Tag Archives: Jun Li

New boron nanostructure—carbon, watch out!

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Carbon nanotubes, buckminsterfullerenes (also known as, buckyballs), and/or graphene are names for different carbon nanoscale structures and, as far as I’m aware,carbon is the only element that merits some distinct names at the nanoscale. By comparison, gold can be gold nanorods, gold nanostars, gold nanoparticles, and so on. In short, nanostructures made of gold (and most other elements) are always prefaced with the word ‘gold’ followed by a word with ‘nano’ in it.

Scientists naming a new boron nanoscale structure seem to have adopted both strategies for a hybrid name. Here’s more from a June 25, 2020 news item on phys.org,

The discovery of carbon nanostructures like two-dimensional graphene and soccer ball-shaped buckyballs helped to launch a nanotechnology revolution. In recent years, researchers from Brown University [located in Rhode Island, US] and elsewhere have shown that boron, carbon’s neighbor on the periodic table, can make interesting nanostructures too, including two-dimensional borophene and a buckyball-like hollow cage structure called borospherene.

Caption: The family of boron-based nanostructures has a new member: metallo-borospherenes, hollow cages made from 18 boron atoms and three atoms of lanthanide elements. Credit: Wang Lab / Brown University

A June 25, 2020 Brown University news release (also on EurekAlert), wbich originated the news item, describes these new structures in detail,

Now, researchers from Brown and Tsinghua University have added another boron nanostructure to the list. In a paper published in Nature Communications, they show that clusters of 18 boron atoms and three atoms of lanthanide elements form a bizarre cage-like structure unlike anything they’ve ever seen.

“This is just not a type of structure you expect to see in chemistry,” said Lai-Sheng Wang, a professor of chemistry at Brown and the study’s senior author. “When we wrote the paper we really struggled to describe it. It’s basically a spherical trihedron. Normally you can’t have a closed three-dimensional structure with only three sides, but since it’s spherical, it works.”

The researchers are hopeful that the nanostructure may shed light on the bulk structure and chemical bonding behavior of boron lanthanides, an important class of materials widely used in electronics and other applications. The nanostructure by itself may have interesting properties as well, the researchers say.

“Lanthanide elements are important magnetic materials, each with very different magnetic moments,” Wang said. “We think any of the lanthanides will make this structure, so they could have very interesting magnetic properties.”

Wang and his students created the lanthanide-boron clusters by focusing a powerful laser onto a solid target made of a mixture of boron and a lanthanide element. The clusters are formed upon cooling of the vaporized atoms. Then they used a technique called photoelectron spectroscopy to study the electronic properties of the clusters. The technique involves zapping clusters of atoms with another high-powered laser. Each zap knocks an electron out of the cluster. By measuring the kinetic energies of those freed electrons, researchers can create a spectrum of binding energies for the electrons that bond the cluster together.

“When we see a simple, beautiful spectrum, we know there’s a beautiful structure behind it,” Wang said.

To figure out what that structure looks like, Wang compared the photoelectron spectra with theoretical calculations done by Professor Jun Li and his students from Tsinghua. Once they find a theoretical structure with a binding spectrum that matches the experiment, they know they’ve found the right structure.

“This structure was something we never would have predicted,” Wang said. “That’s the value of combining theoretical calculation with experimental data.”

Wang and his colleagues have dubbed the new structures metallo-borospherenes, and they’re hopeful that further research will reveal their properties.

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

Spherical trihedral metallo-borospherenes by Teng-Teng Chen, Wan-Lu Li, Wei-Jia Chen, Xiao-Hu Yu, Xin-Ran Dong, Jun Li & Lai-Sheng Wang. Nature Communications volume 11, Article number: 2766 (2020) DOI: https://doi.org/10.1038/s41467-020-16532-x Published: 02 June 2020

This paper is open access.

