A new study conducted by SISSA and the University of Trieste shows the efficacy of carbon nanotube implants to restore motor functions and paves the way for a new therapeutic approach for spinal cord injuries.
Re-establishing motor skills and neuronal connectivity thanks to the implantation of carbon nanotubes in the injury site. This is the result of a new study conducted by SISSA – Scuola Internazionale Superiore di Studi Avanzati and the University of Trieste that rewards a ten years interdisciplinary collaboration. For the first time, the researchers have used nanomaterial implants in animals with spinal injury, observing the regrowth of nerve fibres and the restoration of motor functions.
“We have been studying the interaction between neurons and carbon nanotubes for 15 years. Finally, we have been able to challenge their function in vivo”, say Laura Ballerini, neurophysiologist at SISSA, and Maurizio Prato, chemist at the University of Trieste, who have been investigating nerve cell growth when interfaced to smart materials, such as carbon nanotubes in the last decade, using increasingly complex systems. “In recent years, we passed from single neurons to brain tissue explants and from single nanotubes to two-dimensional structures and, now, three dimensional ones.”
“We studied the effect of the carbon nanotube implant in small mammals with a disease model of incomplete spinal cord injury,” explains Sadaf Usmani, PhD in neurobiology and lead author of the study. “We observed their motor recovery during the next six months through standard protocols for locomotor evaluation which revealed a greater recovery of motor skills when compared to non-implanted animals”.
This phenomenon is associated with nerve fibre regrowth through the injury site, as shown by the magnetic resonance experiments carried out in collaboration with the Center for Cooperative Research in Biomaterials (CIC biomaGUNE). A regrowth that is certainly favoured by nanotube implantation, explain Ballerini and Prato.
“Nerve fibre regeneration is promoted by the physical characteristics of nanomaterials. These implants are able to guarantee mechanical support and, at the same time, interact electrically with neurons.”
“The functionality of the regenerated tissue was not taken for granted, just as the biocompatibility of the implants” continue the researchers “And yet, not only there have been no cases of rejection, but electron microscope observations and the use of specific markers have confirmed that there is no real boundary between the tissue surrounding the injury, the regenerated tissue and the nanomaterials.”
These results not only confirm the possible applications of the nanomaterials in the biomedical sector but also pave the way to new therapeutic approaches which use the physical, mechanical and electrical properties in particular, of the injured zone to favour functional recovery.
The authors acknowledge the support received from the National Science Foundation through the Engineering Research Center for Nanotechnology-Enabled Water Treatment (EEC1449500) and via Grant CBET 1437630. The authors also acknowledge funding from the National Science Foundation Graduate Research Fellowship Program under grant no. DGE-1752134, awarded to C.J.P. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation.
ABSTRACT
Transmembrane protein channels, including ion channels and aquaporins that are responsible for fast and selective transport of water, have inspired membrane scientists to exploit and mimic their performance in membrane technologies. These biomimetic membranes comprise discrete nanochannels aligned within amphiphilic matrices on a robust support. While biological components have been used directly, extensive work has also been conducted to produce stable synthetic mimics of protein channels and lipid bilayers.
However, the experimental performance of biomimetic membranes remains far below that of biological membranes. In this review, we critically assess the status and potential of biomimetic desalination membranes. We first review channel chemistries and their transport behavior, identifying key characteristics to optimize water permeability and salt rejection.
We compare various channel types within an industrial context, considering transport performance, processability, and stability. Through a re-examination of previous vesicular stopped-flow studies, we demonstrate that incorrect permeability equations result in an overestimation of the water permeability of nanochannels. We find in particular that the most optimized aquaporin-bearing bilayer had a pure water permeability of 2.1 L m–2 h–1 bar–1, which is comparable to that of current state-of-the-art polymeric desalination membranes.
Through a quantitative assessment of biomimetic membrane formats, we analytically show that formats incorporating intact vesicles offer minimal benefit, whereas planar biomimetic selective layers could allow for dramatically improved salt rejections. We then show that the persistence of nanoscale defects explains observed subpar performance. We conclude with a discussion on optimal strategies for minimizing these defects, which could enable breakthrough performance.
