Name: microhoneycomb monoliths prepared by the unidirectional freeze-drying of cellulose nanofiber based sols: method and extensions
Uploaded: 2018-05-24T13:30:00
Description: Watch this Scientific Journal Video about Microhoneycomb Monoliths Prepared by the Unidirectional Freeze-drying of Cellulose Nanofiber Based Sols: Method and Extensions at JoVE.com

Este trabajo fue financiado por la nacional básico de investigación programa de China (2014CB932400), Fundación de Ciencias naturales nacionales de China (núms. 51525204 y U1607206) y proyecto de investigación básica de Shenzhen (no. JCYJ20150529164918735). También, nos gustaría agradecer a Daicel Allnex Ltd. y JSR Co. poliuretanos proveedores amablemente y caucho de butadieno del estireno, respectivamente.

1. preparación de 1 wt % 2.2.6.6-Tetramethylpiperidin-1-oxyl (TEMPO)-mediada por celulosa oxidada nanofibras (TOCN) Sol
Nota: El sol se define como una suspensión coloidal de partículas sólidas muy pequeñas en un medio líquido continuo.
<ol><li>Suspender 66,7 g de pulpa de Kraft blanqueado Nadelholz (NBKP, que contiene 12 g de celulosa) en 700 mL de agua desionizada (DI) con un agitador mecánico a 300 rpm por 20 min.</li>
	<li>Añadir 20 mL de solución acuosa de TEMPO (contiene 0,15 ...

<ol>
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R., Mitani, K., Murata, S., Nishihara, H., Tamon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Assembling+of+nanoparticles+using+ice+crystals.">Assembling of nanoparticles using ice crystals.</a> Mater. Chem. Phys. 123 (2), 347-350 (2010).</li><li>Cui, K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Self-assembled+microhoneycomb+network+of+single-walled+carbon+nanotubes+for+solar+cells.">Self-assembled microhoneycomb network of single-walled carbon nanotubes for solar cells.</a> J. Phy. Chem. Lett. 4 (15), 2571-2576 (2013).</li><li>Xu, T., Wang, C. -. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effect+of+two-step+sintering+on+micro-honeycomb+BaTiO3+ceramics+prepared+by+freeze-casting+process.">Effect of two-step sintering on micro-honeycomb BaTiO3 ceramics prepared by freeze-casting process.</a> J. Eur. Ceram. Soc. 36 (10), 2647-2652 (2016).</li><li>Yoshida, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=CO2+Separation+in+a+flow+system+by+silica+microhoneycombs+loaded+with+an+ionic+liquid+prepared+by+the+ice-templating+method.">CO2 Separation in a flow system by silica microhoneycombs loaded with an ionic liquid prepared by the ice-templating method.</a> Ind. Eng. Chem. Res. 56 (10), 2834-2839 (2017).</li><li>Mukai, S. R., Nishihara, H., Tamon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Formation+of+monolithic+silica+gel+microhoneycombs+(SMHs)+using+pseudosteady+state+growth+of+microstructural+ice+crystals.">Formation of monolithic silica gel microhoneycombs (SMHs) using pseudosteady state growth of microstructural ice crystals.</a> Chem. Commun. (7), 874-875 (2004).</li><li>Gutie&#180;rrez, M. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Macroporous+3D+Architectures+of+Self-Assembled+MWCNT+Surface+Decorated+with+Pt+Nanoparticles+as+Anodes+for+a+Direct+Methanol+Fuel+Cell.">Macroporous 3D Architectures of Self-Assembled MWCNT Surface Decorated with Pt Nanoparticles as Anodes for a Direct Methanol Fuel Cell.</a> J. Phys. Chem. C. 111, 5557-5560 (2007).</li><li>Mukai, S. R., Nishihara, H., Tamon, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Morphology+maps+of+ice-templated+silica+gels+derived+from+silica+hydrogels+and+hydrosols.">Morphology maps of ice-templated silica gels derived from silica hydrogels and hydrosols.</a> Micropor. Mesopor. Mat. 116 (1-3), 166-170 (2008).</li><li>Okaji, R., Taki, K., Nagamine, S., Ohshima, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+porous+honeycomb+monolith+from+UV-curable+monomer/dioxane+solution+via+unidirectional+freezing+and+UV+irradiation.">Preparation of porous honeycomb monolith from UV-curable monomer/dioxane solution via unidirectional freezing and UV irradiation.</a> J. Appl. Polym. Sci. 125 (4), 2874-2881 (2012).</li><li>Pan, Z. -. Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cellulose+nanofiber+as+a+distinct+structure-directing+agent+for+xylem-like+microhoneycomb+monoliths+by+unidirectional+freeze-drying.">Cellulose nanofiber as a distinct structure-directing agent for xylem-like microhoneycomb monoliths by unidirectional freeze-drying.</a> ACS Nano. 10 (12), 10689-10697 (2016).</li><li>Saito, T., Nishiyama, Y., Putaux, J. -. L., Vigon, M., Isogai, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Homogeneous+Suspensions+of+Individualized+Microfibrils+from+TEMPO-Catalyzed+Oxidation+of+Native+Cellulose.">Homogeneous Suspensions of Individualized Microfibrils from TEMPO-Catalyzed Oxidation of Native Cellulose.</a> Biomacromolecules. 7 (6), 1687-1691 (2006).</li><li>Saito, T., Kimura, S., Nishiyama, Y., Isogai, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cellulose+Nanofibers+Prepared+by+TEMPO-Mediated+Oxidation+of+Native+Cellulose.">Cellulose Nanofibers Prepared by TEMPO-Mediated Oxidation of Native Cellulose.</a> Biomacromolecules. 8, 2485-2491 (2007).</li><li>Bekyarova, E., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Multiscale+carbon+nanotube&#8722;+carbon+fiber+reinforcement+for+advanced+epoxy+composites.">Multiscale carbon nanotube&#8722; carbon fiber reinforcement for advanced epoxy composites.</a> Langmuir. 23, 3970-3974 (2007).</li><li>Nishihara, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Study on the simultaneous control of the nanostructure and morphology of the porous materials prepared via the ice-templating method [D]. , (2005).</li><li>Zhang, R., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Three-dimensional+porous+graphene+sponges+assembled+with+the+combination+of+surfactant+and+freeze-drying.">Three-dimensional porous graphene sponges assembled with the combination of surfactant and freeze-drying.</a> Nano Research. 7 (10), 1477-1487 (2014).</li><li>Tao, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Towards+ultrahigh+volumetric+capacitance:+graphene+derived+highly+dense+but+porous+carbons+for+supercapacitors.">Towards ultrahigh volumetric capacitance: graphene derived highly dense but porous carbons for supercapacitors.</a> Sci. Rep. 3, 2975 (2013).</li></ol>

