Thiolates molecular synthesis

In mammals, as in yeast, several different metallothionein isoforms are known, each with a particular tissue distribution (Vasak and Hasler, 2000). Their synthesis is regulated at the level of transcription not only by copper (as well as the other divalent metal ions cadmium, mercury and zinc) but also by hormones, notably steroid hormones, that affect cellular differentiation. Intracellular copper accumulates in metallothionein in copper overload diseases, such as Wilson s disease, forming two distinct molecular forms one with 12 Cu(I) equivalents bound, in which all 20 thiolate ligands of the protein participate in metal binding the other with eight Cu(I)/ metallothionein a molecules, with between 12-14 cysteines involved in Cu(I) coordination (Pountney et ah, 1994). Although the role of specific metallothionein isoforms in zinc homeostasis and apoptosis is established, its primary function in copper metabolism remains enigmatic (Vasak and Hasler, 2000). 

Kaifer and coworkers showed interest in the modification of metal nanoparticles with organic monolayers prepared with suitable molecular hosts. They reported the preparation of water-soluble platinum and palladium nanoparticles modified with thiolated /1-cyclodexlrin (/ -CD) [69]. Nanoparticle synthesis was... 

One astute way to obtain macrocyclic systems with TTF is the stepwise method of deprotection/alkylation of cyanoethyl-protected TTF-thiolates. With this method molecular units can be built but with the precaution of preserving one cyanoethyl group in order to be able to iteratively proceed with the oligomerization. Combining such units, larger units can be produced. An example of a TTF dendrimer containing 21 TTFs is shown in Fig. 2.15 (Christensen et al, 1998). Here only the main philosophy of the synthesis is discussed. 

N-Benzoyl-N-methylnitrosamine added to a stirred suspension of 2 eqs. ethyl mercaptan and 1.5 eqs. NaH in dry tetrahydrofuran at room temp, in the presence of 4A molecular sieves, and stirred for 20 min S-ethyl-thiobenzoate. Y 95%. F.e. inch S-aryl thiolates, also (more rapidly) from N-nitrocarboxylic acid amides, s. R. Beren-guer et al.. Synthesis 1989, 305-6. 

Love JC, Estroff LA, Kriebel JK, Nuzzo RG, Whitesides GM (2005) Self-assembled monolayers of thiolates on metals as a form of nanotechnology. Chem Rev 105 1103-1169 Masala O, Seshadri R (2004) Synthesis routes for large volumes of nanopaiticles. Annu Rev Mater Res 34 41-81 Matolin V, Gillet E, Reed NM, Vickerman JC (1990) CO oxidation over small Pd particle model catalysts. A static secondary ion mass spectrometry study. J Chem Soc Ftnaday Trans 86 2749-2755 McConnell WP, Novak JP, Brousseau LCI, Fuierer RR, Tenent RC, Feldheim DL (2000) Electronic and optical properties of chemically modified metal nanoparticles and molecularly bridged nanoparticle arrays. J Phys Chem B 104 8925-8930... 

Khan, M.A., Kumar, R. and Tuck, D.G. (1988) The direct electrochemical synthesis of adducts of bis(diphenylphosphino)methane(dppm) with copper(I) thiolates, and the molecular structure of Cu4(/x-SC5Hu)4(dppm)2 , Polyhedron, 1, 49-55. 

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