Harvesting bioenergy to cure wounds and control weight

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I’m always a sucker for bioenergy harvesting stories but this is the first time I’ve seen research on the topic which combines weight control with wound healing. From a January 17, 2019 news item on Nanowerk,


Although electrical stimulation has therapeutic potential for various disorders and conditions, ungainly power sources have hampered practical applications. Now bioengineers have developed implantable and wearable nanogenerators from special materials that create electrical pulses when compressed by body motions. The pulses controlled weight gain and enhanced healing of skin wounds in rat models.

The work was performed by a research team led by Xudong Wang, Ph.D., Professor of Material Sciences and Engineering, College of Engineering, University of Wisconsin-Madison, and supported by the [US Dept. of Health, National Institutes of Health] National Institute of Biomedical Imaging and Bioengineering (NIBIB).

A January 17, 2019 NIBIB news release, which originated the news item, provides more technical information (Note: Links have been removed),

The researchers used what are known as piezoelectric and dielectric materials, including ceramics and crystals, which have a special property of creating an electrical charge in response to mechanical stress.

“Wang and colleagues have engineered solutions to a number of technical hurdles to create piezoelectric and dielectric materials that are compatible with body tissues and can generate a reliable, self-sufficient power supply. Their meticulous work has enabled a simple and elegant technology that offers the possibility of developing electrical stimulation therapies for a number of major diseases that currently lack adequate treatments,” explained David Rampulla, Ph.D., director of the Program in Biomaterials and Biomolecular Constructs at NIBIB

Shedding weight by curbing appetite

Worldwide, more than 700 million people — over 100 million of them children — are obese, causing health problems such as cardiovascular disease, diabetes, kidney disease, and certain cancers. In 2015 approximately four million people died of obesity-related causes1.

To address this crisis, Wang and his colleagues developed a vagal nerve stimulator (VNS) that dramatically improves appetite suppression through electrical stimulation of the vagus nerve. The approach is a promising one that has previously not proven practical because patients must carry bulky battery packs that require proper programming, and frequent recharging

The VNS consists of a small patch, about the size of a fingernail, which carries tiny devices called nanogenerators. Minimally invasive surgery was used to attach the VNS to the stomachs of rats. The rat’s stomach movements resulted in the delivery of gentle electrical pulses to the vagus nerve, which links the brain to the stomach. With the VNS, when the stomach moved in response to eating, the electric signal told the brain that the stomach was full, even if only a small amount of food was consumed.

The device curbed the rat’s appetite and reduced body weight by a remarkable 40 percent. “The stimulation is a natural response to regulate food intake, so there are no unwanted side effects,” explained Wang. When the device was removed the rats resumed their normal eating patterns and their weight returned to pre-treatment levels.

“Given the simplicity and effectiveness of the system, coupled with the fact that the effect is reversible and carries no side-effects, we are now planning testing in larger animals with the hope of eventually moving into human trials,” said Wang.

Accelerating wound healing

In another NIBIB-funded study in a rat experimental model, the researchers used their nanogenerator technology to determine whether electrical stimulation would accelerate healing of wounds on the skin surface.

For this experiment, a band of nanogenerators was placed around the rat’s chest, where the expansion from breathing created a mild electric field. Small electrodes in a bandage-like device were placed over skin wounds on the rat’s back, where they directed the electric field to cover the wound area.

The technique reduced healing times to just three days compared with nearly two weeks for the normal healing process.

Similar to the case with appetite suppression, it was known that electricity could enhance wound healing, but the devices that had been developed were large and impractical. The nanogenerator-powered bandage is completely non-invasive and produced a mild electric field that is similar to electrical activity detected in the normal wound-healing process.

The researchers observed electrical activation of normal cellular healing processes that included the movement of healthy skin fibroblasts into the wound, accompanied by the release of biochemical factors that promote the growth of the fibroblasts and other cell types that expand to repair the wound space.

“The dramatic decrease in healing time was surprising,” said Wang, “We now plan to test the device on pigs because their skin is very similar to humans.” 

The team believes the simplicity of the electric bandage will help move the technology to human trials quickly. In addition, Wang explained that the fabrication of the device is very inexpensive and a product for human use would cost about the same as a normal bandage.

