Tuesday, November 02, 2010

At the Smallest Scale, Water Is a Sloppy Liquid

Parece ser que día a día encontramos nuevos argumentos que fundamentan el comportamiento impredecible de las moléculas de agua. Nuestro trabajo como químicos es el de intentar explicar ciertos comportamientos moleculares en base a las características de composición molecular, si creíamos que dos pares de electrones sin compartir daban al agua sus singulares características; parece ser que aún nos falta mucho por descubrir sobre esta “simple” molécula. Gracias a que la investigación continua, a mi parecer con la finalidad de no dejar ninguna “laguna” de conocimiento, nos permite seguir teniendo avances científicos. Encontrar las que el agua se comporta de manera distinta a nivel molecular y nos abre un campo para buscar posibles aplicaciones a esta propiedad.

Water may seem like a dull liquid. But at the molecular scale, there's a party going on. New simulations reveal that water molecules actually form two different types of structures that break apart and recombine at lightning speeds. Such complexity just might be the reason why life as we know it sprang forth in a wet environment.

As simple as an individual water molecule is—two atoms of hydrogen bonded with one of oxygen—it forms weak bonds to its neighbors creating more-complex structures. That's allowed it to serve as the medium for the growth and evolution of the most complex molecules in the universe, including enzymes, proteins, and the mother of all known living creatures, DNA. But why water and not, say, hydrogen peroxide or even ammonia? Scientists have been wrestling with this quandary for over a century. Indeed, 5 years ago, Science called this one of the 125 most important unresolved scientific issues.

A new study might have uncovered an essential clue. Researchers used computer models to probe how water molecules form structures, a phenomenon that has resisted visual examination so far. Working with standard desktop computers, the team applied models originally designed to study complex systems, such as the Internet, the spread of viruses, and the folding of proteins, to investigate the configurations of water at the smallest scales.

What the researchers observed, they reported online in The Journal of Physical Chemistry B, is that water molecules bond with one another in a surprisingly complex and dynamic way. Any given volume of water contains two types of molecular structures—one a blobby, loosely packed agglomeration and the other a tight, regular arrangement resembling a crystal lattice. But both structures tend to break apart and recombine frequently, on the order of extremely tiny fractions of a second. The result is a chaotic mix of water molecules. Within that mix, the hydrogen atoms form connections that function like hooks, onto which carbon or nitrogen atoms can presumably grab to form the beginnings of complex organic molecules. And the process can dramatically influence the motion of even more-complex biological systems, such as proteins, by helping their assembly. As far as anyone knows, no other liquid demonstrates this property.

The finding introduces "a framework to understand how water with its [hidden structure] influences protein function at the fundamental level," says physicist and co-author Francesco Rao of the University of Freiburg in Germany. The models present a "very crude" first look at these structures, adds physical chemist and co-author Peter Hamm of the University of Zürich in Switzerland. "It is becoming clearer and clearer," he says, that "water is more than just a solvent, but actually an integral part of the functional structure of proteins."

It's "a fascinating and provocative paper," says physical chemist James Skinner of the University of Wisconsin, Madison. The study, he says, helps to illuminate subtle but important details about molecular motions in water.

The demonstration by a computer model that water exists in two different microscopic constructions is a "wonderful discovery," adds physicist H. Eugene Stanley of Boston University. Although earlier laboratory experiments have suggested this possibility, he says, the authors are the first to model the process in detail. It's a step toward unraveling why this liquid can produce 15 types of ice, for example. More important, Stanley says, "We will never understand biology until we understand water."

Berardelli, P. (8 de Octubre de 2010). Science Now. Recuperado el 2 de Noviembre de 2010, de http://news.sciencemag.org/sciencenow/2010/10/at-the-smallest-scale-water-is-a.html?ref=hp

Química a Todas Horas: Manera Correcta de Servir Champagne

Un grupo de científicos franceses se dieron a la investigación sobre la mejor manera de mantener espumoso el champagne a la hora de servirlo. Aparentemente mantener la botella un poco inclinada y la temperatura baja, llevan a un champagne más espumoso.

La investigación consistió primordialmente en comparar la cantidad de dióxido de carbono disuelto en el champagne cuando se sirve a una copa sostenida de manera vertical a comparación de servir el champagne auna copa ligeramente inclinada. El contenido de CO2 en la copa inclinada era 8% mayor al encontrado en la copa sostenida de manera vertical. Así mismo se encontró que la perdida de CO2 del champagne era menor si la temperatura era disminuida.´

Aún cuando la respuesta a la pregunta ¿Cuál es la mejor manera de servir champagne? parezca un poco obvia, esta es la primera vez que se comprueba de manera experimental las razones por las cuales esto sucede y una comprobación completa mente justificada es obtenida.

