n e w s of t h e w e e k sociate professor of chemistry at the University of Missouri, Columbia. "The idea needs to be tested, of course, but it opens up many options." Robert J. Hamers, professor of chemistry at the University of Wisconsin, Madison, says the work of Bent and Doren is "especially noteworthy" in that it puts on very firm footing the notion that all types of cycloaddition reactions may be used to form well-defined silicon-organic interfaces. And unlike the harsh conditions or heoreticians in Delaware predicted The calculations were conducted by long reaction times of other methods it; experimentalists in New York Douglas J. Doren, associate professor of used to deposit organic layers on semiproved it. "It" refers to the ability of chemistry at Delaware, and graduate stu- conductors, "some cycloaddition reacpairs of silicon atoms on a solid silicon sur- dent Robert Konecny. Assistant profes- tions have been shown to give nicely orface to react with butadiene or other sor Stacey F. Bent, postdoctoral research- dered interfaces right off the b a t dienes in organic chemistry's classic Diels- er Andrew V. Teplyakov, and graduate without heating," Hamers adds. He has Alder reaction. This type of reaction might student MaynardJ. Kong of NYU's chem- investigated the mechanism and stereobe used to prepare microelectronic devic- istry department performed the experi- chemistry of the surface analog of [2+2] cycloaddition reactions—the ones leades or to synthesize materials with custom- mental work. ing to formation of four-membered rings ized nonlinear optical properties. I find the work interesting for two Using first-principles-type calculations, reasons," Doren says. "First, theoretical \J. Phys. Chem. B, 101, 1489 (1997)]. "The work is certainly exciting in researchers at the University of Delaware, methods predict the reaction will run efNewark, showed that the Diels-Alder ficiently on this surface—and that predic- terms of the variety of reactions that [4+2] cycloaddition reaction—long associ- tion has been confirmed with experi- might be used to modify surfaces," Bent ated with solution-phase chemistry- ment. And second, this shows that sur- notes. "But conceptually it's also very incould be applied to the reaction of gas- face modifications may be done using teresting because now you can view siliphase 1,3-diene molecules with a surface surface analogs of standard organic reac- con as a big molecule and think about of silicon capped with silicon dimers to tions. Now you can think about applying the chemistry on its surface in traditional form stable six-membered rings \J. Am. traditional methods of organic synthesis organic terms." to designing surfaces or interfaces with Chem. Soc, 119, 11098 (1997)]. Mitch Jacoby Working independently, chemists at technologically useful properties." New York University verified that the inThe cycloaddition reaction leaves the dicated reaction proceeds as predicted, surface coated with a layer of sixnoting excellent agreement between the membered rings. The rings are each comcalculated and measured vibrational posed of two silicon atoms and four spectrum of the product material \J. Am. carbon atoms. As is the case with the textbook version of the Diels-Alder reaction, Acting on recommendations of his advisoChem. Soc, 119, 11100 (1997)]. the product mole- ry panel just days before Veterans Day, cules contain a C-C President Bill Clinton announced a suite of double bond. programs to ferret out the causes of illDiels-Alder reaction forms six-membered nesses of some Persian Gulf War veterans. "The Diels-Alder ring on silicon surface The President will have the National reaction may be used as a starting point for Academy of Sciences review all ongoing subsequent surface research on Gulf War illnesses. He plans chemistry," Bent to allocate an additional $13.2 million for points out. "It's con- new research on low-level exposure to ceivable that a second chemical warfare (CW) agents and to and third Diels-Alder other environmental factors that troops reaction may be done may have been exposed to during their on top of the first lay- service in the gulf area. All Defense Deer" owing to the partment CW agent research must be product layer's alkene completed by September 1998. functionality, she Implementing a key recommendation says. of the Presidential Advisory Committee "Essentially, any on Gulf War Veterans' Illnesses' final reunsaturated hydro- port, Clinton has called on former New Gas-phase butadiene reacts with a silicon surface to form carbon reaction you Hampshire Sen. Warren B. Rudman to the [4+2] cycloaddition product. The six-membered ring incan think of is now a head an oversight board whose other cludes two silicon atoms and four carbon atoms. The reactive surface, Si(100)-2xl, consists of rows of doubly bondpossibility on that members have yet to be named. The ed silicon dimers that serve as dienophiles. surface," remarks C. board's function will be to hold the DeMichael Greenlief, as- fense Department to "the highest stan-
DIELS-ALDER APPLIED TO SILICON SURFACE Classic organic chemistry reaction usefully modifies silicon surfaces
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Gulf War panel advises, Clinton acts
4 NOVEMBER 17, 1997 C&EN
Lashof: sustained effort needed