Biomimetic Desalination Membranes
As stressors like population growth, industrialization, and climate change threaten to deplete and contaminate our freshwater resources, larger bodies of saline water could provide a vast supply of water for drinking, agricultural, and industrial use.(1) However, desalination of these waters requires more energy and financial resources than traditional freshwater purification methods.(2) Currently, the state-of-the-art technology for desalination is reverse osmosis (RO) using thin-film-composite (TFC) polyamide membranes.(3,4) Fully aromatic TFC-RO membranes are readily produced at industrial scale through interfacial polymerization, whereby a rapid reaction occurs at the interface of immiscible organic and aqueous phases to form a highly cross-linked polyamide selective layer on a porous support(5) (Figure 1). With the advent of the TFC-RO membrane and energy recovery devices, seawater desalination energy requirements for the RO stage have drastically reduced from ∼15 kWh m–3 using the original cellulose acetate membranes of the 1970s down to only ∼2 kWh m–3, only ∼25% above the practical minimum energy.(2)
Figure 1. Transition in desalination research from focusing on dense polymers that reject salt by a solution-diffusion mechanism to considering sub-nanometer channels capable of molecularly sieving ions. In the solution-diffusion panel (left), common reactants for TFC-RO membranes are represented, which rapidly react at an organic–aqueous interface during interfacial polymerization to form a cross-linked, fully aromatic polyamide selective layer with characteristic ridge-valley morphology. Salt rejection determined by a solution-diffusion mechanism results from the higher partitioning and/or diffusion rates of water over ions. In the ion sieving panel (right), common molecular sieves that have been considered for desalination are shown, with ideal water pathways illustrated. In pores similar in size to water, single-file water transport is induced. Nanotubes and nanochannels can be synthetic (e.g., carbon nanotubes) or biological (e.g., aquaporins). To produce nanoporous sheets, sub-nanometer pores where only a few atoms are vacant have been etched in single-layer graphene using chemical oxidation, electron beam irradiation, doping, and ion bombardment.(12) For 2D laminates, the water pathway is through interlayer spaces between sheets. Studies so far have primarily considered graphene oxide nanosheets for 2D laminates.(13,14) The molecular sieving mechanism for ion rejection is by size exclusion, where highly uniform pores exclude larger solutes and ideally transport only molecules similar in size to water.
Reduced Operational Costs, Improved Reliability and Efficiency and Enhanced Product Water Quality
Despite the substantial reduction in energy consumption and overall cost, seawater RO still has room for improvement. While current water permeabilities enable near-optimal performance, increased water-solute selectivity would allow for reduced operational costs, improved reliability and efficiency, and enhanced product water quality.(4) For example, TFC-RO membranes inadequately retain chloride and some small neutral solutes, such as boron in seawater desalination and trace organic contaminants in wastewater reuse, necessitating extra purification steps which increase the cost of desalination.(4)Transport through the polyamide layer is well described by the solution-diffusion model, in which permeants (i.e., water and solutes) partition into the dense polyamide layer and diffuse through it (Figure 1).(6)
The resultant permselectivity of the membrane is attributed to differences in abilities and rates of species to dissolve into and diffuse through the polyamide membrane material.(7) Although intrinsic water permeability can far exceed salt permeability during solution diffusion, as it does for polyamide, historical data suggest that it will be difficult to significantly advance performance with polymeric systems. Commercial desalination and water purification membranes typically exhibit a permeability–selectivity trade-off, similar to the Robeson plot for polymeric gas separations.(8−11)
Furthermore, despite many decades of extensive research, no polymeric material has yet surpassed the desalination performance (i.e., water permeability, water-salt selectivity, and cost-effectiveness) of fully aromatic polyamide.