El artículo puede ser encontrado en la siguiente liga:

Krishnaswamy, D. J. (11 de Agosto de 2010). Science Now. Recuperado el 2 de Noviembre de 2010, de http://news.sciencemag.org/sciencenow/2010/08/scienceshot-how-to-pour-champagne.html?ref=hp

Los resultados exhaustivos de la investigación realizada se encuentran en la siguiente liga:

Liger-Belair, G., Bourget, M., Villaumert, S., Jeandet, P., Pron, H., & Polidori, G. (13 de Julio de 2010). ACS Publications. Recuperado el 2 de Noviembre de 2010, de Journal of Agricultural and Food Chemistry: http://pubs.acs.org/stoken/presspac/presspac/full/10.1021/jf101239w

Cosméticos Egipcios con Altos Contenidos en Plomo

Descubrimientos interesantes sobre la utilización de plomo en cosméticos utilizados por los egipcios, han hecho que los científicos se cuestionen sobre la fuerte creencia de que todo el plomo en el cuerpo lleva a severas intoxicaciones. Aparentemente, los egipcios no sólo utilizaban delineador de ojos con propósitos de belleza (al igual que se hacía en otras culturas) si no que también, los preparaban con sales especiales de plomo con la finalidad de evitar infecciones de ojos. No obstante, hoy en día sabemos el gran peligro que representa el plomo. Investigadores hicieron pruebas con la finalidad de descubrir si había algún error en nuestra teoría actual sobre el plomo. Los resultados indicaron que la liberación de oxido nítrico por la piel llevara a células blancas a atacar ciertas infecciones de ojos; así que era cierto, las sales en plomo les ayudaban sanar infecciones de ojos. Si estas planeando añadir sales de plomo a tu delineador te aconsejo que llegues al final del artículo, donde se indica que los egipcios no llegaban a mas de los 30 años y aún cuando lo hubieran hecho, la alta exposición al plomo los hubiera acabado poco a poco. Espero que disfruten el artículo.

Egyptian Eyeliner May Have Warded Off Disease
Clearly, ancient Egyptians didn't get the memo about lead poisoning. Their eye makeup was full of the stuff. Although today we know that lead can cause brain damage and miscarriages, the Egyptians believed that lead-based cosmetics protected against eye diseases. Now, new research suggests that they may have been on to something.

Previous work indicates that the Egyptians added lead to their cosmetics on purpose. When analytical chemist Philippe Walter and colleagues at CNRS and the Louvre Museum in Paris analyzed the composition of several samples of the Egyptians' famous bold, black eyeliner in the Louvre's collection, they identified two types of lead salt not found in nature. That means that ancient Egyptians must have synthesized them. But making lead salt is a tricky, delicate process that requires tending for weeks--and unlike other common makeup components, the salts are not glossy. So why did they bother?

Ancient manuscripts gave the scientists a clue. It turns out that in those days, people made lead salts and used them as treatments for eye ailments, scars, and discolorations. When Walter told analytical chemist Christian Amatore of the Ecole Normale Supérieure in Paris about the findings, Amatore says he was intrigued because lead is now known to have so many toxic effects.

To see if the lead might confer any health benefits, Amatore, Walter, and colleagues added lead salts to human skin cells called keratinocytes, which were grown in the lab. The researchers hypothesized that the lead would stress the cells and cause them to make hydrogen peroxide, nitric oxide, and other compounds involved in the body's immune response. And indeed, cells treated with lead began pumping out more nitric oxide than did control cells, the team reports online in Analytical Chemistry.

Amatore says that nitric oxide sets off a series of biochemical processes in the body that ultimately send immune cells called macrophages to the site of infection, where they engulf invading organisms. That's probably not what's happening in keratinocytes, says immunologist Martin Olivier of McGill University in Montreal, Canada, who was not involved in the study. It's unlikely that macrophages or other immune cells would exit the body and burst through the skin to fight off infectious agents at the surface, he notes. Instead, nitric oxide released by keratinocytes could directly kill eye-disease-causing bacteria on the skin or near the eye by breaking down a bacterium's structure or DNA. Another plausible scenario, says Olivier, is that lead itself could directly stimulate immune cells already present in the eyelid.

This potential benefit of lead is contrary to everything we know about the substance, but it could fit the model of hormesis, says epidemiologist Jennifer Weuve of Rush University Medical Center in Chicago, Illinois. "The premise behind hormesis is that, for certain exposures, there might be a window where the exposure is harmful but also one where it's helpful," she explains.

Still, Weuve cautions against adding lead to the eyeliner in your makeup case. Modern people live a lot longer than did the ancient Egyptians--many of whom died in their 30s--and the dangers of prolonged lead exposure outweigh any antimicrobial benefit, she says. Indeed, the Egyptians' eyeliner strategy would have backfired on them if they had lived long enough, she notes, as long-term exposure to lead may increase the risk of developing cataracts.

Cottingham, K. (8 de Enero de 2010). Science Now . Recuperado el 2 de Noviembre de 2010, de http://news.sciencemag.org/sciencenow/2010/01/08-01.html?ref=hp

Tela Fenomenal: ¿Cómo una tela puede limpiar desechos tóxicos?


