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May 14, 2018

No Use Crying Over Spilled Chocolate

Last summer, we wrote about a hagfish accident that covered an Oregon highway in slime.  Another sticky situation has come to our attention – on May 9 at 5:30 a.m., a tanker of liquid milk chocolate flipped over on the A2 in western Poland, spilling a dozen tons onto the six lane highway. Until authorities closed the motorway, drivers continued to drive over the spilled chocolate, tracking it a mile in either direction.

Cleanup crews sprayed the congealed chocolate with hot water to re-melt it and wash it off the road. Additionally, a bulldozer pushed chocolate sludge off the motorway – a technique also used to clear the Oregon highway of hagfish slime.

"Removing the chocolate will take a couple of hours. The chocolate congeals on the pavement, and it's worse than snow," one member of the fire brigade told TVN24

At the time of the accident, the temperature in Slupca, Poland was 12 °C, a bit lower than the 20-25 °C usually considered room temperature but not nearly as cold as the 0° to -4°C of a Western Polish January.  What if the temperature had been much lower? Could cars and people have been trapped in the sugary non-Newtonian fluid as it quickly cooled, like the victims of the 1919 Boston Molasses Flood?

The ease at which drivers sped through the spilled chocolate seems to indicate the muck was not impassably sticky. The air temperature must have been warm enough to keep the flow thin enough to allow for mobility. Fortunately, injuries from the May 9th accident were limited to the tanker driver’s broken arm and a reporter’s wounded pride after slipping into a chocolate-filled ditch.

Our CPG application note on chocolate mentions the importance of slow cooling for successful chocolate tempering. Did the change in temperature from tanker (>28 °C) to brisk morning air (12 °C) allow for proper tempering of the highway chocolate? The brown goo would have cooled too quickly for optimal confectionery quality. Probably a moot point, considering highway chocolate will never meet the quality standards of 21CFR163, Subpart B: Requirements for Specific Standardized Cacao Products or EU Directive 2000/36/EC. The only consumers of the Slupca spill are likely to be local wildlife.

 

Posted by CatherineCerasuolo
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April 13, 2018

Vikings and Polarization

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Calcite crystal showing double refraction (from Redpath Museum, McGill University)

We previously wrote about the Mantis shrimp’s use of birefringence as a means of hunting for transparent aquatic prey. Vikings are alleged to have used birefringence as well, but for navigational purposes. A calcite crystal found in a British warship that sank in 1592 was included amongst other navigational tools in the wreck.

The crystal would refract light depending on its orientation relative to the principle axis of the incoming light. When the crystal's principle axis is aligned east-west, an image viewed through the crystal resolves from a double image into a single image, thus providing a means of orientation. Since magnetic compasses were not fully utilized until the end of the 16th century, the crystal may have been used to augment compasses.

Called “sunstones” in Viking sagas, these crystals were believed to be used by Vikings in the 10th century, well before the use of compasses in Europe, to navigate from Norway to Greenland, a journey of 1,600 miles. They can be used in cloudy weather to locate the sun, as well as the afore-mentioned east-west orientation. There is still not direct evidence that Vikings used the sunstones for navigation, but computer simulation has shown that Viking navigation with these crystals would have been possible.

Calcite crystals are still used today as polarizers for the more pedestrian use of examining crystal structure and stress concentration in polymeric materials.

Posted by CatherineCerasuolo
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April 6, 2018

New ASTM F2459-18 Standard Test Method for Extracting Residue

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ASTM F2459 Standard Test Method for Extracting Residue from Metallic Medical Components and Quantifying via Gravimetric Analysis

The latest draft of ASTM F2459 Standard Test Method for Extracting Residue from Metallic Medical Components and Quantifying via Gravimetric Analysis just published. The key difference in this version is the inclusion of the method to determine extractable residue by measuring the medical device before and after extraction. This approach is particularly useful for smaller parts, a method CPG routinely uses to assist clients in cleaning validation. Please contact us if you have any questions about this standard or the associated testing.

