Tag Archives: hydrophilic

A carbon nanomaterial ‘pot’ for drug delivery

Japanese scientists have developed a new material, which could be used as a carrier for drugs. From an Aug. 5, 2016 news item on phys.org,

A novel, pot-shaped, carbon nanomaterial developed by researchers from Kumamoto University, Japan is several times deeper than any hollow carbon nanostructure previously produced. This unique characteristic enables the material to gradually release substances contained within and is expected to be beneficial in applications such as drug delivery systems.

An Aug. 5, 2016 Kumamoto University press release on EurekAlert, which despite the discrepancy in the dates originated the news item, discusses carbon and the discovery in more detail,

Carbon is an element that is light, abundant, has a strong binding force, and eco-friendly. The range of carbon-based materials is expected to become more widespread in the eco-friendly society of the future. Recently, nanosized (one-billionth of a meter) carbon materials have been developed with lengths, widths, or heights below 100 nm [nanometre]. These materials take extreme forms such as tiny grained substances, thin sheet-like substances, and slim fibrous substances. Example of these new materials are fullerenes, which are hollow cage-like carbon molecules; carbon nanotubes, cylindrical nanostructures of carbon molecules; and graphene, one-atom thick sheets of carbon molecules.

Why are these tiny substances needed? One reason is that reactions with other materials can be much larger if a substance has an increased surface area. When using nanomaterials in place of existing materials, it is possible to significantly change surface area without changing weight and volume, thereby improving both size and performance. The development of carbon nanomaterials has provided novel nanostructured materials with shapes and characteristics that surpass existing materials.

Now, research from the laboratory of Kumamoto University’s Associate Prof. Yokoi has resulted in the successful development of a container-type carbon nanomaterial with a much deeper orifice than that found in similar materials. To create the new material, researchers used their own, newly developed method of material synthesis. The container-shaped nanomaterial has a complex form consisting of varied layers of stacked graphene at the bottom, the body, and the neck areas of the container, and the graphene edges along the outer surface of the body were found to be very dense. Due to these innovate features, Associate Prof. Yokoi and colleagues named the material the “carbon nanopot.”

The carbon nanopot has an outer diameter of 20 ~ 40 nm, an inner diameter of 5 ~ 30 nm, and a length of 100 ~ 200 nm. During its creation, the carbon nanopot is linked to a carbon nanofiber with a length of 20 ~ 100 μm [micrometre] meaning that the carbon nanopot is also available as a carbon nanofiber. At the junction between nanopots, the bottom of one pot simply sits on the opening of the next without sharing a graphene sheet connection. Consequently, separating nanopots is very easy.

“From a detailed surface analysis, hydrophilic hydroxyl groups were found clustered along the outer surface of the carbon nanopot body,” said Associate Prof. Yokoi. “Graphene is usually hydrophobic however, if hydroxyl groups are densely packed on the outer surface of the body, that area will be hydrophilic. In other words, carbon nanopots could be a unique nanomaterial with both hydrophobic and hydrophilic characteristics. We are currently in the process of performing a more sophisticated surface analysis in order to get that assurance.”

Since this new carbon nanopot has a relatively deep orifice, one of its expected uses is to improve drug delivery systems by acting as a new foundation for medicine to be carried into and be absorbed by the body.

Here’s a link to and a citation for the paper,

Novel pot-shaped carbon nanomaterial synthesized in a submarine-style substrate heating CVD method by Hiroyuki Yokoi, Kazuto Hatakeyama, Takaaki Taniguchi, Michio Koinuma, Masahiro Hara, and Yasumichi Matsumoto. Journal of Materials Research / Volume 31 / Issue 01 / 2016, pp 117-126 DOI: http://dx.doi.org/10.1557/jmr.2015.389 (About DOI) Published online: 13 January 2016

Copyright © Materials Research Society 2016

I’m not sure why there’s this push for publicity so long after the publication date. In any event, this paper is behind a paywall.

Better and greener oil recovery

A June 27, 2016 news item on phys.org describes research on achieving better oil recovery,

As oil producers struggle to adapt to lower prices, getting as much oil as possible out of every well has become even more important, despite concerns from nearby residents that some chemicals used to boost production may pollute underground water resources.

Researchers from the University of Houston have reported the discovery of a nanotechnology-based solution that could address both issues – achieving 15 percent tertiary oil recovery at low cost, without the large volume of chemicals used in most commercial fluids.