El paso más crítico para lograr el MHMs es el paso de congelación unidireccional, en que el agua se solidifica para formar cristales de hielo cilíndrico y empuje la dispersión a un lado para formar el marco. El proceso de congelación unidireccional básicamente consiste en la transferencia térmica entre el sol del precursor y el refrigerante. En nuestra instalación, una máquina que se utilizó para insertar un tubo de los PP que contienen un sol precursor en el refrigerante (nitrógeno líquido) con una velocida...

Como un material nuevo, microhoneycomb monolito (denota MHM) recientemente ha atraído enorme atención desde campos multidisciplinarios1,2,3,4,5, 6 , 7 , 8. el MMH primero fue preparado por Mukai S. et al. , a través de un acercamiento unidireccional modificado de liofilización (UDF) como un monolito con una serie de microcanales recta con panal-como secciones9. MHM posee las ventajas generales de las estructuras de panal, es decir, Teselación eficiente, alto cociente del energía-a-peso y baja caída de presión. Por otra parte, en comparación con el monolito de nido de abeja con un mayor tamaño del canal, el MHM tiene un mucho mayor área de superficie específica. El método UDF implica el crecimiento unidireccional de cristales de hielo y separación de fases simultáneas en congelación. Después de la eliminación de los cristales de hielo, se obtiene un componente sólido moldeado por el cristal de hielo. La morfología formada sobre la separación de fase depende de la naturaleza intrínseca del precursor (sol o gel) y en la mayoría de los casos, láminas10, fibra11, y12 estructuras de espina de pez son propensos a formar en lugar del MHMs. Como resultado, la formación de MHMs se ha divulgado solamente en precursores limitadas, y esto ha dificultado significativamente la diversidad de sus propiedades químicas. Recientemente hemos encontrado que nanofibras de celulosa tienen una función de dirección de estructura fuerte hacia la formación de la estructura MHM a la UDF proceso13. Simplemente mezclando las nanofibras de celulosa con otros componentes solubles en agua, es posible preparar una variedad de MHMs con diferentes propiedades químicas. Por otra parte, sus formas exteriores y tamaños de canal son flexible y fácilmente controlados13. Por lo tanto, se espera que MHMs utilizar como filtros, soportes de catalizador, electrodos del tipo de flujo, sensores y andamios para biomateriales.
En este artículo, explicamos primero la técnica de preparación básica de MHMs de la dispersión acuosa de nanofibras de celulosa a través del proceso de la UDF en detalle. Por otra parte, se demuestra la preparación de diferentes tipos de compuestos MHMs.