Posted by CatherineCerasuolo
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December 20, 2017

From Pine to Renewable Plastic

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Of the estimated 95 million Americans celebrating with Christmas trees this December, 81% are expected to choose plastic trees.  Why is plastic preferred? The cost of buying a live tree is 5%-10% higher this year, due to fewer trees planted during the Great Recession. Although the initial purchase of a plastic tree can cost as much as a live tree, plastic can be re-used, year after year.

In addition to thrift, allergies, ubiquitous needle spikes and fire phobia also play a role in tree material selection. However, an artificial tree is not fireproof. While not as prone to combustion as a dried-out pine, plastic trees can still burn when subjected to holiday hazards such as frayed light cords, candles, or discarded cigarettes.

Despite the benefits of plastic trees, 19% of American tree buyers opt for natural. For some, this decision is an environmental choice, since the purchase of a fresh-cut tree supports tree farms, conserving green space and farm land. Others simply love the smell of a live tree, a fragrance brought to you by the chemical pinene, from the terpene family. Recently, scientists at the University of Bath developed a renewable material from the fragrant beta-pinene that can be used in place of the petrochemical-derived caprolactone.

The Power of Pinene

Bio-based polyesters like (polylactide) PLA are susceptible to brittleness and are often mixed with caprolactone to improve mechanical properties. Although the addition of caprolactone is essential to expanding the plastic's suitability for medical and engineering applications, the resulting plastic is not renewable, since the caprolactone is made from crude oil. The University of Bath researchers' pinene material allows for the creation of sustainable PLA. The chemical similarity between caprolactone and pinene (both are hydrocarbons) makes the possibility of pinene substitution more economically feasible for manufacturers.

Be not afraid, fans of the Tannenbaum au naturel; the researchers have no Grinchly designs on your trees. The concentration of b-pinene in individual trees is fairly low. However, the paper industry produces pinene in large quantities as a waste byproduct of crude sulfate turpentine, making it cheap and readily available.

Possible applications of the new plastic include food packaging, bags, and medical devices. Thus far, only a few grams of the material have been created, and researchers seek to make their production of the pinene-sourced material both scalable and green.

Sustainable Raw Materials

Even the abundant supply of b-pinene generated by the paper industry is still not enough to replace all caprolactone in products currently in use. University of Bath is also investigating how to manipulate bacteria into transforming their natural terpene stores into more useful chemical precursors. If successful, terpene could be produced in mass quantities by fermentation of plant sugars and cellulose waste.

Pinene is just one of many bio-based chemicals currently under consideration as a crude oil alternative. Limonene, from citrus fruit, is another terpene of interest that could be used to create terephthalic acid, a monomer essential to the production of PET - poly(ethylene terephthalate), from renewable sources. The market for PET is huge, so a breakthrough on this front would have a significant environmental impact.

The ability to use bio-based, renewable sources as starting materials could revolutionize the plastics industry and help to mitigate climate change. 

Posted by CatherineCerasuolo
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November 17, 2017

Turkey-Inspired Supraballs

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It’s that time of year when the turkey takes center stage, er, table. Although many claim Ben Franklin lobbied for the turkey to become the United States’ national symbol, Franklin was taken out of context. Franklin neither publicly championed the turkey nor opposed the bald eagle, and he characterized the turkey as “a little vain and silly.” Although the wild turkey was never a candidate for national symbolism, it has played a significant role in the culture of many Native American tribes, from sacred warrior to fabric to favorite meal.  Wild turkey was important to European settlers as well; historical record puts wild turkey on the menu at the first Plymouth Thanksgiving, unlike pumpkin pie, potatoes and cranberry sauce, which wouldn’t have been available to the Pilgrim colonists.