A June 27, 2016 University of Houston news release (also on EurekAlert) by Jeannie Kever, which originated the news item, provides more detail,

The solution – graphene-based Janus amphiphilic nanosheets – is effective at a concentration of just 0.01 percent, meeting or exceeding the performance of both conventional and other nanotechnology-based fluids, said Zhifeng Ren, MD Anderson Chair professor of physics. Janus nanoparticles have at least two physical properties, allowing different chemical reactions on the same particle.

The low concentration and the high efficiency in boosting tertiary oil recovery make the nanofluid both more environmentally friendly and less expensive than options now on the market, said Ren, who also is a principal investigator at the Texas Center for Superconductivity at UH. He is lead author on a paper describing the work, published June 27 [2016] in the Proceedings of the National Academy of Sciences.

“Our results provide a novel nanofluid flooding method for tertiary oil recovery that is comparable to the sophisticated chemical methods,” they wrote. “We anticipate that this work will bring simple nanofluid flooding at low concentration to the stage of oilfield practice, which could result in oil being recovered in a more environmentally friendly and cost-effective manner.”

In addition to Ren, researchers involved with the project include Ching-Wu “Paul” Chu, chief scientist at the Texas Center for Superconductivity at UH; graduate students Dan Luo and Yuan Liu; researchers Feng Wang and Feng Cao; Richard C. Willson, professor of chemical and biomolecular engineering; and Jingyi Zhu, Xiaogang Li and Zhaozhong Yang, all of Southwest Petroleum University in Chengdu, China.

The U.S. Department of Energy estimates as much as 75 percent of recoverable reserves may be left after producers capture hydrocarbons that naturally rise to the surface or are pumped out mechanically, followed by a secondary recovery process using water or gas injection.

Traditional “tertiary” recovery involves injecting a chemical mix into the well and can recover between 10 percent and 20 percent, according to the authors.

But the large volume of chemicals used in tertiary oil recovery has raised concerns about potential environmental damage.

“Obviously simple nanofluid flooding (containing only nanoparticles) at low concentration (0.01 wt% or less) shows the greatest potential from the environmental and economic perspective,” the researchers wrote.

Previously developed simple nanofluids recover less than 5 percent of the oil when used at a 0.01 percent concentration, they reported. That forces oil producers to choose between a higher nanoparticle concentration – adding to the cost – or mixing with polymers or surfactants.

In contrast, they describe recovering 15.2 percent of the oil using their new and simple nanofluid at that concentration – comparable to chemical methods and about three times more efficient than other nanofluids.

Dan Luo, a UH graduate student and first author on the paper, said when the graphene-based fluid meets with the brine/oil mixture in the reservoir, the nanosheets in the fluid spontaneously go to the interface, reducing interfacial tension and helping the oil flow toward the production well.

Ren said the solution works in a completely new way.

“When it is injected, the solution helps detach the oil from the rock surface,” he said. Under certain hydrodynamic conditions, the graphene-based fluid forms a strong elastic and recoverable film at the oil and water interface, instead of forming an emulsion, he said.

Researchers said the difference is due to the asymmetric property of the 2-dimensional material. Nanoparticles are usually either hydrophobic – water-repelling, like oil – or hydrophilic, water-like, said Feng Wang, a post-doctoral researcher who shared first author-duties with Luo.

“Ours is both,” he said. “Ours is Janus and also strictly amphiphilic.”

Here’s a link to and a citation for the paper,

Nanofluid of graphene-based amphiphilic Janus nanosheets for tertiary or enhanced oil recovery: High performance at low concentration by Dan Luo, Feng Wang, Jingyi Zhu, Feng Cao, Yuan Liu, Xiaogang Li, Richard C. Willson, Zhaozhong Yang, Ching-Wu Chu, and Zhifeng Ren. PNAS 2016 doi: 10.1073/pnas.1608135113 published ahead of print June 27, 2016,

This paper is behind a paywall.

A rose by any other name: water pinning nanostructures and wettability

There are two items about rose petals as bioinspiration for research in this posting. The first being the most recent research where scientists in Singapore have made an ultrathin film modeled on rose petals. From an Aug. 13, 2014 news item on Nanowerk (Note: A link has been removed),

A*STAR [based in Singapore] researchers have used nanoimprinting methods to make patterned polymeric films with surface topography inspired by that of a rose petal, producing a range of transparent films with high water pinning forces (“Bioinspired Ultrahigh Water Pinning Nanostructures”).