<table border="0" cellpadding="0" cellspacing="0" width="572">
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Nadelholz Bleached Kraft Pulp</td>
			<td style="width:100px;">Seioko PMC company</td>
			<td style="width:89px;">CSF=600</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">TEMPO</td>
			<td style="width:100px;">Macklin Inc.</td>
			<td style="width:89px;">T819129</td>
			<td style="width:167px;">98%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">NaBr</td>
			<td style="width:100px;">Macklin Inc.</td>
			<td style="width:89px;">S818075</td>
			<td style="width:167px;">AR, 99%</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">NaClO</td>
			<td style="width:100px;">Aladin Inc.</td>
			<td style="width:89px;">S101636</td>
			<td style="width:167px;">6-14 wt% active chlorine basis</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">SBR colloid</td>
			<td style="width:100px;">JSR corp.</td>
			<td style="width:89px;">TRD102A</td>
			<td style="width:167px;">48.5 wt%</td>
		</tr>
		<tr height="84">
			<td height="84" style="height:84px;width:216px;">TiO2</td>
			<td style="width:100px;">Sinopharm Chemical Reagent Co., Ltd.</td>
			<td style="width:89px;">A63725402</td>
			<td style="width:167px;">crystalline anatase phase</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">carbon fiber</td>
			<td style="width:100px;">Shenzhen Xian&#8217;gu Ltd.</td>
			<td style="width:89px;">XGCP-300</td>
			<td style="width:167px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Nitric acid</td>
			<td style="width:100px;">Huada Reagent Ltd.</td>
			<td style="width:89px;">7697-37-2</td>
			<td style="width:167px;">65-68 wt%</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:216px;">Mixer</td>
			<td style="width:100px;">Scientific Industries, Inc</td>
			<td style="width:89px;">G-560</td>
			<td style="width:167px;">the mixer&#160;</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:216px;">Mechanical blender</td>
			<td style="width:100px;">Waring Lab Ltd.</td>
			<td style="width:89px;">MX1000XTX</td>
			<td style="width:167px;">For disintegrating cellulose bundles into nanofibers.</td>
		</tr>
		<tr height="46">
			<td height="46" style="height:46px;width:216px;">Homogenizer</td>
			<td style="width:100px;">Scientz Ltd.</td>
			<td style="width:89px;">HXF-DY</td>
			<td style="width:167px;">For dispersing TiO2 nanoparticles</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:216px;">pH meter&#160;</td>
			<td style="width:100px;">Horiba Ltd.</td>
			<td style="width:89px;">F-74BW</td>
			<td></td>
		</tr>
	</tbody>
</table>

microhoneycomb monoliths prepared by the unidirectional freeze-drying of cellulose nanofiber based sols: method and extensions

Las estructuras de panal monolítico han sido atractivas para los campos multidisciplinarios debido a su alto cociente del fuerza-a-peso. Particularmente, se espera que microhoneycomb monolitos (MHMs) con canales de micrómetro-escala como plataformas eficientes para reacciones y separaciones debido a sus grandes superficies. Hasta ahora, MHMs han sido preparadas por un método unidireccional de liofilización (UDF) sólo a partir de precursores muy limitadas. Adjunto, Divulgamos un protocolo que puede obtenerse una serie de MHMs consisten en diversos componentes. Recientemente, hemos encontrado esa función de nanofibras de celulosa como un agente de dirección de estructura distintivo hacia la formación de MHMs a través del proceso UDF. Mezclando las nanofibras de celulosa con sustancias solubles del agua que no den MHMs, puede preparar una variedad de compuestos MHMs. Esto enriquece significativamente la constitución química de MHMs hacia usos versátiles.

