Iridium immobilization

A similar type of immobilization was obtained by reacting the phosphonylated 2,2 -bipyridine ligand depicted in Figure 42.10 with excess titanium alkoxide. Rhodium and iridium complexes of this immobilized ligand showed activity for... 

The preparation of polymer-supported iridium catalysts (61) and (62) for the stereoselective isomerization of double bonds using polystyrene based immobilized triphenyl phosphine were recently reported by Ley and coworkers (Fig. 4.5). The immobilized catalyst is potentially useful for deprotection strategies of aUyl ethers [130]. 

Scientists at Huddersfield University in collaboration with Avecia have developed a DKR process involving the combination of immobilized Candida rugosa lipase and an iridium-based racemization catalyst (Scheme 2.30). By using carbonate 62 as the acyl donor, the racemic secondary amine 61 was converted to the corresponding carbamate (R)-63 in high yield and enantiomeric excess [32]. 

Abstract Pressure-sensitive paint (PSP) is applied to the areodynamics measurement. PSP is optical sensor based on the luminescence of dye probe molecules quenching by oxygen gas. Many PSPs are composed of probe dye molecules, such as polycyclic aromatic hydrocarbons (pyrene, pyrene derivative etc.), transition metal complexes (ruthenium(II), osumium(II), iridium(III) etc.), and metalloporphyrins (platinum (II), palladium(II), etc.) immobilized in oxygen permeable polymer (silicone, polystyrene, fluorinated polymer, cellulose derivative, etc.) film. Dye probe molecules adsorbed layer based PSPs such as pyrene derivative and porphyrins directly adsorbed onto anodic oxidised aluminium plat substrate also developed. In this section the properties of various oxygen permeable polymer for matrix and various dye probes for PSP are described. 

The intense and long-lived luminescence of these complexes has been utilized in the development of the oxygen sensor. Four mononuclear and dinuclear cyclometalated iridium(III) diimine complexes were immobilized in polymerized poly(ethylene glycol) ethyl ether methacrylate matrices, and the oxygen quenching on the luminescence of the films was studied. Tinear Stem-Vohner plots were obtained. Despite the difference in the luminescence energy and lifetimes of the complexes, similar Stem-Volmer slopes were observed. The size and charge of the complexes played an important role in the sensitivity of the systems. 

In the Ir-AljOa system migration does not play a role in crystallite growth when heating in an oxygen environment above 713 K. Sintering was inhibited by BaO, CaO, and SrO up to 923 K oxidative stabilization of iridium crystallites is consistent with the formation of an immobile surface iridate by reaction between a mobile molecular iridium oxide species and the well dispersed Group IIA oxide. 

While the majority of enzyme electrodes fabricated have been rather large devices, there have been some recent reports concerning the development of miniaturized and even microsensors. For example, MeyerhoflF (M5) prepared an essentially disposable urea sensor (tip diameter 3 mm) by immobilizing urease at the surface of a new type of polymer-membrane electrode-based ammonia sensor (see Fig. 4). Alexander and Joseph (Al) have also prepared a new miniature urea sensor by immobilizing urease at the surface of pH-sensitive antimony wire. Similarly, lannello and Ycynych (II) immobilized urease on a pH-sensitive iridium dioxide electrode. In these latter investigations, ammonia liberated from the enzyme-catalyzed reaction alters the pH in the thin film of enzyme adjacent to the pH-sensitive wire. 

II. lanniello, R. M., and Yacynych, A. M., Urea sensor based on iridium dioxide electrodes with immobilized urease. Anal. Chhn. Acta 146, 249-253 (1983). 

Other pH-sensing transducers used in biosensors are metal oxide electrodes. Beside the common antimony oxide electrode, palladium oxide and iridium oxide probes have been coupled with immobilized enzymes. These sensors may be miniaturized by using chemical vapor deposition technology. Moreover, they are mechanically more stable than glass electrodes. Unfortunately the measuring signal of metal oxide electrodes is affected by redox active substances. 

The same reaction system, immobilized on porous glass, has been used by Winquist et al. (1986) in two reactors combined with an ammonia sensitive iridium metal oxide semiconductor structure in an FLA system. NH3 up to 0.2 mmol/1 could be completely removed in the glutamate dehydrogenase reactor. 

Many fluorescence sensors are based, not on direct fluorescence, but on the quenching of fluorescence. Molecular oxygen, for example, is one of the best col-lisional quenchers. Oxygen can quench the fluorescence from polycyclic aromatic hydrocarbons complexes of ruthenium, osmium, iridium, and platinum and a number of surface-adsorbed heterocyclic molecules. An oxygen sensor can be made by immobilizing the fluorophore in a thin layer of silicone on the end of a fiber-optic bundle. Sensors for SO-, haliilcs, H-O-, and several other molecules have been ba.sed on fluorescence quenching. 

Use of the immobilized iridium double-bond isomerizing catalyst (70) developed for the carpanone synthesis again worked well to convert commercially available 73 to the conjugated product (74). This was then methylated in the presence of PS-BEMP (7), a reaction that proceeds in almost quantitative yield. Next, an asymmetric dihydroxylation was performed according to methods developed by Sharpless. However, instead of using a conventional workup procedure for the vicinal diol (75), a new catch-and-release protocol was developed. This made use of the immobilized boronic acid (76) to trap the chiral diol... 

Itsimo [25] has also shown that polymer-supported OPEN monosulfonamides containing sulfonated pendent group (Scheme 16) are able to catalyze the HTR reduction of ketones in water with sodium formiate as hydrogen donor (S/C = 100). However, TsDPEN immobilized on polystyrene crosslinked or not, polymer 30 and 31 respectively, shrank in water. Sodium /j-styrene sulfonate was copolymerized with chiral A-(vinylbenzene-p-sulfonyl)-DPEN (20) imder radical polymerization conditions with or without DVB leading respectively to ligand 32 and 33. Control of the balance hydrophilicity/hydrophobieity of the polymer support is carried out by changing the salt from Na to quaternary ammonium. All of these polymers swelled in water, and their respective ruthenium, rhodium or iridium complexes were prepared. Compared to sodium salt polymer-supported catalyst from 32a and 33a, ammonium... 

---