. Conductive polymers, poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT), and a semiconducting polymer, poly(thieno[3,2-b]thiophene) (PTT), were deposited on unconventional highly-disordered and textured substrates with high surface areas, such as paper, towels and fabrics. This reported deposition chamber is an improvement of previous vapor reactors because our system can accommodate both volatile and nonvolatile monomers, such as 3,4-propylenedioxythiophene and thieno[3,2-b]thiophene. Utilization of both solid and liquid oxidants are also demonstrated. One limitation of this method is that it lacks sophisticated in situ thickness monitors. Polymer coatings made by the commonly used solution-based coating methods, such as spin-coating and surface grafting, are often not uniform or susceptible to mechanical degradation. This reported vapor phase deposition method overcomes those drawbacks and is a strong alternative to common solution-based coating methods. Notably, polymer films coated by the reported method are uniform and conformal on rough surfaces, even at a micrometer scale. This feature allows for future application of vapor deposited polymers in electronics devices on flexible and highly textured substrates.

This paper presents a protocol for reactive vapor deposition of poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), and poly(thieno[3,2-b]thiophene) films on glass slides and rough substrates, such as textiles and paper.

We demonstrate a method of conformally coating conjugated polymers on arbitrary substrates using a custom-designed, low-pressure reaction chamber. ...

Gene-therapy Inspired Polycation Coating for Protection of DNA Origami Nanostructures

DNA origami nanostructures hold an immense potential to be used for biological and medical applications. However, low-salt conditions and nucleases in physiological fluids induce denaturation and degradation of self-assembled DNA nanostructures. In non-viral gene delivery, enzymatic degradation of DNA is overcome by the encapsulation of the negatively charged DNA in a cationic shell. Herein, inspired by gene delivery advancements, a simple, one-step and robust methodology is presented for the stabilization of DNA origami nanostructures by coating them with chitosan and linear polyethyleneimine. The polycation coating efficiently protects DNA origami nanostructures in Mg-depleted and nuclease-rich media. This method also preserves the full addressability of enzyme- and aptamer-based functionalization of DNA nanostructures.

Here, a protocol for the protection of DNA origami nanostructures in Mg-depleted and nuclease-rich media using natural cationic polysaccharide chitosan and synthetic linear polyethyleneimine (LPEI) coatings is presented.

DNA origami nanostructures hold an immense potential to be used for biological and medical applications. However, low-salt conditions and nucleases in ...

Niobium Oxide Films Deposited by Reactive Sputtering: Effect of Oxygen Flow Rate

Reactive sputtering is a versatile technique used to form compact films with excellent homogeneity. In addition, it allows easy control over deposition parameters such as gas flow rate that results in changes on composition and thus in the film required properties. In this report, reactive sputtering is used to deposit niobium oxide films. A niobium target is used as metal source and different oxygen flow rates to deposit niobium oxide films. The oxygen flow rate was changed from 3 to 10 sccm. The films deposited under low oxygen flow rates show higher electrical conductivity and provide better perovskite solar cells when used as electron transport layer.

Here, we present a protocol for niobium oxide films deposition by reactive sputtering with different oxygen flow rates for use as an electron transport layer in perovskite solar cells.

Reactive sputtering is a versatile technique used to form compact films with excellent homogeneity. In addition, it allows easy control over deposition ...

Applying Dynamic Strain on Thin Oxide Films Immobilized on a Pseudoelastic Nickel-Titanium Alloy

Direct alteration of material structure/function through strain is a growing area of research that has allowed for novel properties of materials to emerge. Tuning material structure can be achieved by controlling an external force imposed on materials and inducing stress-strain responses (i.e., applying dynamic strain). Electroactive thin films are typically deposited on shape or volume tunable elastic substrates, where mechanical loading (i.e., compression or tension) can affect film structure and function through imposed strain. Here, we summarize methods for straining n-type doped titanium dioxide (TiO2) films prepared by a thermal treatment of a pseudo-elastic nickel-titanium alloy (Nitinol). The main purpose of the described methods is to study how strain affects electrocatalytic activities of metal oxide, specifically hydrogen evolution and oxygen evolution reactions. The same system can be adapted to study the effect of strain more broadly. Strain engineering can be applied for optimization of a material function, as well as for design of adjustable, multifunctional (photo)electrocatalytic materials under external stress control.

Dynamic, tensile strain is applied on TiO2 thin films to study the effects of strain on electrocatalysis, specifically proton reduction and water oxidation. TiO2 films are prepared by thermal treatment of the pseudo-elastic NiTi alloy (Nitinol).

Direct alteration of material structure/function through strain is a growing area of research that has allowed for novel properties of materials to ...

Designed for Molecular Recycling: A Lignin-Derived Semi-aromatic Biobased Polymer

The development of chemically recyclable biopolymers offers opportunities within the pursuit of a circular economy. Chemically recyclable biopolymers make a positive effort to solve the issue of polymer materials in the disposal phase after the use phase. In this paper, the production of biobased semi-aromatic polyesters, which can be extracted entirely from biomass such as lignin, is described and visualized. The polymer poly-S described in this paper has thermal properties similar to certain commonly used plastics, such as PET. We developed a Green Knoevenagel reaction, which can efficiently produce monomers from aromatic aldehydes and malonic acid. This reaction has been proven to be scalable and has a remarkably low calculated E-factor. These polyesters with ligno-phytochemicals as a starting point show an efficient molecular recycling with minimal losses. The polyester poly(dihydrosinapinic acid) (poly-S) is presented as an example of these semi-aromatic polyesters, and the polymerization, depolymerization, and re-polymerization are described.

An example of a closed-loop approach towards a circular materials economy is described here. A whole sustainable cycle is presented where biobased semi-aromatic polyesters are designed by polymerization, depolymerization, and then re-polymerized with only slight changes in their yields or final properties.

The development of chemically recyclable biopolymers offers opportunities within the pursuit of a circular economy. Chemically recyclable biopolymers make ...