Las morfologías en diferentes posiciones de la TOCN MHM a lo largo de la dirección de congelación unidireccional se investigó y se muestra en la figura 2. Con la posición está más lejos de la parte inferior de la TOCN MHM, se reveló un cambio gradual de la morfología (figura 2, discusión). Al introducir un segundo componente en la sol TOCN para formar un sol de mezcla homogénea, es posible preparar var...

Watch this Scientific Journal Video about Microhoneycomb Monoliths Prepared by the Unidirectional Freeze-drying of Cellulose Nanofiber Based Sols: Method and Extensions at JoVE.com

Microhoneycomb Monoliths Prepared by the Unidirectional Freeze-drying of Cellulose Nanofiber Based Sols: Method and Extensions

Aquí, presentamos un protocolo general para preparar una gran variedad de monolitos de microhoneycomb (MHMs) en qué fluido puede pasar con una muy baja caída de presión. MHMs obtenidos deben utilizarse como filtros, catalizador apoya, electrodos del tipo de flujo, sensores y andamios de biomateriales.

Monolitos de Microhoneycomb preparados por la liofilización unidireccional de nanofibras de celulosa basan Sols: método y extensiones

Monolithic honeycomb structures have been attractive to multidisciplinary fields due to their high strength-to-weight ratio. Particularly, microhoneycomb ...

This method can help answer key questions about achieving functional MHM materials for applications such as filtration, catalyst supporting, flow type batteries, sensors and bio-scaffolds. The main advantage of this technique is that it utilizes the structure directing function of cellulose nanofibers and can realize constitutional control of the targeted MHMs. This method can help answer key questions about achieving functional MHM materials for applications such as filtration, catalyst supporting, flow type batteries, sensors and bio-scaffolds.Demonstrating the procedure with myself and Cong Wang, a grad student from our laboratory. To begin preparing the tempo-mediated oxidized cellulose nanofiber sol, first combine 66.7 grams of softwood bleached kraft pulp with 700 microliters of deionized water. Mechanically agitate the mixture for 20 minutes at 300 rpm.Over the course of one minute, slowly add to the stirring kraft pulp suspension 20 milliliters each of a 7.5 gram per liter aqueous tempo solution and 75 gram per liter aqueous sodium bromide solution. Begin continuously monitoring the pH of the mixture with a pH meter. Adjust the mixture pH to about 10.5 with a three molar sodium hydroxide solution.Then, over the course of several minutes, slowly pipette into the suspension 63.8 grams of aqueous sodium hypochlorite with 6 to 14%active chlorine. After addition is complete, continue adjusting the pH back to 10.5 whenever it drops to about 10. Once the pH decrease slows, time how long it takes for the pH to drop from 10.5 to 10 to determine how often to check on the mixture during the reaction.Allow the tempo mediated oxidation to proceed normally for a bout 2.5 hours from the start of the sodium hypochlorite addition. Afterwards, filtrate the reaction mixture through a filter. And collect the oxidized cellulose nanofiber.Then, agitate the oxidized cellulose fibers in 1.2 liters of deionized water. Rinse the fibers three times in this way. Dry a small portion of the washed fiber paste overnight in an oven at 60 degrees Celsius to determine the solid content of the paste.Calculate the quantity of water needed to make a 1%by weight sol from the paste. Then transfer the washed fiber paste to laboratory grade blender. Add an appropriate amount of DI water to adjust the concentration of the mixture to 2%by weight.Vigorously blend the paste to disintegrate the oxidized cellulose fibers into nanofibers. Begin with low power blending before vigorously blending the paste at high power. Add one fifth of the needed volume of deionized water to the paste, and blend thoroughly.Repeat this process four more times to obtain the 1%by weight tempo mediated oxidized cellulose nanofiber sol. Store the sol at four degrees Celsius. We hear extracting is constant of the resulting TOCN sol.If it is hot enough, the MHM is likely to be obtained through the newly added process. Normally, the viscosity must be greater than 20, 000 millipascal second. Prior to preparing the tempo mediated oxidized cellulose nanofiber surface oxidized carbon fiber mixed sol, reflux 1.7 grams of 300 mesh carbon fiber in 150 milliliters of concentrated nitric acid to obtain the surface oxidized carbon fibers.Then, place in a 20 milliliter glass vial, 01 grams of the prepared surface oxidized carbon fibers, and 10 grams of the 1%by weight tempo mediated oxidized cellulose nanofiber sol. Manually shake the mixture until the surface oxidized carbon fibers are evenly distributed throughout the sol. Sonicate the mixture for five minutes to obtain an evenly dispersed TOCN SOCF mixed sol.Store the sol at four degrees Celsius. To begin preparing a microhoneycomb monolith, fill the bottom five centimeters of the 13 by 150 millimeter or similarly sized polypropylene tube with glass beads as filler material. Slowly load at least 2.7 milliliters of the chosen sol into the tube, ensuring that the sol level is about 22 millimeters or more above the glass beads.Avoid disturbing the sol unnecessarily to minimize the formation of bubbles in the tube. Use a narrow tipped pipette to carefully remove from the sol any bubbles that were introduced during the loading process. Store the sol sample at four degrees Celsius overnight.Then connect the sample tube to a dipping instrument for a unidirectional freezing. Place a Dewar of liquid nitrogen under the tube. Freeze the sol at an emerging speed of either 50 centimeters per hour for the TOCN sol or 20 centimeters per hour for the mixed sols.Keep the sol frozen once unidirectional freezing is complete. We use our cool time to constantly cool the frozen TOCN sol side hook to prevent it from sleep which will lead to the deterioration of the micromorphology of the resulting monolith. Use a saw to cut open the polypropylene tube.Crack the frozen sol into several pieces using pliers. Freeze dry the frozen sol pieces at minus ten degrees Celsius, minus five degrees Celsius, and zero degrees Celsius for one day each sequentially to obtain the microhoneycomb monolith. Unidirectionally freezing 1%by weight TOCN sol at 50 centimeters per hour without glass beads resulted in a gradual change in orientation and channel size along the freezing direction.The microhoneycomb morphology was retained longitudinally throughout the monolith. The bottom centimeter of the monolith was oriented toward the center of the bulk. A well-aligned honeycomb morphology was obtained two centimeters from the bottom.The microhoneycomb channel size increased from 10 micrometers between the second and third centimeters of the monolith and then remained stable. Overall, the unidirectional freezing effect showed no influence on the morphology past three centimeters. The channel size could be tuned by altering the dipping speed and the temperature of the coolant.Tempo oxidized cellulose nanofibers strongly tended to form the microhoneycomb structure via the unidirectional freezing process even in the presence of a second component. A mixed sol with styrene butadiene rubber yielded a composited microhoneycomb monolith with smooth walls. Tempo oxidized cellulose nanofiber microhoneycomb monoliths also supported titanium oxide nanoparticles in a well-ordered microhoneycomb monolith with nanoparticles adhering to the microhoneycomb walls.A mixed sol with SOCF yielded a novel substructure in which the carbon fibers bridged the neighboring microhoneycomb walls. The unidirectional freeze-drying technique is a novel approach through which many regular microstructures can be obtained. We first had the idea for this method will be so well in random microhoneycomb morphology in a wood pattern.It seems the major component of the wood is cellulose. We began to try imbuing up a similar construction with cellulose. Once mastered, this technique can be used to construct many other functional composite MHMs for targeted applications.

