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WHAT'S HOT IN... CHEMISTRY , Mar./Apr. 2008

Beating Cancers to Death with Nanorods of Gold
by John Emsley
Chemistry Top Ten Papers
Rank   Papers Citations This Period (Sep-Oct 07) Rank Last Period (Jul-Aug 07)
1 X. Huang, et al., "Cancer cell imaging and photothermal therapy in the near-infrared region by using gold nanorods," J. Am. Chem. Soc., 128(6): 2115-20, 15 February 2006. [Georgia Inst. Tech., Atlanta; U. Calif., San Francisco] *014AX 29
2 E.V. Shevchenko, et al., "Structural diversity in binary nanoparticle superlattices," Nature, 439(7072): 55-9, 5 January 2006. [IBM, Yorktown Heights, NY; Columbia U., New York, NY; U. Michigan, Ann Arbor] *999HA 24
3 M.J. Earle, et al., "The distillation and volatility of ionic liquids," Nature, 439(7078): 831-4, 16 February 2006. [Queen’s U. Belfast, U.K.; U. Nova de Lisboa, Portugal; NIST, Boulder, CO] *012JA 22
4 J.L. Rowsell, O.M. Yaghi, "Effects of functionalization, catenation, and variation of the metal oxide and organic linking units on the low-pressure hydrogen adsorption properties of metal-organic frameworks," J. Am. Chem. Soc., 128(4): 1304-15, 1 February 2006. [U. Michigan, Ann Arbor] *007BA 20
5 D. Enders, et al., "Control of four stereocentres in a triple cascade organocatalytic reaction," Nature, 441(7095): 861-3, 15 June 2006. [Aachen U., Germany] *052SL 18 8
6 J.K. Holt, et al., "Fast mass transport through sub-2-nanometer carbon nanotubes," Science, 312(5776): 1034-7, 19 May 2006. [Lawrence Livermore Natl. Lab., Livermore, CA; U. Calif., Berkeley] *043UX 18
7 D.I. Enache, et al., "Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/TiO2 catalysts," Science, 311(5759): 362-5, 20 January 2006. [Cardiff U., U.K.; Lehigh U., Bethlehem, PA] *007AE 18 3
8 G.K. Mor, et al., "Use of highly-ordered TiO2 nanotube arrays in dye-sensitized solar cells," Nano Lett., 6(2): 215-8, February 2006. [Pennsylvania State U., University Park] *015DS 17
9 S.Z. Luo, et al., "Functionalized chiral ionic liquids as highly efficient asymmetric organocatalysts for Michael addition to nitroolefins," Angew. Chem.-Int. Ed., 45(19): 3093-7, 5 May 2006. [Chinese Acad. Sci., Beijing; Nankai U., Tianjin, China] *042MY 15
10 A. Corma, P. Serna, "Chemoselective hydrogenation of nitro compounds with supported gold catalysts," Science, 313(5785): 332-4, 21 July 2006. [U. Polytec. Valencia, Spain] *065IV 15
SOURCE: Thomson Scientific's
Hot Papers Database. Read the Legend.

Nano-sized particles of gold feature in the papers which top and tail the current Hot Ten, offering hope in the treatment of cancer (#1) and a new, environmentally preferred method of industrial synthesis (#10).

Paper #1 comes from a group lead by Mostafa El-Sayed at the Laser Dynamics Laboratory of the Georgia Institute of Technology, in collaboration with his son Ivan El-Sayed, of the Comprehensive Cancer Center of the University of California at San Francisco. It reports the first combined application of the optical and photothermal properties of gold nanorods, whose method of preparation and mode of operation the El-Sayeds have been researching for several years, and which now demonstrate that they can be used in the diagnosis and treatment of cancer.

The gold nanorods are attractive compared to other contrast agents because of the ease of synthesis, their optical tunability, and their absorption in the near infrared (NIR) which allows for in vivo and clinical applications. The nanorods can be incorporated into monoclonal antibodies which bind selectively to the surface of malignant cells. The El-Sayeds have developed simple and unique techniques in cancer imaging and photothermal therapy based on them.

When exposed to light, electrons in the conduction band of a gold nanorod oscillate in a way that resonates with electromagnetic radiation of a frequency that depends on the size and shape of the nanorods. Due to their strong scattering, they are ideal for probing and imaging sites within the body and in particular cancerous growths. Not only are the nanorods ideal for imaging, they are also the right shape for absorbing near-infrared low-energy radiation from a continuous-wave laser and converting this to heat. It is this which offers remarkable benefits.

This localized heating of a gold nanorod is so powerful it can cause it to melt, and even to result in the rapid sublimation of its atoms which may be propelled at jet-speed velocities. These projectiles, and the heating of the associated cancer cell, can lead to its destruction.

Gold nanorods are grown from a dilute solution of auric acid (HAuCl4) to which has been added cetyltrimethylammonium bromide, benzyldimethylhexadecylammonium chloride, a silver salt, and ascorbic acid. The solution is seeded by adding gold nanoparticles smaller than 5 nm. The overall dimension of the nanorods is the key to their success, and this is measured in terms of the aspect ratio, which is the length divided by the width.

This ratio can be varied by changing the concentration of silver ions in the growth medium. It is critical to the way the nanorods absorb and scatter the near-infrared radiation (NIR) to which the tissues are most transparent, and this will be the key to their successful use in medicine. By changing the shape of the nanorods it became possible to change their absorption and scattering wavelengths from the visible to the NIR region.

Recently the El-Sayeds have extended the work in paper #1. In Nano Letters, (see X.H. Huang, et al., 7[6]: 1591-7; 2007), they report that human oral cancer cells are found to assemble and align gold nanorods conjugated to anti-epidermal growth factor receptor (anti-EGFR) antibodies. Molecules on the cancer near the nanorods are found to give a strong, sharp, polarized Raman spectrum which is greatly enhanced and so can be used as diagnostic signatures for these cancer cells. Currently they are doing animal-model experiments using nanorods, and these show great promise.

Gold nanoparticles also appear in the current Hot Ten at #10, which comes from Avelino Corma and Pedro Serna of the Instituto de Tecnologia Quimica at Valencia, Spain. This paper reports their use as catalysts when supported on substrates of titanium oxide or iron(III) oxide, and especially for the reaction of nitroarenes with hydrogen gas.

For example, 3-nitrosytrene undergoes 99% conversion and 96% selectivity to 3-vinylaniline in six hours at 120° C. What is more, there is no formation of the by-product hydroxylamine styrene, and it is the non-formation of this which Corma says gives their discovery commercial significance. The reaction reported in #10 offers an environmentally preferred way to the industrially important chemical cyclohexanone whose production at present involves this undesirable by-product.

Dr. John Emsley is based at the Department of Chemistry, Cambridge University, U.K.



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