Tela "común y corriente" puede usarse para filtrar y destruir materiales increíblemente tóxicos, incluso cuando sólo están presentes en pequeñas cantidades, de acuerdo con una nueva investigación en la Universidad de Abertay Dundee.
El grupo de investigación encontró que una tela de carbón activado puede ser usada para crear químicos extremadamente reactivos llamados radicales hidroxilo. Estos son tan inestables que reaccionan instantáneamente con contaminantes, incluso en concentraciones muy pequeñas.

Este barato material podría ser usado a escala pequeña e hospitales para filtrar desperdicios, o a escala masiva para remover químicos difíciles de detectar que matan bacterias esenciales en nuestro sistema de agua y arriesgan la salud humana.

La investigación fue publicada recientemente en el diario Water, Science & Technology.

Rashmi Chand, Raul Molina, Ian Johnson, Anna Hans, David H Bremner. Activated carbon cloth: a potential adsorbing/oxidizing catalyst for phenolic wastewater.Water Science & Technology, 2010; 61 (11): 2817 DOI:10.2166/wst.2010.091
University of Abertay Dundee (2010, November 2). Phenomenal fabric: How can a cloth clean up toxic waste?. ScienceDaily. Retrieved November 2, 2010, from http://www.sciencedaily.com/releases/2010/11/101102124424.htm


Captura de CO2


La habilidad de mantener el CO2 fuera de la atmósfera para ayudar a prevenir el calentamiento climático es un asunto global. El reto es utilizar materiales que puedan capturar el CO2 y liberarlo fácilmente para almacenamiento permanente. Los investigadores de la Universidad de Calgary y de Ottawa nos proveen de una vista más profunda al "ver" los sitios exactos en los que se contiene el CO2 en un material de captura. Su descubrimiento, publicado en el diario Science, permitirá que los científicos diseñen mejores materiales para así capturar más CO2. Lo que encuentren puede ayudar a aprender cómo se puede mejorar el desempeño.

La investigación puede utilizarse para una gran variedad de aplicaciones. "Podríamos llegar a ver que este proceso ayude a mitigar las emisiones de gases invernadero o para remover CO2 de reservas no convencionales de gas natural," dice el Dr Ramanathan Vaidhyanathan, el autor principal del artículo e investigador asociado en la universidad de Calgary.

Fuente: Universidad de Calgary

Binary Boron-Rich Borides of Magnesium: Single-Crystal Investigations and Properties of MgB7 and the New Boride Mg5B44


Single crystals of dark-red MgB7 were grown from the elements in a Cu-melt. The crystal structure (Pearson symbol oI64; space group Imma; a = 10.478(2) Å, b = 5.977(1) Å, c = 8.125(2) Å, 2842 reflns, 48 params, R1(F) = 0.018, R2(I) = 0.034) consists of a hexagonal-primitive packing of B12-icosahedra and B2-units in trigonal-prismatic voids. According to the UV−vis spectra and band structure calculations MgB7 is semiconducting with an optical gap of 1.9 eV. The long B−B distance of 2.278 Å within the B2-unit can be seen as a weak bonding interaction. The new Mg5B44 occurs beside the well-known MgB12 as a byproduct. Small fragments of the black crystals are dark-yellow and transparent. The crystal structure (Pearson symbol tP196, space group P41212, a = 10.380(2) Å, c = 14.391(3) Å, 4080 reflns, 251 params, R1(F) = 0.025, R2(I) = 0.037) is closely related to tetragonal boron-II (t-B192). It consists of B12-icosahedra and B19+1-units. With a charge of −6 for the B19+1-units and a Mg-content of 20 Mg-atoms per unit cell the observed Mg content in Mg5B44 is quite close to the expected value derived from simple electron counting rules. All compositions were confirmed by EDXS. The microhardness was measured on single crystals for MgB7 (HV = 2125, HK = 2004) and MgB12 (HV = 2360, HK = 2459).

Photoinduced Electron Transfer from Tryptophan to RuIITAP Complexes: The Primary Process for Photo-Cross-Linking with Oligopeptides


The photoreaction mechanism of [Ru(TAP)2(phen)]2+ and [Ru(TAP)3]2+ (TAP = 1,4,5,8-tetraazaphenanthrene) with tryptophan (Trp), N-acetyl-Trp, and Lys-Trp-Lys is examined. The existence of a photoelectron-transfer process from the amino acid unit is demonstrated by laser flash photolysis experiments. The back electron transfer (BET) from the reduced complex to the oxidized amino acid, occurring at the microsecond time scale, corresponds approximately to an equimolecular−bimolecular process; however, it is disturbed by another reaction, originating from the oxidized Trp. Moreover, in competition with the BET, the reduced and oxidized intermediates give rise to an adduct. The latter is clearly detected by gel electrophoresis experiments in denaturing conditions, with a system composed of an oligonucleotide derivatized at the 3′ end by the RuIITAP complex and hybridized with the complementary sequence functionalized at the 5′ end by the tripeptide Lys-Trp-Lys. Thus, upon illumination, a cross-linking between the two strands is observed, which originates from the presence of a Trp residue.

http://pubs.acs.org/doi/full/10.1021/ic101214m

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