dards" in its investigations into the caus es of the so-called Gulf War syndrome, Clinton explained. Filling a gap in the current medical record-keeping practices of the Pentagon and the Department of Veterans Affairs (VA), the President has created a Force Health Protection Program. It is to en sure that a comprehensive record is kept of all illnesses and injuries suffered and all care and treatment received by all ser vice personnel. Another of the panel's main recom mendations calls for a statutory program to ensure continued attention to the problems of Gulf War veterans. Panel Chairwoman Joyce C. Lashof says her panel hopes the recommendation will set "in motion a process—both in and outside government—to sustain current interest in resolving the uncertainties sur rounding this difficult issue." Acting on this advice, Clinton has set up a new sys tem to ensure appropriate care and ben efits for the veterans. He intends to work with Congress to get legislation enacted that will ensure continuation of this ben efits system by future administrations. For the most part, the advisory panel is fairly laudatory about the progress the Pentagon and VA have made in imple menting many of its earlier recommenda tions (C&EN, Sept. 29, page 21). But the panel still faults the Pentagon for its "superficial" investigations into possible CW incidents, saying these investigations are unlikely to overcome suspicions of a cover-up. To regain some credibility, the panel recommends that all government-funded research be subjected to external compe
tition and to independent peer review. The sole exceptions are small, shortterm, narrowly focused projects that can be done only by specific researchers. But even the protocols for these should be peer reviewed, the advisory panel insists. The panel again calls on the Pentagon to adopt an objective standard against which all future investigations of possi ble CW agent exposures can be scruti nized. Now, the panel contends, the Pen tagon's use of "a subjective decision making process" in lieu of an objective standard only serves to undermine the Pentagon's credibility. Earlier this month, the House Com mittee on Government Reform & Over sight's Subcommittee on Human Re sources issued a report sharply critical of the Pentagon's research efforts into the causes of Gulf War syndrome (C&EN, Nov. 3, page 17). The report called for an independent panel of "expert scien tists to oversee how research dollars are spent. We're not talking about former Congressmen or military [officers]," ex plains subcommittee spokesman Robert A. Newman. Lois Ember
Engineering firms join to pursue ethylene plants Faced with growing competition and a worldwide glut of the ethylene and ethyl ene derivative plants they build, engineer ing and construction giants Fluor Daniel of Irvine, Calif., and Stone & Webster of Bos ton have joined forces to pursue ethylene plant construction contracts. Until they settle on a final name, the partners are calling their Houston-based 50-50 joint venture Stone & Webster/ Fluor Daniel Petrochemical. It links Fluor Daniel's process facility design and pro gram management strengths with Stone & Webster's proprietary ethylene and downstream derivatives technologies. "Our clients around the world will ben efit from operational and financial en hancements, faster schedule completions, and lower installed costs of their projects," says Fluor Daniel President Jim Stein. The partners offer better responsiveness and project implementation than if they com peted separately, adds Stone & Webster Chairman and Chief Executive Officer H. Kerner Smith. The new engineering entity faces at
least a few difficult years. Asia, site of many new ethylene projects, is undergo ing a financial upheaval that could delay many planned projects. And world petro chemical markets are headed into a down turn, according to Tarrytown, N.Y.-based consultants Chem Systems, which says, "Currently, petrochemical margins and prices are falling as new capacity comes onstream." Demand will catch up with supply by 2000 with the next peak in the 2002-03 period, forecasts Chem Systems. Meanwhile, the venture will encoun ter competition for available projects from outfits such as ABB Lummus Glo bal, Bloomfield, N.J., and its Japanese partner Toyo; Brown & Root, Houston, and its two partners, ΚΉ of the Nether lands and Mitsui of Japan; Bechtel, Hous ton, and its German partner Linde; and M. W. Kellogg and its Japanese partner Chiyoda. Michael A. Pears, formerly a Stone & Webster processing group vice president and marketing director, is president of the new firm, which starts with a core operating group of about 30 employees. A spokesman says the company will draw additional personnel from its own ers, who retain their respective engineer ing businesses, as they are needed. Marc Reisch
Contractor selection for Brookhaven Lab stalls Selection of a new contractor to operate Brookhaven National Laboratory, in Up ton, N.Y., is being put off until early next year. A decision was expected Nov. 17. Two groups have bid for the chance to oversee the $400 million operation and collect a $4 million annual fee. Energy Secretary Federico Pefia blamed the delay on a provision in DOE's fiscal 1998 appropriation bill that re quires competitive bids on DOE con tracts. Department attorneys believe the Brookhaven bidding process is not in compliance with that provision because it requires that the primary contractor be a nonprofit organization. The provision, however, allows Pena to waive its terms but only after a 60-day waiting period, which would put off award of the contract until Jan. 5. House Appropriations Committee staff disagrees with DOE's interpretation, how ever, and says the provision does not block the contract award. DOE spokes men stuck to their guns, saying DOE reNOVEMBER 17, 1997 C&EN 5