The experiments on appetite suppression were reported in the December issue of Nature Communications2. The wound-healing studies were reported in the December issue of ACS Nano3. Both studies were supported by grant EB021336 from the National Institute of Biomedical Imaging and Bioengineering, and grant CA014520 from the National Cancer Institute.

Here are links to and citations for the papers,

Effective weight control via an implanted self-powered vagus nerve stimulation device by Guang Yao, Lei Kang, Jun Li, Yin Long, Hao Wei, Carolina A. Ferreira, Justin J. Jeffery, Yuan Lin, Weibo Cai & Xudong Wang. Nature Communications volume 9, Article number: 5349 (2018) DOI: https://doi.org/10.1038/s41467-018-07764-z Published 17 December 2018

Effective Wound Healing Enabled by Discrete Alternative Electric Fields from Wearable Nanogenerators by Yin Long, Hao Wei, Jun Li, Guang Yao, Bo Yu, Dalong Ni, Angela LF Gibson, Xiaoli Lan, Yadong Jiang, Weibo Cai, and Xudong Wang. ACS Nano, 2018, 12 (12), pp 12533–12540 DOI: 10.1021/acsnano.8b07038 Publication Date (Web): November 29, 2018

Copyright © 2018 American Chemical Society

Both papers are open access.

Bandage with nanogenerator promotes healing

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This bandage not only heals wounds (on rats) much faster; it’s cheap, according to a November 29, 2018 news item on Nanowerk,

A new, low-cost wound dressing developed by University of Wisconsin-Madison engineers could dramatically speed up healing in a surprising way.

The method leverages energy generated from a patient’s own body motions to apply gentle electrical pulses at the site of an injury.

In rodent tests, the dressings reduced healing times to a mere three days compared to nearly two weeks for the normal healing process.

“We were surprised to see such a fast recovery rate,” says Xudong Wang, a professor of materials science and engineering at UW-Madison. “We suspected that the devices would produce some effect, but the magnitude was much more than we expected.”

A November 29, 2018 University of Wisconsin-Madison news release (also on EurekAlert) by Sam Million-Weaver, which originated the news item, expands on the theme,

Researchers have known for several decades that electricity can be beneficial for skin healing, but most electrotherapy units in use today require bulky electrical equipment and complicated wiring to deliver powerful jolts of electricity.

“Acute and chronic wounds represent a substantial burden in healthcare worldwide,” says collaborator Angela Gibson, professor of surgery at UW-Madison and a burn surgeon and director of wound healing services at UW Health. “The use of electrical stimulation in wound healing is uncommon.”

In contrast with existing methods, the new dressing is much more straightforward.

“Our device is as convenient as a bandage you put on your skin,” says Wang.

The new dressings consist of small electrodes for the injury site that are linked to a band holding energy-harvesting units called nanogenerators, which are looped around a wearer’s torso. The natural expansion and contraction of the wearer’s ribcage during breathing powers the nanogenerators, which deliver low-intensity electric pulses.

“The nature of these electrical pulses is similar to the way the body generates an internal electric field,” says Wang.

And, those low-power pulses won’t harm healthy tissue like traditional, high-power electrotherapy devices might.

In fact, the researchers showed that exposing cells to high-energy electrical pulses caused them to produce almost five times more reactive oxygen species — major risk factors for cancer and cellular aging — than did cells that were exposed to the nanogenerators.

Also a boon to healing: They determined that the low-power pulses boosted viability for a type of skin cell called fibroblasts, and exposure to the nanogenerator’s pulses encouraged fibroblasts to line up (a crucial step in wound healing) and produce more biochemical substances that promote tissue growth.

“These findings are very exciting,” says collaborator Weibo Cai, a professor of radiology at UW-Madison. “The detailed mechanisms will still need to be elucidated in future work.”

In that vein, the researchers aim to tease out precisely how the gentle pulses aid in healing. The scientists also plan to test the devices on pig skin, which closely mimics human tissue.

And, they are working to give the nanogenerators additional capabilities–tweaking their structure to allow for energy harvesting from small imperceptible twitches in the skin or the thrumming pulse of a heartbeat.