To overcome the limitations of the solution-diffusion-based polyamide membranes, research focus has shifted toward the development of desalination membranes that remove solutes via molecular sieving. In this mechanism of ion rejection, highly uniform, rigid pores that are smaller than the diameter of hydrated salt ions transport water and nearly completely reject ions by size exclusion (Figure 1). Recent formats of molecular sieves considered for desalination include nanotubes and nanochannels, two-dimensional (2D) laminates, and nanoporous sheets (Figure 1).(14)
However, these top-down efforts have failed so far to achieve adequate salt rejection due to the persistence of defects coupled with the daunting challenges of tuning interlayer spacing or pore size.(12,13,15)
Biomimetic membranes, or composites comprising an amphiphilic matrix with discrete, aligned nanochannels on a robust support, may provide a platform for industrial-scale molecular sieves that overcome the limitations of solution-diffusion-based polyamide membranes.
After over 3.5 billion years of evolution,(16,17) the cell membranes of modern organisms can perform an array of highly complicated functions, which rely on a system of complex transmembrane proteins aligned within the amphiphilic lipid bilayer. In this system, water and only select ions pass through channel pores and pumps, depending on the energy and nutrient needs of the cell.(18,19) In pioneering work, Preston et al. determined that an integral membrane protein formed a biological channel that selectively transports water in and out of many types of cells. This protein was the CHannel-forming Integral Protein of 28 kDa (CHIP28),(20,21) later called the aquaporin. For these discoveries, Peter Agre and Roderick MacKinnon shared the 2003 Nobel Prize in Chemistry. Through additional biophysical studies, ion channels also showed impressive selectivity, inspiring the design of synthetic ion channels.(22−25)
Eventually, researchers realized the potential implications of these channels for industrial-scale water purification, especially aquaporin in the use of desalination, and attempted to produce biomimetic membranes, or materials that mimic the structure and performance of biological membranes.(26−35)
While much of the work has focused on water-solute separations, the biomimetic membrane format also presents opportunities to develop membranes with tunable selectivity based on a chosen channel type.However, translating biological mechanisms into industrial-scale technology necessitates scale-up by orders of magnitude—from the microscopic size of a cell membrane to tens of square meters.(36) For industrial relevance, the synthesis of a biomimetic membrane would need to be cost-effective and simple. Simultaneously, such a membrane would need to be mechanically stable under RO pressures exceeding 70 bar and chemically stable during repeated membrane cleaning and usage.(37) Notably, even at the lab scale, sufficiently high-salt rejection has not yet been achieved for biomimetic desalination membranes after over a decade of research.(37,38)
Therefore, channels, selective layer formats, synthesis strategies, and support layer types must be carefully considered to attain the capabilities of this technology. While certain aspects of biomimetic desalination membranes have been reviewed recently,(37−42) a critical analysis of their performance and their potential application in water-treatment processes remains necessary.In this critical review, we examine efforts toward biomimetic desalination membranes for water purification in order to identify the best strategies to realize their full potential for both desalination and solute–solute selectivity. We first examine molecular transport, contrasting solution-diffusion with molecular sieving and assessing transport through the mixed matrix of biomimetic selective layers. We next identify the key characteristics of the aquaporin that explain its ultraselectivity and fast water transport, comparing this biological channel to several synthetic channels and placing each in industrial context. Using corrected analysis of reported permeability measurements, we then show that the water permeabilities of many channels have been overestimated. Subsequently, we predict best-case-scenario outcomes for common biomimetic formats, including membranes with intact vesicles and membranes with planar biomimetic layers. For the more promising planar format, the biggest challenge is the presence of nanoscale defects. Through mathematical models, we estimate the defect density for several reported biomimetic membranes. We then discuss synthesis pathways that could limit both the presence of defects and the effect of defects on transport performance.
We conclude with a discussion on the practicality of biomimetic desalination membranes and how to best exploit the strengths of discrete nanochannels as molecular sieves in other applications beyond desalination.
Figure 2. Channel types for biomimetic membranes, including biological as well as bioinspired and bioderived. (a) Single channel water permeability versus pore interior diameter. The pore interior diameter here is defined as the inner diameter of the most constricted region. For PAH[4], the pore diameter shown refers to the average width of dynamic voids that formed in channel clusters.