An Aug. 13, 2014 A*STAR news highlight, which originated the news item, describes the nature of the research,

A surface to which a water droplet adheres, even when it is turned upside down, is described as having strong water pinning characteristics. A rose petal and a lotus leaf are both superhydrophobic, yet dissimilarities in their water pinning properties cause a water droplet to stick to a rose petal but roll off a lotus leaf. The two leaf types differ in their micro- and nanoscale surface topography and it is these topographical details that alter the water pinning force. The rose petal has almost uniformly distributed, conical-shaped microscale protrusions with nanoscale folds on these protrusions, while the lotus leaf has randomly distributed microscale protrusions.

The imprinted surfaces developed by Jaslyn Law and colleagues at the A*STAR Institute of Materials Research and Engineering and the Singapore University of Technology and Design have uniformly distributed patterns of nanoscale protrusions that are either conical or parabolic in shape. The researchers found that the water pinning forces on these continuously patterned surfaces were much greater than on non-patterned surfaces and surfaces composed of isolated nanopillared structures or nanoscale gratings. They could then achieve high water pinning forces by patterning the nanoprotrusions onto polymeric films with a range of different non-patterned hydrophobicities, including polycarbonate, poly(methyl methacrylate) and polydimethylsiloxane (see image).

“Other methods that recreate the water pinning effect have used actual rose petals as the mold, but unless special care is taken, there are likely to be defects and inconsistencies in the recreated pattern,” says co-author Andrew Ng. “While bottom-up approaches for making patterns — for example, laser ablation, liquid flame spray or chemical vapor deposition — are more consistent, these methods are limited in the types of patterns that can be used and the scale at which a substrate can be patterned.”

In contrast, nanoimprinting methods are capable of fabricating versatile and large-scale surfaces, and can be combined with roll-to-roll techniques, hence potentially enabling more commercial applications.

The patterned polycarbonate surfaces were also shown to reduce the ‘coffee-ring’ effect: the unevenly deposited film left behind upon the evaporation of a solute-laden droplet. This mitigation of the coffee-ring effect may assist microfluidic technologies and, more generally, the patterned surfaces could be used in arid regions for dew collection or in anti-drip applications such as in greenhouses.

The study which was published online in Dec. 2013, was featured in a Jan. 22, 2014 article by Katherine Bourzac for C&EN (Chemistry and Engineering News),

In the early morning, dew clings to rose petals; when the sun rises, the dewdrops act like tiny lenses, making diffraction patterns that attract pollinating insects, says Jaslyn Bee Khuan Law, a materials scientist at the Agency for Science, Technology, and Research (A*STAR), in Singapore. A drop of water will cling to a rose petal even when it’s tilted or held upside down. The petals can hold onto these droplets because their surfaces consist of closely packed conical structures a few micrometers across. These microscale surface patterns tweak the surface tension of the water droplets, causing them to cling to the petals.

But none of these fabrication methods are amenable to large-scale, low-cost manufacturing, preventing commercialization of the water-clinging surfaces. So Law turned to a specialty of her lab: nanoimprint lithography. This printing method utilizes metal or silicon drums molded with nanoscale features on their surfaces. When the molds are heated and pressed against sheets of plastic, the plastic is embossed with the nanoscale pattern. This roll-to-roll printing process resembles the way newspapers are printed. It’s capable of producing large-area films in a short amount of time.

Water droplets easily slid off plastic films patterned with simple nanoscale gratings; isolated nanoscale pillars hung onto water slightly better. But the films with the best properties consisted of tightly packed cones about 300 nm tall. Plastic patterned with these structures could hold onto water droplets as massive as 69 mg. The team could print a 110- by 65-mm sheet of this plastic film at a speed of 10 m per minute. Currently, the dimensions of the films are limited by the size of the premade molds, Law says.

While the Singapore group has made good progress on manufacturing these materials, very basic, vexing questions about how water clings to these surfaces remain, Hayes says. For example, very small changes in the surface’s roughness can switch it from water-pinning to super hydrophobic, and researchers don’t have a detailed understanding of why.

Here’s a link to and a citation for the paper,

Bioinspired Ultrahigh Water Pinning Nanostructures by Jaslyn Bee Khuan Law, Andrew Ming Hua Ng, Ai Yu He, and Hong Yee Low. Langmuir, 2014, 30 (1), pp 325–331 DOI: 10.1021/la4034996 Publication Date (Web): December 20, 2013
Copyright © 2013 American Chemical Society

This paper appears to be open access (I was able to access it by clicking on the HTML option).

