(i) In vivo CRS was validated as a technique to measure SC thickness on both palmoplantar and, particularly, on nonpalmoplantar skin sites. (ii) Moisturizers improve skin moisturization but in this study only formulation A improved SC thickness, water gradients and hydration as measured by CRS. We hypothesize that this was due to compositional differences between the products. We believe that niacinamide (nicotinamide, vitamin B(3)) is probably contributing significantly to this effect, as it has been proven to increase epidermal lipogenesis and SC barrier function in other studies. These results show that by using CRS, we were able for the first time to determine the effect of moisturizer on multiple SC barrier endpoints including SC thickness, and water content as a function of depth and total SC water content.

Thermolysis of Ru 2 (CO) 6 (µ-PPh 2 )(C 2 Bu t ) (1) in toluene afforded Ru 4 (CO) 9 (µ-PPh 2 ) 2 (C 2 Bu t ) 2 (2) in which the acetylide ligands are coordinated to a novel 64-electron butterfly platform. Upon thermolysis, this complex underwent C-C bond coupling to give the diyne complexes Ru 4 (CO) 8 (µ-PPh 2 ) 2 (C 4 Bu t 2 ) (3) and Ru 3 (CO) 7 (µ-PPh 2 ) 2 (C 4 Bu t 2 ) (4) through sequential CO elimination and fragmentation, respectively.The coupling of terminal or functionalized metal acetylides via methodologies such as oxidative 1 or Cadiot-Chodkiewicz 2 coupling has been extensively exploited recently to generate polycarbon ligand complexes and new molecular materials possessing extended carbon unsaturation. 3 In principle, it should be possible to effect head-to-head or tail-to-tail linkage of acetylides or polyacetylides coordinated in a multisite fashion on a binuclear or cluster framework to synthesize new multimetallic polycarbon complexes in which the full potential of σ-and π-electrons of the alkynyl fragments are used in bonding. This strategy has as yet been little exploited in organometallic chemistry. 4 In this communication, we describe the stereospecific high-yield head-to-head intermolecular coupling of µ-η 1 : η 2 -alkynyl groups in Ru 2 (CO) 6 (µ-PPh 2 )(CtCBu t ) 5 (1) molecules to produce an eight-electron-donor butadiyne ligand on an Ru 4 framework. Although the cleavage of diynes by transition-metal clusters has been reported, 6

The binuclear butadiynyl compounds RU~(CO)~(~-~~,~~,,,-C_C-C_CR)(I.L-PP~~) (R = But l a or Ph 1 b), with one n-coordinated and one free triple bond, synthesised via thermolysis of R u ~( C O ) ~~( P P ~~C -C -C -C R ) , react with NEt2H to generate the novel diethylaminobutatriene complexes Ru2(C0)&-~llql-Et2N=C=C=C=C(H)Rl(t_l-PPh~) (R = But 2a or Ph 2b) in high yields: the molecular structures of l a and 2a are determined. Transition metal diynyls (M-C-C-C-CR) are members of a rapidly expanding family of organometallic molecules bearing a carbon-rich, extended chain hydrocarbyl ligand. 1 Interest in such molecules stems from the favourable electronic and structural features of ynyl [C-CR, (CS),, (CrC),R] ligands for