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Novel calamitic side chain metallomesogenic polymers with ferrocene in the backbone: synthesis and properties of thermotropic liquid crystalline poly(ferrocenylsilanes) Chem Commun (3):289 290 Liu ZF, Hashimoto K, Fujishima A 1990 Photoelectrochemical information storage using an azobenzene derivative Nature 347:658 660 Liu ZF, Morigaki K, Enomoto T, Hashimoto K, Fujishima A 1992 Kinetic studies on the thermal cis trans isomerization of an azo compound in the assembled monolayer lm J Phys Chem 96(4):1875 1880 Losche M, Schmitt J, Decher G, Bouwman WG, Kjaer K 1998 Detailed structure of molecularly thin polyelectrolyte multilayer lms on solid substrates as revealed by neutron re ectometry Macromolecules 31(25):8893 8906 Luk Y Y, Abbott NL 2003 Surface driven switching of liquid crystals using redox active groups on electrodes Science 301(5633):623 626 Lvov Y, Ariga K, Onda M, Ichinose I, Kunitake T 1997 Alternate assembly of ordered multilayers of SiO2 and other nanoparticles and polyions.

(5.6.15)

247 248 248 248 248 249 249

Langmuir 13(23):6195 6203 Ma H, et al 2002 Highly ef cient and thermally stable electro optical dendrimers for photonics Adv Funct Mater 12(9):565 574 Magennis SW, Mackay FS, Jones AC, Tait KM, Sadler PJ 2005 Two photon induced photoisomerization of an azo dye Chem Mater 17(8):2059 2062..

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Fig. 5.37 Steady-state concentration distribution (reaction layer) in the case of a chemical volume reaction preceding an electrode reaction (q (Eq. 5 ( ) ) \ k x = 0.04 s"1, D = 10~5cm s \\ \i is the 004 1 (5.6.12)); K = 10\ k effective reaction layer thickness

Malcolm BR, Pieroni O 1990 The photoresponse of an azobenzene containing poly(L lysine) in the monolayer state Biopolymers 29(6 7):1121 1123 Malkin S, Fischer E 1962 Temperature dependence of photoisomerization Part II1 Quantum yields of cis trans isomerizations in azo compounds J Phys Chem 66(12):2482 2486 Mallia VA, Tamaoki N 2003 Photoresponsive vitri able chiral dimesogens: photo thermal modulation of microscopic disordering in helical superstructure and glass forming properties J Mater Chem 13(2):219 224 Mattoussi H, Rubner MF, Zhou F, Kumar J, Tripathy SK 2000 Photovoltaic hetero structure devices made of sequentially adsorbed poly(phenylene vinylene) and functio nalized C60 Appl Phys Lett 77(10):1540 1542 Maxein G, Zentel R 1995 Photochemical inversion of the helical twist sense in chiral polyisocyanates Macromolecules 28(24):8438 8440 McAloney RA, Dudnik V, Goh MC 2003 Kinetics of salt induced annealing of a polyelectrolyte multilayer lm morphology Langmuir 19(9):3947 3952 Mekelburger HB, Rissanen K, Voegtle F.

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349 This relationship forms the basis for the method of determining the rate constants of fast chemical reactions from the kinetic current. A similar procedure can be employed for subsequent and parallel chemical reactions and for higher-order reactions. The reduction of formaldehyde at a mercury electrode is an example of a system in which a chemical reaction precedes the electrode reaction. Formaldehyde is present in aqueous solution as the hydrated form (as dihydroxymethane), which cannot be reduced at a mercury electrode. This form is in equilibrium with the carbonyl form

1993 Repetitive synthesis of bulky dendrimers a reversibly photoactive dendrimer with six azobenzene side chains Chem Ber 126(5):1161 1169 Mendelsohn JD, et al 2000 Fabrication of microporous thin lms from polyelectrolyte multilayers Langmuir 16(11):5017 5023 Meng X, Natansohn A, Barrett C, Rochon P 1996 Azo polymers for reversible optical storage 10 Cooperative motion of polar side groups in amorphous polymers Macro molecules 29(3):946 952 Mermut O, Barrett CJ 2001 Stable sensor layers self assembled onto surfaces using azobenzene containing polyelectrolytes Analyst (Cambridge, UK) 126(11):1861 1865 Mermut O, Barrett CJ 2003 Effects of charge density and counterions on the assembly of polyelectrolyte multilayers J Phys Chem B 107(11):2525 2530 Mermut O, Lefebvre J, Gray DG, Barrett CJ 2003 Structural and mechanical properties of polyelectrolyte multilayer lms studied by AFM Macromolecules 36(23):8819 8824 Minoura N, et al 2004 Preparation of azobenzene containing polymer membranes that function in photoregulated molecular recognition.

251 251 251 252 252 252 253 253 253

According to R. Brdicka and K. Vesely the carbonyl form of formaldehyde is reduced and the limiting kinetic current is given by the rate of the chemical volume reaction of dehydration. An analogous situation occurs for the equilibria among complexes, metal ions and complexing agents if the rates of complex formation and decomposition are insufficient to preserve the equilibrium. A simple example is the deposition of cadmium at a mercury electrode from its complex with nitrilotriacetic H N + ^ C O O H = H3X. Here, a single X3~ species is bound in the COOH complex. According to J. Koryta, equilibrium in solution in the pH range from 3 to 5 can be described by the equation Cd2+ + HX2~ <=^ CdX" + H + (5.6.17)

Macromolecules 37(25):9571 9576 Mita I, Horie K, Hirao K 1989 Photochemistry in polymer solids 9 Photoisomerization of azobenzene in a polycarbonate lm Macromolecules 22(2):558 563 Mohlmann G, van der Vorst C 1989 Side Chain Liquid Crystal Polymers Glasgow: Plenum and Hall Moller G, Harke M, Motschmann H, Prescher D 1998 Controlling microdroplet formation by light Langmuir 14(18):4955 4957 Momotake A, Arai T 2004a Photochemistry and photophysics of stilbene dendrimers and related compounds J Photochem Photobiol C 5(1):1 25 Momotake A, Arai T 2004b Synthesis, excited state properties, and dynamic structural change of photoresponsive dendrimers Polymer 45(16):5369 5390 Montagnoli G, Pieroni O, Suzuki S 1983 Control of peptide chain conformation by photoisomerising chromophores: Enzymes and model compounds Polymer Photochem 3(4):279 294..

The symbols kf and kd are the rate constants for the formation and dissociation of the complex. The equilibrium constant of reaction (5.6.17) is given by the relationship KC6xK3 = ^

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