High-throughput catalyst screening

High-throughput methods have revolutionized how the biotechnology and pharmaceutical industries screen for potential drug targets; however, the use of such methods for discovering catalysts in organometallic systems has lagged behind. Completely random libraries are not desirable in organometallic research because only a few compounds have properties that are suitable for catalysis, making the hit rate extremely low. One way to enhance the number of hits is to generate smaller more focused libraries. Kevin Burgess and co-workers at Texas A&M University describe an approach for doing just that based on divergent solution-phase ligand syntheses. They demonstrate how such syntheses when combined with highthroughput screening improve the efficiency of asymmetric catalyst discovery Divergent ligand synthesis involves the production of a large amount of a key optically pure material, from which many ligands are then prepared. In this case, the authors prepared a diverse set of phosphine oxazoline ligands via divergent syntheses involving the intermediate, phosphinesubstituted amino alcohol. The ligands are evaluated in parallel under various reaction conditions using a sim-

Apparatus for running catalytic reactions in parallel. The U-shaped channel allows for circulation of cooling fluid.

pie apparatus consisting of an aluminum block with 34 holes, each capable of holding a 1.1-mL microtube reaction vessel. Metal salts and other insoluble materials are weighed into the appropriate vessels, and aliquots of standard solutions of the soluble ligands, reagents, and additives are added. Reaction vessels are capped, and the block is placed on a 96-well microplate shaker. The reactions are monitored by TLC and, after a designated time, are filtered and analyzed by HPLC using a chiral stationary phase. The use of an autosampler is found to greatly

reduce the analysis time relative to traditional sequential approaches. Several parameters are varied in an attempt to discover and optimize the catalyst systems. Because not all variables are independent, the authors sometimes use a "twodimensional" screen (e.g., enantiomeric excess is evaluated as a function of both the solvent and ligand substituent). The ligandto-metal ratio is found to be a most critical variable, with enantioselectivity dropping and eventually reversing at ratios >1:1. (J. Am. Chem. Soc. 1199 120 9180-87)

Etching tin oxide film

Plasma display panels traditionally have relied on the use of indium tin oxide as the transparent electrode material; however, less expensive tin oxide would be preferable. The problem is that tin OXlde is difficult to etch because of its high chemical stability. Etching methods based on complicated electrochemical processes that involve the reduction of tin oxide to Sir* have been previously reported; such systems, however, require additional cells for the removal of Sir+ from the electrolyte solution. Y. Matsuo, K. Hashimoto, and Y. Sugie of Himeji Institute of Technology and T Nakamura and J Tsunoda of Joyo Company (both in Japan) describe a much simpler electrochemical reduction for micromachining tin oxide that does not require 'in addition'il redox couple Tin oxide film (200-nm thickness) is deposited on a glass plate and serves as the working electrode, and the counter electrode is a platinum wire. Electrochemical etching is performed by the galvano-

static method using three different approach esspot machining with a stationary electrode (both the substrate and the platinum cathode are fixed), line machining with a microscanning electrode (the gap between the platinum wire and substrate is fixed and the substrate is scanned), and line machining with a resistance coating (the substrate is photolithographically patterned and then etched). Etching is performed in HC1, HNO!, NaNOi, NaOH, NaCl, and HL,SO solutions of varying concentration (0.01-1 M), and the electrolyte concentra tion/type electrode gap (0.1-0.3 mm) etching time (1-2 s) and current density optimized High resolution is achieved with an electrode gap of 0.1 mm in 0.1 M neutral or basic solution at high current density (5 A/cm2) and short electrolysis time (1 s). In addition, highresolution results when the substrate is photo lithographically patterned with five parallel straight lines (0.02-1 mm widths) and the Apparatus for etching tin oxide film. platinum plate serves as the counter electrode (Adapted with permission. Copyright 1998 (J. Elcctrochem. Soc. 1998, 145,3(Xi7-69) the Electrochemical Society.)

Analytical Chemistry News & Features, November 1, 1998 701 A