Finally, here’s an image supplied by the A*Star researchers to illustrate their work,

[downloaded from http://pubs.acs.org/doi/full/10.1021/la4034996]

[downloaded from http://pubs.acs.org/doi/full/10.1021/la4034996]

This second rose petal item comes from Australia and dates from Fall 2013. From a Sept. 18, 2013 news item on ScienceDaily,

A new nanostructured material with applications that could include reducing condensation in airplane cabins and enabling certain medical tests without the need for high tech laboratories has been developed by researchers at the University of Sydney [Australia].

“The newly discovered material uses raspberry particles — so-called because of their appearance — which can trap tiny water droplets and prevent them from rolling off surfaces, even when that surface is turned upside down,” said Dr Andrew Telford from the University’s School of Chemistry and lead author of the research recently published in the journal, Chemistry of Materials.

The ability to immobilise [pin] very small droplets on a surface is, according to Dr Telford, a significant achievement with innumerable potential applications.

A Sept. 17, 2013 University of Sydney news release, which originated the news item, provides more insight into the research where the scientists have focused on ‘raspberry particles’ which could also be described as the ‘conical structures’ mentioned in the A*STAR work to achieve what appear to be similar ends,

Raspberry particles mimic the surface structure of some rose petals.

“Water droplets bead up in a spherical shape on top of rose petals,” Dr Telford said. “This is a sign the flower is highly water repellent.”

The reasons for this are complex and largely due to the special structure of the rose petal’s surface. The research team replicated the rose petal by assembling raspberry particles in the lab using spherical micro- and nanoparticles.

The result is that water droplets bead up when placed on films of the raspberry particles and they’re not able to drip down from it, even when turned upside down.

“Raspberry particle films can be described as sticky tape for water droplets,” Dr Telford said.

This could be useful in preventing condensation issues in airplane cabins. It could also help rapidly process simple medical tests on free-standing droplets, with the potential for very high turnover of tests with inexpensive equipment and in remote areas.

Other exciting applications are under study: if we use this nanotechnology to control how a surface is structured we can influence how it will interact with water.

“This means we will be able to design a surface that does whatever you need it to do.

“We could also design a surface that stays dry forever, never needs cleaning or able to repel bacteria or even prevent mould and fungi growth.

“We could then tweak the same structure by changing its composition so it forces water to spread very quickly.

“This could be used on quick-dry walls and roofs which would also help to cool down houses.

“This can only be achieved with a very clear understanding of the science behind the chemical properties and construction of the surface,” he said.

The discovery is also potentially viable commercially.

“Our team’s discovery is the first that allows for the preparation of raspberry particles on an industrial scale and we are now in a position where we can prepare large quantities of these particles without the need to build special plants or equipment,” Dr Telford said.

Here’s a link to and a citation for the Australian paper,

Mimicking the Wettability of the Rose Petal using Self-assembly of Waterborne Polymer Particles by A. M. Telford, B. S. Hawkett, C. Such, and C. Neto. Chem. Mater., 2013, 25 (17), pp 3472–3479 DOI: 10.1021/cm4016386 Publication Date (Web): July 23, 2013
Copyright © 2013 American Chemical Society

This paper is behind a paywall.

Hydrophobic and hydrophilic for beginners

Anyone who’s interested in biomimicry (mimicking nature, for one reason or another) is likely to come across the terms hydrophobic (e.g. lotus leaves where water beads up into little balls) and hydrophilic, materials where water spreads itself evenly (e.g. desert beetles such as the stenocara are partly hydrophilic).  David L. Chandler at MIT (Massachusetts Institute of Technology) has written a good explanation (H/T phys.org) of these two states and the surface tensions which cause them in his article, Explained: Hydrophobic and hydrophilic; Better understanding of how surfaces attract or repel water could improve everything from power plants to ketchup bottles of July 16, 2013,

Materials with a special affinity for water — those it spreads across, maximizing contact — are known as hydrophilic. Those that naturally repel water, causing droplets to form, are known as hydrophobic. Both classes of materials can have a significant impact on the performance of power plants, electronics, airplane wings and desalination plants, among other technologies, says Kripa Varanasi, an associate professor of mechanical engineering at MIT. Improvements in hydrophilic and hydrophobic surfaces could provide ketchup bottles where the condiment just glides right out, glasses that never fog up, or power plants that wring more electricity from a given amount of fuel.