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A Net Mold-based Method of Scaffold-free Three-Dimensional Cardiac Tissue Creation

Un método basado en el molde neto creación libre de andamio tridimensional de tejido cardiaco

This protocol describes a novel and easy net mold-based method to create three-dimensional (3-D) cardiac tissues without additional scaffold material. ...

Detection of Endotoxin in Nano-formulations Using Limulus Amoebocyte Lysate (LAL) Assays

Detection of Endotoxin in Nano-formulations Using Limulus Amoebocyte Lysate LAL Assays

Detección de endotoxinas en las formulaciones Nano mediante ensayos de Limulus Amoebocyte Lysate (LAL)

When present in pharmaceutical products, a Gram-negative bacterial cell wall component endotoxin (often also called lipopolysaccharide) can cause ...

Seeding and Implantation of a Biosynthetic Tissue-engineered Tracheal Graft in a Mouse Model

Siembra e implantación de un injerto traqueal tejido-dirigida biosintético en un modelo murino

Treatment options for congenital or secondary long segment tracheal defects have historically been limited due to an inability to replace functional ...

3D Printed Porous Cellulose Nanocomposite Hydrogel Scaffolds

3D impreso celulosa poroso nanocompuesto hidrogel andamios

This work demonstrates the use of three-dimensional (3D) printing to produce porous cubic scaffolds using cellulose nanocomposite hydrogel ink, with ...