Channel permeabilities from stopped-flow data and simulations were adjusted to 25 °C and corrected for any previous errors in permeability calculation (see SI, Section S1 for details). (b) (left) Overhead view of AqpZ tetramer and (right) side view of single AqpZ channel with characteristic hourglass shape. (c) GramA dimer as it exists in biological and vesicular environments. In organic solvents, the monomers can intertwine to form a parallel or antiparallel helix. AqpZ and GramA diagrams were drawn using PyMOL(69) with protein sequences from the Research Collaboratory for Structural Bioinformatics Protein Data Bank (RCSB-PDB, https://www.rcsb.org/), PDB-ID codes 1RC2(70) and 1NRM.(71) (d) Dependence of water diffusivity through pores on the number of interior hydrogen-bond points.
Data extracted from ref (56). (e) Cyclic peptide nanotubes. (left) Hydrogen-bonding pattern of pore-forming, stacked cyclic peptides. A polyglycine structure is shown for simplicity; side residues would typically be present. (right) Modified cyclic peptide with interior peptide-mimicking functional groups. The analogous unmodified cyclic peptide is radially symmetrical with a fourth primary amine side chain (cyclo[(d-Ala-Lys)4]).(72) (f) Single-walled carbon nanotube porins (wide and narrow) with armchair pattern. Number of carbons approximate those of wCNTP and nCNTP. (g) (left) PAP[5] and (right) PAH[4] nanochannels with peptide appendages that form interarm hydrogen bonds. (h) (left) Aquafoldamer subunits with “sticky” ends. Differences in end groups that comprise Aqf1 and Aqf2 subunits are illustrated. (right) Weak hydrogen-bonding pattern of pore-forming, stacked aquafoldamers. Six subunits are needed to cross a DOPC membrane. (i) Pure water permeability versus total channel areal coverage in a DOPC bilayer. Single channel permeabilities from (a) were divided by channel cross-sectional area and converted into channel water permeability (A) coefficients using eq 3. Overall biomimetic layer A coefficients were calculated for various densities of channels within a DOPC bilayer using eq 7. DOPC bilayer hydraulic permeability was taken as 0.15 L m–2 h–1 bar–1.(73) The shaded region indicates the water permeability of current commercial TFC-RO membranes, an adequate range for desalination performance. Permeabilities are listed in Table S1.
** Read the Complete Paper and Conclusions from AZ Nano by Following the Link Below
Cassandra J. Porter: Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut
Jay R. Werber: Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut and Department of Chemistry, University of Minnesota, Minneapolis, Minnesota
Mingjiang Zhong: Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut
Corey J. Wilson: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
Menachem Elimelech: Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut
Happy Holiday (Labor Day) Weekend Everyone! Here are our Top Posts from this past week … Just in case you missed them! We hope all of you are well and safe and continuing to ‘get back to normal’ as the COVID-19 Pandemic of 2020 continues to restrain all of us in one way or another.
Thankfully however, COVID-19 has NOT restricted the Forward Advance of Innovation and Technology Solutions from the small worlds of Nanotechnology – “Great Things from Small Things” – Read and Enjoy and wonderful Holiday Weekend! – Team GNT
Carbon Nanotube Second Skin Protects First Responders and Warfighters against Chem, Bio Agents – Lawrence Livermore National Laboratory
The same materials (adsorbents or barrier layers) that provide protection in current garments also detrimentally inhibit breathability.
Recent events such as the COVID-19 pandemic and the use of chemical weapons in the Syria conflict have provided a stark reminder of the plethora of chemical and biological threats that soldiers, medical personnel and first responders face during routine and emergency operations. Researchers have developed a smart, breathable fabric designed to protect the wearer against biological and chemical warfare agents. Material of this type could be used in clinical and medical settings as well.
Recent events such as the COVID-19 pandemic and the use of chemical weapons in the Syria conflict have provided a stark reminder of the plethora of chemical and biological threats that soldiers, medical personnel and first responders face during routine and emergency operations.