“The impressive results in this study represent an exciting new spin on electrical stimulation for many different wound types, given the simplicity of the design,” says Gibson, who will collaborate with the team to confirm the reproducibility of these results in human skin models.

If the team is successful, the devices could help solve a major challenge for modern medicine.

“We think our nanogenerator could be the most effective electrical stimulation approach for many therapeutic purposes,” says Wang.

And because the nanogenerators consist of relatively common materials, price won’t be an issue.

“I don’t think the cost will be much more than a regular bandage,” says Wang. “The device in itself is very simple and convenient to fabricate.”

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

Effective Wound Healing Enabled by Discrete Alternative Electric Fields from Wearable Nanogenerators by Yin Long, Hao Wei, Jun Li, Guang Yao, Bo Yu, Dalong Ni, Angela LF Gibson, Xiaoli Lan, Yadong Jiang, Weibo Cai, and Xudong Wang. ACS Nano, Article ASAP DOI: 10.1021/acsnano.8b07038 Publication Date (Web): November 29, 2018

Copyright © 2018 American Chemical Society

This paper is open access.

I assume it will be a while before there are human clinical trials.

Boron as a ‘buckyball’ or borospherene

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First there was the borophene (like graphene but using boron rather than carbon) announcement from Brown University in my Jan. 28, 214 posting and now US (Brown University again) and Chinese researchers have developed a boron ‘buckyball’. Coincidentally, this announcement comes just after the 2014 World Cup final (July 13, 2014). Representations of buckyballs always resemble soccer balls. (Note: Germany won.)

From a July 14, 2014 news item on Azonano,

The discovery 30 years ago of soccer-ball-shaped carbon molecules called buckyballs helped to spur an explosion of nanotechnology research. Now, there appears to be a new ball on the pitch.

Researchers from Brown University, Shanxi University and Tsinghua University in China have shown that a cluster of 40 boron atoms forms a hollow molecular cage similar to a carbon buckyball. It’s the first experimental evidence that a boron cage structure—previously only a matter of speculation—does indeed exist.

“This is the first time that a boron cage has been observed experimentally,” said Lai-Sheng Wang, a professor of chemistry at Brown who led the team that made the discovery. “As a chemist, finding new molecules and structures is always exciting. The fact that boron has the capacity to form this kind of structure is very interesting.”

The researchers have provided an illustration of their borospherene,

The carbon buckyball has a boron cousin. A cluster for 40 boron atoms forms a hollow cage-like molecule. Courtesy Brown University

The carbon buckyball has a boron cousin. A cluster for 40 boron atoms forms a hollow cage-like molecule. Courtesy Brown University

A July 9, 2104 Brown University news release (also on EurekAlert), which originated the news item, describes the borosphene’s predecessor, the carbon buckyball, and provides more details about this new molecule,

Carbon buckyballs are made of 60 carbon atoms arranged in pentagons and hexagons to form a sphere — like a soccer ball. Their discovery in 1985 was soon followed by discoveries of other hollow carbon structures including carbon nanotubes. Another famous carbon nanomaterial — a one-atom-thick sheet called graphene — followed shortly after.

After buckyballs, scientists wondered if other elements might form these odd hollow structures. One candidate was boron, carbon’s neighbor on the periodic table. But because boron has one less electron than carbon, it can’t form the same 60-atom structure found in the buckyball. The missing electrons would cause the cluster to collapse on itself. If a boron cage existed, it would have to have a different number of atoms.

Wang and his research group have been studying boron chemistry for years. In a paper published earlier this year, Wang and his colleagues showed that clusters of 36 boron atoms form one-atom-thick disks, which might be stitched together to form an analog to graphene, dubbed borophene. Wang’s preliminary work suggested that there was also something special about boron clusters with 40 atoms. They seemed to be abnormally stable compared to other boron clusters.

Figuring out what that 40-atom cluster actually looks like required a combination of experimental work and modeling using high-powered supercomputers.