Hydrophilic and hydrophobic materials are defined by the geometry of water on a flat surface — specifically, the angle between a droplet’s edge and the surface underneath it. This is called the contact angle.

If the droplet spreads, wetting a large area of the surface, then the contact angle is less than 90 degrees and that surface is considered hydrophilic, or water-loving (from the Greek words for water, hydro, and love, philos). But if the droplet forms a sphere that barely touches the surface — like drops of water on a hot griddle — the contact angle is more than 90 degrees, and the surface is hydrophobic, or water-fearing.

I recommend  reading this piece in its entirety if you want find out more about this unexpectedly interesting topic. For those who don’t have the patience to read the whole article or like to augment their reading with videos, there’s the Bouncing Droplets: Superhydrophobic and Superhydrophilic Surfaces video at the Khan Academy. This well-paced  video was produced by MIT’s Bioinstrumentation Laboratory and is suitable for older children and adults.

Hands off the bubbles in my boiling water!

The discovery that boiling water bubbled was important to me. I’ve never really thought about it until now when researchers at Northwestern University have threatened to take my bubbles away, metaphorically speaking. From the Sept. 13, 2012 news item on ScienceDaily,

Every cook knows that boiling water bubbles, right? New research from Northwestern University turns that notion on its head.

“We manipulated what has been known for a long, long time by using the right kind of texture and chemistry to prevent bubbling during boiling,” said Neelesh A. Patankar, professor of mechanical engineering at Northwestern’s McCormick School of Engineering and Applied Science and co-author of the study.

This discovery could help reduce damage to surfaces, prevent bubbling explosions and may someday be used to enhance heat transfer equipment, reduce drag on ships and lead to anti-frost technologies.

The Sept. 13, 2012 news release from McCormick University (which originated the news item) provides details,

This phenomenon is based on the Leidenfrost effect. In 1756 the German scientist Johann Leidenfrost observed that water drops skittered on a sufficiently hot skillet, bouncing across the surface of the skillet on a vapor cushion or film of steam. The vapor film collapses as the surface falls below the Leidenfrost temperature. When the water droplet hits the surface of the skillet, at 100 degrees Celsius, boiling temperature, it bubbles.

To stabilize a Leidenfrost vapor film and prevent bubbling during boiling, Patankar collaborated with Ivan U. Vakarelski of King Abdullah University of Science and Technology, Saudi Arabia. Vakarelski led the experiments and Patankar provided the theory. The collaboration also included Derek Chan, professor of mathematics and statistics from the University of Melbourne in Australia.

In their experiments, the stabilization of the Leidenfrost vapor film was achieved by making the surface of tiny steel spheres very water-repellant. The spheres were sprayed with a commercially available hydrophobic coating — essentially self-assembled nanoparticles — combined with other water-hating chemicals to achieve the right amount of roughness and water repellency. At the correct length scale this coating created a surface texture full of tiny peaks and valleys.

When the steel spheres were heated to 400 degrees Celsius and dropped into room temperature water, water vapors formed in the valleys of the textured surface, creating a stable Leidenfrost vapor film that did not collapse once the spheres cooled to the temperature of boiling water. In the experiments, researchers completely avoided the bubbly phase of boiling.

To contrast, the team also coated tiny steel spheres with a water-loving coating, heated the objects to 700 degrees Celsius, dropped them into room temperature water and observed that the Leidenfrost vapor collapsed with a vigorous release of bubbles.

The scientists have provided a video illustrating their work,

This movie shows the cooling of 20 mm hydrophilic (left) and superhydrophobic (right) steel spheres in 100 C water. The spheres’ initial temperature is about 380 C. The bubbling phase of boiling is completely eliminated for steel spheres with superhydrophobic coating. (from Vimeo, http://vimeo.com/49391913)

I understand there are advantages to not having bubbles in hot water but it somehow seems wrong. I’ve given up a lot over the years: gravity, boundaries between living and non-living (that was a very big thing to give up), and other distinctions that I have made based on traditional science but, today, this is one step too far.

It may seem silly but that memory of my mother explaining that you identify boiling water by its bubbles is important to me. It was one of my first science lessons. I imagine I will recover from this moment but it does remind me of how challenging it can be when your notions of reality/normalcy are challenged by various scientific endeavours. The process can get quite exhausting as you keep recalibrating everything you ‘know’ all the time.