Better Color Through Chemistry

In addition to these cultural and culinary roles, Meleagris gallopavo has another claim to fame. Turkey feathers have inspired an international team of researchers to create a new type of structural coloring, a nanoparticle made of melanin and silica, called a “supraball.” Changing the thickness of the silica shell surrounding the melanin core determines the shade and intensity of color.

Chemical pigments, produced by the absorption of light by molecules, fade as they break down. Structural colors, created by the scattering of light by nanostructures, are resistant to bleaching and are less dependent on toxic materials than pigments. Although structural colors have obvious advantages to chemical pigments, obstacles remain to the mass production of structurally colored materials.

Many structural colors are iridescent and not practical for wide-angle displays. Non-iridescent structural colors often lack adequate color saturation due to incoherent scattering. Although a partial “solution” for non-iridescent colors has been found, it is not scalable; core-shell nanoparticles with a shell refractive index (RI) comparable to water have been used to tune core spacing to attain optimal scattering for non-iridescent colors, but only in solution.

The discovery of the supraball technique could overcome these challenges. Supraballs tune core spacing without the need for a solution, and yield a full spectrum of colors. Additionally, the reverse emulsion process used to create the supraballs is simple and scalable. The nanoparticles cluster into supraballs at room temperature in water and octanol, and can be extracted as a powder.

Paint It Black

Melanin is a dark biological pigment found in skin, hair, feathers (including turkey), scales, eyes, and some internal membranes. The use of melanin, with its high RI and broadband absorption of lights, increases the brightness and saturation of the supraballs. The spacing between the balls of melanin produces different colors, although only from normal distance; under a microscope, the supraballs are black.

The low RI clear silica shell forces the melanin cores farther apart or closer together, depending on the thickness of the shell.  This color tuning technique, using high-RI cores and low-RI shells to increase reflectance and brighten colors, was inspired by the hollow, high RI contrast melansomes of wild turkeys, and the hexagonal nonclose-packed melansomes of green-winged teal (see below).

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Researchers believe this technology can be replicated at the industrial scale, and has many potential applications. Since melanin can dissipate 90% of UV radiation, supraballs could be used to color UV-resistant inks. Supraballs could also be used in paints, plastics, coatings, and, since melanin is biocompatible, cosmetics and food.

Posted by CatherineCerasuolo
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November 16, 2017

Cranberry Polymers

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Some of us dread Thanksgiving - the prospect of awkward political discussions, family dysfunction, and, last but not least, the debate over home-made vs. canned cranberry sauce. This annual cranberry conflict seems like a subject fit for a Seussian Butter Battle sequel. Many households solve the problem by offering both a thick, homemade sauce and a can-shaped, store-bought jelly. In either version of the cranberry condiment, pectin polymerization plays a vital role.

Pectin Polymerization

Regardless of whether the sauce is made in the kitchen or factory, the first step is dissolving sugar in water. Once the sugar is dissolved, it is safe to add the cranberries. Heating the berries before adding the sugar will result in a runny pink liquid, unappealing to all.

Cranberries contain a great deal of pectin, a naturally occurring polymer found in the cell walls of plants. When the berries are heated, their cell walls pop open and break apart, releasing the pectin. Pectin is usually attracted to water molecules; however, if most of the water molecules are already bonded to sugar molecules, pectin polymers will bind to other pectin polymers, giving your cranberry concoction more structure. The linked pectin increases the viscosity of the sauce, thereby thickening it in a fashion similar to gravy.

Cooking the sauce for longer will release more pectin, increasing the stability of the sauce, and resulting in a more gelled dish.

Pectin has been used by the food and beverage industry for years as a gelling agent, a thickening agent, and a colloidal stabilizer. The pharmaceutical and biotechnology industries are also discovering applications for pectin; its distinctive properties allow it to be used as a matrix for drug delivery or cell/protein entrapment.

