Bimetallic nanoparticles (Ru(6)Pd(6), Ru(6)Sn, Ru(10)Pt(2), Ru(5)Pt, Ru(12)Cu(4), and Ru(12)Ag(4)) anchored within silica nanopores exhibit high activities and frequently high selectivities, depending upon the composition of the nanocatalyst, in a number of single-step (and often solvent-free) hydrogenations at low temperatures (333-373 K). The selective hydrogenations of polyenes (such as 1,5,9-cyclododecatriene and 2,5-norbornadiene) are especially efficient. Good performance is found with these nanoparticle catalysts in the hydrogenation of dimethyl terephthalate to 1,4 cyclohexanedimethanol and of benzoic acid to cyclohexanecarboxylic acid or to cyclohexene-1-carboxylic acid, and also in the conversion of benzene to cyclohexene (or cyclohexane), the latter being an increasingly important reaction in the context of the production of Nylon. Isolated atoms of noble metals (Pd, Rh, and Pt) in low oxidation states, appropriately complexed and tethered to the inner walls of nanoporous (ca. 3 nm diameter) silica, are very promising enantioselective hydrogenation catalysts. Nanoporous carbons, as well as other nanoporous oxides, may also be used to anchor and tether the kind of catalysts described here.
Extensive chemical, spectrophotometric, and x-ray structural studies have shown that trivalent rhenium is strongly homophilic-that is, it tends to form bonds to other Re(111) atoms-and it forms at least three different series of [ReX(4)](n)(n-) complexes. The mononuclear, square complex, [ReBr(4)](-), adds two water molecules to give trans-[ReBr(4)(H(2)O)(2)](-). The binuclear complexes [Re(2)Cl(8)](2-) and [Re(2)Br(8)](2-) have strong Re-Re bonds, unsupported by halide bridges. The trinuclear species, [Re(3)X(12)](3-) or Re(3)X(9)L(3), contain the triangular Re(3)X(9) clusters. Use of ReCI(3) appears always to lead directly to products containing Re(3)Cl(9); this unit exists in ReCl(3) itself and does not appear to be kinetically labile. The [Re(2)X(8)](2-) ions are obtained by reduction of ReO(4)(-) in aqueous HCl or HBr. Salts of [ReBr(4)(H(2)O)(2)](-) can be obtained directly from solutions of ReBr(3) in HBr along with numerous other compounds, some containing trinuclear clusters.
This study investigated changes in the deep venous system and the development of the postthrombotic syndrome (PTS) after an episode of acute deep vein thrombosis (DVT). Methods: Seventy-eight patients (41 male patients, 37 female patients) with acute DVT in 83 legs (31 right, 42 left, five bilateral) underwent annual follow-up examinations for 1 to 6 years (median, 3 years) for symptoms and signs of the PTS. A venous duplex scan was performed at each visit to detect obstruction and reflux in the veins, both of which may contribute to the development of the PTS. DVT was primal, in 69 limbs and recurrent in 14 limbs. Results: When last examined 49 limbs were free of symptoms, and 34 had the PTS (23 edema only, 11 hyperpigmentation). Only two patients had ulcers during the follow-up period; both patients had the ulcers in areas of hyperpigmentation in limbs with recurrent DVT. The extent of disease was similar in limbs with the PTS (79% multisegment, 18% single segment) and those without the PTS (69% multisegment, 12% single segment). In limbs with the PTS the deep veins were normal in only one (3%), six (18%) showed reflux only, five (15%) obstruction only, and 22 had features of both obstruction and reflux (65%). In limbs without the PTS the deep veins showed no abnormality in nine (18%), reflux only in 17 (35%), obstruction only in six (12%), and reflux with obstruction in 17 (35%). In the 11 limbs with hyperpigmentation nine had obstruction and reflux noted, one had obstruction only, and one had reflux alone. Conclusions: After an episode of acute DVT 12% of the limbs returned to normal by duplex criteria. Although only 13% developed skin complications, 41% had features of the PTS. Limbs with the PTS had more than three times the odds of having combined reflux and obstruction than did limbs without the PTS (odds ratio -3.5, 0.95 confidence intervals = 1.4, 8.6). Continued study of these patients will determine the course of those limbs with venous abnormalities that have not yet developed symptoms and signs of the PTS.
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