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Beautiful 'flowers' self-assemble in a beaker
With the hand of nature trained on a beaker of chemical fluid, the most delicate flower structures have been formed in a Harvard laboratory -- and not at the scale of inches, but microns.
These minuscule sculptures, curved and delicate, don't resemble the cubic or jagged forms normally associated with crystals, though that's what they are. Rather, fields of carnations and marigolds seem to bloom from the surface of a submerged glass slide, assembling themselves a molecule at a time.
By simply manipulating chemical gradients in a beaker of fluid, Wim L. Noorduin, a postdoctoral fellow at the Harvard School of Engineering and Applied Sciences (SEAS) and lead author of a paper appearing on the cover of the May 17 issue of Science, has found that he can control the growth behavior of these crystals to create precisely tailored structures.
The precipitation of the crystals depends on a reaction of compounds that are diffusing through a liquid solution. The crystals grow toward or away from certain chemical gradients as the pH of the reaction shifts back and forth. The conditions of the reaction dictate whether the structure resembles broad, radiating leaves, a thin stem, or a rosette of petals.
It is not unusual for chemical gradients to influence growth in nature; for example, delicately curved marine shells form from calcium carbonate under water, and gradients of signaling molecules in a human embryo help set up the plan for the body. Similarly, Harvard biologist Howard Berg has shown that bacteria living in colonies can sense and react to plumes of chemicals from one another, which causes them to grow, as a colony, into intricate geometric patterns.
Replicating this type of effect in the laboratory was a matter of identifying a suitable chemical reaction and testing, again and again, how variables like the pH, temperature, and exposure to air might affect the nanoscale structures.
To create the flower structures, Noorduin and his colleagues dissolve barium chloride (a salt) and sodium silicate (also known as waterglass) into a beaker of water. Carbon dioxide from air naturally dissolves in the water, setting off a reaction which precipitates barium carbonate crystals. As a byproduct, it also lowers the pH of the solution immediately surrounding the crystals, which then triggers a reaction with the dissolved waterglass. This second reaction adds a layer of silica to the growing structures, uses up the acid from the solution, and allows the formation of barium carbonate crystals to continue.
"You can really collaborate with the self-assembly process," says Noorduin. "The precipitation happens spontaneously, but if you want to change something then you can just manipulate the conditions of the reaction and sculpt the forms while they're growing."
Increasing the concentration of carbon dioxide, for instance, helps to create 'broad-leafed' structures. Reversing the pH gradient at the right moment can create curved, ruffled structures.
Noorduin and his colleagues have grown the crystals on glass slides and metal blades; they've even grown a field of flowers in front of President Lincoln's seat on a one-cent coin.
"When you look through the electron microscope, it really feels a bit like you're diving in the ocean, seeing huge fields of coral and sponges," describes Noorduin. "Sometimes I forget to take images because it's so nice to explore."
In addition to her roles at Harvard SEAS, the Department of Chemistry and Chemical Biology, and the Wyss Institute, Joanna Aizenberg is Director of the Kavli Institute for Bionano Science and Technology at Harvard and Director of the Science Program at the Radcliffe Institute for Advanced Study.
Coauthors included Alison Grinthal, a research scientist at Harvard SEAS, and L. Mahadevan, who is the Lola England de Valpine Professor of Applied Mathematics at SEAS, Professor of Organismic and Evolutionary Biology and of Physics, and a Core Faculty Member at the Wyss Institute.
The project was supported by National Science Foundation grants to the Harvard Materials Research Science and Engineering Center (DMR-0820484) and the Harvard Center for Nanoscale Systems (ECS-0335765); and by the Netherlands Organization for Scientific Research.
Source: Harvard School of Engineering and Applied Sciences http://www.harvard.edu/
The researchers start by putting a glass plate in a beaker containing water, a salt (barium chloride) and liquid glass (sodium metasilicate). These minerals precipitate onto the plate in shapes dictated by variables such as temperature and carbon dioxide concentration. To build a miniature tulip, for example, the researchers add some table salt to the solution, and the minerals precipitate as a dome shape, about 25 micrometers across at the base. This spurs new chemistry that prompts slender stems to emerge. When Aizenberg’s team lets a little carbon dioxide diffuse into the solution, the stems bloom into dainty cups, the team reports in the May 17 Science.