On the computer, Wang’s colleagues modeled over 10,000 possible arrangements of 40 boron atoms bonded to each other. The computer simulations estimate not only the shapes of the structures, but also estimate the electron binding energy for each structure — a measure of how tightly a molecule holds its electrons. The spectrum of binding energies serves as a unique fingerprint of each potential structure.

The next step is to test the actual binding energies of boron clusters in the lab to see if they match any of the theoretical structures generated by the computer. To do that, Wang and his colleagues used a technique called photoelectron spectroscopy.

Chunks of bulk boron are zapped with a laser to create vapor of boron atoms. A jet of helium then freezes the vapor into tiny clusters of atoms. The clusters of 40 atoms were isolated by weight then zapped with a second laser, which knocks an electron out of the cluster. The ejected electron flies down a long tube Wang calls his “electron racetrack.” The speed at which the electrons fly down the racetrack is used to determine the cluster’s electron binding energy spectrum — its structural fingerprint.

The experiments showed that 40-atom-clusters form two structures with distinct binding spectra. Those spectra turned out to be a dead-on match with the spectra for two structures generated by the computer models. One was a semi-flat molecule and the other was the buckyball-like spherical cage.

“The experimental sighting of a binding spectrum that matched our models was of paramount importance,” Wang said. “The experiment gives us these very specific signatures, and those signatures fit our models.”

The borospherene molecule isn’t quite as spherical as its carbon cousin. Rather than a series of five- and six-membered rings formed by carbon, borospherene consists of 48 triangles, four seven-sided rings and two six-membered rings. Several atoms stick out a bit from the others, making the surface of borospherene somewhat less smooth than a buckyball.

As for possible uses for borospherene, it’s a little too early to tell, Wang says. One possibility, he points out, could be hydrogen storage. Because of the electron deficiency of boron, borospherene would likely bond well with hydrogen. So tiny boron cages could serve as safe houses for hydrogen molecules.

But for now, Wang is enjoying the discovery.

“For us, just to be the first to have observed this, that’s a pretty big deal,” Wang said. “Of course if it turns out to be useful that would be great, but we don’t know yet. Hopefully this initial finding will stimulate further interest in boron clusters and new ideas to synthesize them in bulk quantities.”

The theoretical modeling was done with a group led by Prof. Si-Dian Li from Shanxi University and a group led by Prof. Jun Li from Tsinghua University. The work was supported by the U.S. National Science Foundation (CHE-1263745) and the National Natural Science Foundation of China.

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

Observation of an all-boron fullerene by Hua-Jin Zhai, Ya-Fan Zhao, Wei-Li Li, Qiang Chen, Hui Bai, Han-Shi Hu, Zachary A. Piazza, Wen-Juan Tian, Hai-Gang Lu, Yan-Bo Wu, Yue-Wen Mu, Guang-Feng Wei, Zhi-Pan Liu, Jun Li, Si-Dian Li, & Lai-Sheng Wang. Nature Chemistry (2014) doi:10.1038/nchem.1999 Published online 13 July 2014

This paper is behind a paywall.

Borophene at Brown University (US)

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It’s still theory at this point but researchers at Brown University (Rhode Island, US) have produced experimental proof that a single layer of boron atoms in a lattice reminiscent of  but not identical to a graphene layer is possible. A Jan. 28, 2014 news item on Azonano describes the research,

Researchers from Brown University have shown experimentally that a boron-based competitor to graphene is a very real possibility.

Graphene has been heralded as a wonder material. Made of a single layer of carbon atoms in a honeycomb arrangement, graphene is stronger pound-for-pound than steel and conducts electricity better than copper. Since the discovery of graphene, scientists have wondered if boron, carbon’s neighbor on the periodic table, could also be arranged in single-atom sheets. Theoretical work suggested it was possible, but the atoms would need to be in a very particular arrangement.

Boron has one fewer electron than carbon and as a result can’t form the honeycomb lattice that makes up graphene. For boron to form a single-atom layer, theorists suggested that the atoms must be arranged in a triangular lattice with hexagonal vacancies — holes — in the lattice.