Cranberry is a Type-A Fruit

The American cranberry, one of only three fruits native to North America, contains large amounts of A-type proanthocyanidins (PACs). Cranberry proanthocyanidins are a varied group of polymeric structures made up of flavan- 3-ols, ranging greatly in size and structure. Unlike most other fruits which contain B-type PACs, cranberry’s A-type PACs have been shown to impede bacterial adhesion to cellular or biomaterial surfaces. Recent research published in Nature:Scientific Reports demonstrates that cranberry PACs interfere with bacteria’s ability to spread and become virulent.

So let’s all stop fighting about the preferred viscosity of our turkey condiment, and be thankful that the cranberry is a red beacon of hope in our war on drug resistant bacteria.

Posted by CatherineCerasuolo
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November 6, 2017

Crosslinked Polymers Guest Star on The CW's Flash

Elongated Man: Silly Putty Vs. Rubber Band 

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Warning: This blog post contains spoilers from Season 4, Episode 4 of DC Comics/The CW's The Flash.

“Elongated Journey Into Night" introduces Ralph Dibny, a former cop turned private investigator, recently endowed with superhuman stretching abilities by a dark matter bus accident. Dibny doesn't know how to control his newly acquired powers and can't shrink his limbs back to normal after being stretched off a six story building. Team Flash takes Dibny to S.T.A.R. Labs for diagnosis and treatment.

Dr. Harry Wells: The dark matter has polymerized Dibny’s cells.

Dr. Caitlin Snow: You’re saying the walls of every cell in his body have elasticized?

Harry: I’m saying that they’ve formed an unbreakable bond on the atomic level and they stretch these cells and stretch these cells...Like Silly Putty!

CPG scientists, choosing not to take artistic license into account, provide a scientific rebuttal, and anxiously await notification of a writer’s credit from The CW.

CPG's Response

From a molecular structure point of view, Silly Putty is an incorrect analogy, since the crosslinking bonds formed in Silly Putty are transient boron-linkages that readily de-form and reform under extensional deformation, and are hence breakable.

Silly Putty is best described as visco-elastic, having both viscous and elastic properties. If Dibny were truly like Silly Putty, he would eventually settle into a shallow, liquid-like pool due to the viscous behavior of Silly Putty. 

A better analogy for Dibny would be a rubber band, which has covalent bonds which are more permanent, and hence ‘unbreakable’. Rubber bands are primarily elastic, meaning they can stretch but then retain their normal shape once the stress is removed.

More troublesome in this clinical description of Dibny is the idea that his cells have undergone polymerization, which presumably means that each cell has become covalently bonded to another cell. Would this be the case, Dibny would effectively have become a crosslinked system, which would resist, rather than encourage, elastic deformation.

Dibny's Treatment: Crosslinking or Depolymerization?

In an attempt to return Dibny's overextended extremities to regular sizes, Snow synthesizes a crosslinking serum:

Caitlin: Drink this...It’s a serum of sulfur, zinc oxide and steric acid to crosslink your polymerized cells.

Dibny: You did it! I’m cured!!!

Caitlin: Well, not cured. All I did was introduce a stabilizing enzyme to reset your body to default shape through vulcanization.

CPG's Response

Interestingly, none of the serum components described by Caitlin are an enzyme. Stearic acid is a wax-like compound derived from animal and vegetable fats, and would play no role in crosslinking. Zinc oxide would also play no role in crosslinking, but would help Dibny avoid sunburn.

However, the sulfur mentioned is used in vulcanization of rubber, which crosslinks the rubber so that it can be used in tires, so it is sort of in line with Caitlin’s crosslinking statement. However, high temperatures are required for vulcanization (normally in excess of 150°C), so Dibny would have other issues beyond an unusual level of cellular stretchiness.

From the diagnosis above, however, Dibny’s problems are not due to the need for more crosslinking, but rather less crosslinking. So Dibny really needs a depolymerization process. For this, we would recommend either a peroxide-based catalyst, an unhealthy dose of ultraviolet light, a good amount of heat, or lots of mechanical deformation, all of which could cause depolymerization.

Posted by CatherineCerasuolo
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