MIT: Lighting the Way to Better Battery Technology
Supratim Das is determined to demystify lithium-ion batteries, by first understanding their flaws. Photo: Lillie Paquette/School of Engineering
Doctoral candidate Supratim Das wants the world to know how to make longer-lasting batteries that charge mobile phones and electric cars.
Supratim Das’s quest for the perfect battery began in the dark. Growing up in Kolkata, India, Das saw that a ready supply of electric power was a luxury his family didn’t have. “I wanted to do something about it,” Das says. Now a fourth-year PhD candidate in MIT chemical engineering who’s months away from defending his thesis, he’s been investigating what causes the batteries that power the world’s mobile phones and electric cars to deteriorate over time.
Lithium-ion batteries, so-named for the movement of lithium ions that make them work, power most rechargeable devices today. The element lithium has properties that allow lithium-ion batteries to be both portable and powerful; the 2019 Nobel Prize in Chemistry was awarded to scientists who helped develop them in the late 1970s. But despite their widespread use, lithium-ion batteries, essentially a black box during operation, harbor mysteries that prevent scientists from unlocking their full potential. Das is determined to demystify them, by first understanding their flaws.
Nuclear Diamond Batteries could disrupt Energy/ Energy Storage as we know it … “Imagine a World where you wouldn’t need to charge your battery for …. Decades!”
Illustration of the NDB Battery in a Most Recognizable ‘18650’ Format
“They will blow any energy density comparison out of the water, lasting anywhere from a decade to 28,000 years without ever needing a charge.”
“They will offer higher power density than lithium-ion. They will be nigh-on indestructible and totally safe in an electric car crash.”
And in some applications, like electric cars, they stand to be considerably cheaper than current lithium-ion packs despite their huge advantages.
In the words of Dr. John Shawe-Taylor, UNESCO Chair and University College London Professor: “NDB has the potential to solve the major global issue of carbon emissions in one stroke without the expensive infrastructure projects, energy transportation costs, or negative environmental impacts associated with alternate solutions such as carbon capture at fossil fuel power stations, hydroelectric plants, turbines, or nuclear power stations.
“Practical and Viable” Hydrogen Production from Solar – Long Sought Goal of Renewable Energy – Is Close … Oh So Close
Technology developed at the Technion: the oxygen and hydrogen are produced and stored in completely separate cells.
Technion Israel Institute of Technology
Israeli and Italian scientists have developed a renewable energy technology that converts solar energy to hydrogen fuel — and it’s reportedly at the threshold of “practical” viability.The new solar tech would offer a sustainable way to turn water and sunlight into storable energy for fuel cells, whether that stored power feeds into the electrical grid or goes to fuel-cell powered trucks, trains, cars, ships, planes or industrial processes.Think of this research as a sort of artificial photosynthesis, said Lilac Amirav, associate professor of chemistry at the Technion — Israel Institute of Technology in Haifa. (If it could be scaled up, the technology could eventually be the basis of “solar factories” in which arrays of solar collectors split water into stores of hydrogen fuel——as well as, for reasons discussed below, one or more other industrial chemicals.)Read More … https://genesisnanotech.wordpress.com/2020/09/02/practical-and-viable-hydrogen-production-from-solar-long-sought-goal-of-renewable-energy-is-close-oh-so-close/
Watch More … The EV ‘Revolution and Evolution’ … Will the Era of the ICE be over in 2025? 2030?
Tony Seba, Silicon Valley entrepreneur, Author and Thought Leader, Lecturer at Stanford University, Keynote The reinvention and connection between infrastructure and mobility will fundamentally disrupt the clean transport model. It will change the way governments and consumers think about mobility, how power is delivered and consumed and the payment models for usage.
Israeli and Italian scientists have developed a renewable energy technology that converts solar energy to hydrogen fuel — and it’s reportedly at the threshold of “practical” viability.