“That was the prediction,” said Lai-Sheng Wang, professor of chemistry at Brown, “but nobody had made anything to show that’s the case.”

Wang and his research group, which has studied boron chemistry for many years, have now produced the first experimental evidence that such a structure is possible. In a paper published on January 20 in Nature Communications, Wang and his team showed that a cluster made of 36 boron atoms (B36) forms a symmetrical, one-atom thick disc with a perfect hexagonal hole in the middle.

Here’s an image that illustrates ‘borophene’,

Caption: This shows a 36-atom cluster of boron, left, arranged as a flat disc with a hexagonal hole in the middle, fits the theoretical requirements for making a one-atom-thick boron sheet, right, a theoretical nanomaterial dubbed "borophene." Credit: Wang Lab / Brown University

Caption: This shows a 36-atom cluster of boron, left, arranged as a flat disc with a hexagonal hole in the middle, fits the theoretical requirements for making a one-atom-thick boron sheet, right, a theoretical nanomaterial dubbed “borophene.”
Credit: Wang Lab / Brown University

The Jan. 27, 2014 Brown University news release (also on EurekAlert), which originated the news item, provides details about how the research was conducted,

The work required a combination of laboratory experiments and computational modeling. In the lab, Wang and his student, Wei-Li Li, probe the properties of boron clusters using a technique called photoelectron spectroscopy. They start by zapping chunks of bulk boron with a laser to create vapor of boron atoms. A jet of helium then freezes the vapor into tiny clusters of atoms. Those clusters are then zapped with a second laser, which knocks an electron out of the cluster and sends it flying down a long tube that Wang calls his “electron racetrack.” The speed at which the electron flies down the racetrack is used to determine the cluster’s electron binding energy spectrum — a readout of how tightly the cluster holds its electrons. That spectrum serves as fingerprint of the cluster’s structure.

Wang’s experiments showed that the B36 cluster was something special. It had an extremely low electron binding energy compared to other boron clusters. The shape of the cluster’s binding spectrum also suggested that it was a symmetrical structure.

To find out exactly what that structure might look like, Wang turned to Zachary Piazza, one of his graduate students specializing in computational chemistry. Piazza began modeling potential structures for B36 on a supercomputer, investigating more than 3,000 possible arrangements of those 36 atoms. Among the arrangements that would be stable was the planar disc with the hexagonal hole.

“As soon as I saw that hexagonal hole,” Wang said, “I told Zach, ‘We have to investigate that.'”

To ensure that they have truly found the most stable arrangement of the 36 boron atoms, they enlisted the help of Jun Li, who is a professor of chemistry at Tsinghua University in Beijing and a former senior research scientist at Pacific Northwest National Laboratory (PNNL) in Richland, Wash. Li, a longtime collaborator of Wang’s, has developed a new method of finding stable structures of clusters, which would be suitable for the job at hand. Piazza spent the summer of 2013 at PNNL working with Li and his students on the B36 project. They used the supercomputer at PNNL to examine more possible arrangements of the 36 boron atoms and compute their electron binding spectra. They found that the planar disc with a hexagonal hole matched very closely with the spectrum measured in the lab experiments, indicating that the structure Piazza found initially on the computer was indeed the structure of B36.

That structure also fits the theoretical requirements for making borophene, which is an extremely interesting prospect, Wang said. The boron-boron bond is very strong, nearly as strong as the carbon-carbon bond. So borophene should be very strong. Its electrical properties may be even more interesting. Borophene is predicted to be fully metallic, whereas graphene is a semi-metal. That means borophene might end up being a better conductor than graphene.

“That is,” Wang cautions, “if anyone can make it.”

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

Planar hexagonal B36 as a potential basis for extended single-atom layer boron sheets by Zachary A. Piazza, Han-Shi Hu, Wei-Li Li, Ya-Fan Zhao, Jun Li, & Lai-Sheng Wang. Nature Communications 5, Article number: 3113 doi:10.1038/ncomms4113 Published 20 January 2014

This paper is behind a paywall.