The new solar tech would offer a sustainable way to turn water and sunlight into storable energy for fuel cells, whether that stored power feeds into the electrical grid or goes to fuel-cell powered trucks, trains, cars, ships, planes or industrial processes.
Think of this research as a sort of artificial photosynthesis, saidLilac Amirav, associate professor of chemistry at theTechnion— Israel Institute of Technology in Haifa. (If it could be scaled up, the technology could eventually be the basis of “solar factories” in which arrays of solar collectors split water into stores of hydrogen fuel——as well as, for reasons discussed below, one or more other industrial chemicals.)
“We [start with] a semiconductor that’s very similar to what we have in solar panels,” says Amirav. But rather than taking the photovoltaic route of using sunlight to liberate a current of electrons, the reaction they’re studying harnesses sunlight to efficiently and cost-effectively peel off hydrogen from water molecules.
The big hurdle to date has been that hydrogen and oxygen just as readily recombine once they’re split apart—that is, unless a catalyst can be introduced to the reaction that shunts water’s two component elements away from one another.
Enter the rod-shaped nanoparticles Amirav and co-researchers have developed. The wand-like rods (50-60 nanometers long and just 4.5 nm in diameter) are all tipped with platinum spheres 2–3 nm in diameter, like nano-size marbles fastened onto the ends of drinking straws.
Since 2010, when the team first began publishing papers about such specially tuned nanorods, they’ve been tweaking the design to maximize its ability to extract as much hydrogen and excess energy as possible from “solar-to-chemical energy conversion.”
Which brings us back to those “other” industrial chemicals. Because creating molecular hydrogen out of water also yields oxygen, they realized they had to figure out what to do with that byproduct.
“When you’re thinking about artificial photosynthesis, you care about hydrogen—because hydrogen’s a fuel,” says Amirav. “Oxygen is not such an interesting product. But that is the bottleneck of the process.”
There’s no getting around the fact that oxygen liberated from split water molecules carries energy away from the reaction, too. So, unless it’s harnessed, it ultimately represents just wasted solar energy—which means lost efficiency in the overall reaction.
Technology developed at the Technion: the oxygen and hydrogen are produced and stored in completely separate cells.
Prof. Avner Rothschild from the Faculty of Materials Science and Engineering
So, the researchers added another reaction to the process. Not only does their platinum-tipped nanorod catalyst use solar energy to turn water into hydrogen, it also uses the liberated oxygen to convert the organic molecule benzylamine into the industrial chemical benzaldehyde (commonly used in dyes, flavoring extracts, and perfumes).
All told, the nanorods convert 4.2 percent of the energy of incoming sunlight into chemical bonds. Considering the energy in the hydrogen fuel alone, they convert 3.6 percent of sunlight energy into stored fuel.
These might seem like minuscule figures. But 3.6 percent is still considerably better than the 1-2 percent range that previous technologies had achieved.
And according to the U.S. Department of Energy, 5-10 percent efficiency is all that’s needed to reach what the researchers call the “practical feasibility threshold” for solar hydrogen generation.
Between February and August of this year, Amirav and her colleagues published about the above innovations in the journalsNanoEnergyandChemistry Europe. They also recently presented their research at the fall virtual meeting of the American Chemical Society.
In their presentation, which hinted at future directions for their work, they teased further efficiency improvements courtesy of new new work with AI data mining experts.
“We are looking for alternative organic transformations,” says Amirav. This way, she and her collaborators hope, their solar factories can produce hydrogen fuel plus an array of other useful industrial byproducts.
In the future, their artificial photosynthesis process could yield low-emission energy, plus some beneficial chemical extracts as a “practical” and “feasible” side-effect.
Supratim Das’s quest for the perfect battery began in the dark. Growing up in Kolkata, India, Das saw that a ready supply of electric power was a luxury his family didn’t have. “I wanted to do something about it,” Das says. Now a fourth-year PhD candidate in MIT chemical engineering who’s months away from defending his thesis, he’s been investigating what causes the batteries that power the world’s mobile phones and electric cars to deteriorate over time.
Genesis Nanotechnologyo and l o 
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