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Table 4-3 and the ‘flat’ and ‘tilted’ modes of adsorbed cinchonidine are indicated by a vibration band e.g. at 768 cm -1 and at 1514 cm -1 are illustrated in the Fig. 4-10 and Fig. 4-11, respectively. Fig. 4-10. Flat adsorbed cinchonidine demonstrates vibration mode at 768 cm -1 with dipole moment (big arrow) orientated mostly perpendicularly to the metal surface. The most intensive displacement of atoms is shown by small arrows. 39
Fig. 4-11. Tilted adsorbed cinchonidine demonstrates vibration mode at 1514 cm -1 with dipole moment (big arrow) orientated mostly perpendicularly to the metal surface. The most intensive displacement of atoms is shown by small arrows. It should be noted, that observed “blue and red shifts” in frequencies (see Table 4-3) indicate the changes in the bond force constants and thus changes in the skeletal geometry of an adsorbed molecule with respect to the free species. However, for the purpose of this work, we will leave these considerations aside, since they do not hinder determination of the orientation of adsorbed cinchonidine and other used molecules (see below). Calculated (correlation coefficient 1.06) and measured IR spectra of free quinoline (mostly medium and strong peaks were chosen) were used as a particular reference for facilitating assignment of the spectra of the cinchonidine (as well as quiphos with aniline from the next chapter), Fig. 4-12. 3 A Relative units 2 B 1 C 0 D 1600 1400 1200 1000 800 600 Wavenumber cm -1 Fig. 4-12 Comparison of IR peaks between free cinchonidine (A), quinoline (B), quiphos (C) and aniline (D). Table 4-3. Assignment of some frequencies (cm -1 ) from IR spectrum of adsorbed and free cinchonidine and free quinoline. Cinchonidine on Pt Free cinchonidine Quinoline Cinchonidine theoretical Vibration description Orientation of adsorbed cinchonidine 1634 (sh) 1636 (med) - 1709 19,20 C strch. Flat 1613 (sh) 1619 (wk3) 1620 (med) 1594 (med) 1590 (str4) 1596 (med) 1670 C-Qu. strch., H- Qu. b. 1643 C-Qu. strch., H- Qu. b. Tilted Tilted 40
Page 1 and 2: Preparation and Characterization of
Page 3 and 4: 5.4 Summary 66 Chapter 6 Cinchonidi
Page 5 and 6: Abstract Studies of the interaction
Page 7 and 8: many compounds are biologically act
Page 9 and 10: Fig. 1-7. Hexahelicene [3]. 7. Chir
Page 11 and 12: R H COOH C OH CH 3 H COO - Bricine-
Page 13 and 14: Catalyst activity, expressed in the
Page 15 and 16: In fact, there are only two heterog
Page 17 and 18: similar way as relative abundance o
Page 19 and 20: surface concentration of cinchonidi
Page 21 and 22: site on Pt surface formed by a adso
Page 23 and 24: Chapter 2 Introduction to the nanos
Page 25 and 26: Triangular prism 5 4 Comments: A -
Page 27 and 28: precursors and building-up. This me
Page 29 and 30: 2.3 Preparation of nanoclusters on
Page 31 and 32: Paris Marseille Ljubljana Synphos Q
Page 33 and 34: Chapter 4 Cinchonidine modified Pt
Page 35 and 36: dihydrocinchonidine (355 mg or 1.2
Page 37 and 38: Table 4-1. Comparison between 5 % P
Page 39 and 40: widening can be used in estimation
Page 41 and 42: 1 Absorbance 0.1 2 1600 1400 1200 1
Page 43: the focus of these prior experiment
Page 47 and 48: sci., QL. comp. 768 (str) 756 (str)
Page 49 and 50: Conversion, % 100 80 60 40 ITP time
Page 51 and 52: 6A c 10 19.5 B, 20 61 0 3 0.18 0.51
Page 53 and 54: pressure, exposing time, cinchonidi
Page 55 and 56: Fig. 4-16. Linear relationship betw
Page 57 and 58: 1 , 1209 cm -1 and 1382 cm -1 remai
Page 59 and 60: Our results are in line with previo
Page 61 and 62: eaction. The stability of the catal
Page 63 and 64: Table 5-1. Ee and reaction rate ind
Page 65 and 66: Enantiomeric excess, % 85 80 75 A2
Page 67 and 68: 35 30 Before After Percent of parti
Page 69 and 70: catalyst activation seems to indica
Page 71 and 72: Table 5-3. Assignment of some vibra
Page 73 and 74: 6.2 Experimental Materials Cinchoni
Page 75 and 76: Fig. 6-3. TEM image of cinchonidine
Page 77 and 78: From the results of EP and EB hydro
Page 79 and 80: enhancement. However the exact fact
Page 81 and 82: Further, this family of man-made li
Page 83 and 84: Fig. 7-2. TEM of quiphos modified P
Page 85 and 86: of quiphos adsorbed on Pt and Pd an
Page 87 and 88: Fig. 7-8 Flat adsorbed quiphos via
Page 89 and 90: comp., H 11,12,13,14 2 C b., 2 P 11
Page 91 and 92: Chapter 8 “Quiphos-spider” modi
Page 93 and 94: flat crystal surface due to the hig
Page 95 and 96:
Chapter 9 Diphos and diop modified
Page 97 and 98:
Table 9-1. Average crystal size of
Page 99 and 100:
Fig. 9-4. Conformation of diphos mo
Page 101 and 102:
ings. Due to these reasons we can n
Page 103 and 104:
Fig. 9-9. Proposed orientation of a
Page 105 and 106:
The model of adsorption of diop on
Page 107 and 108:
The calculation of energy of formin
Page 109 and 110:
For the preparation of synphos modi
Page 111 and 112:
1 2 20 40 60 80 2Θ Fig. 10-3. XRD
Page 113 and 114:
The DRIFT spectra of synphos (Fig.
Page 115 and 116:
peaks which can be used for analysi
Page 117 and 118:
References [1] G.E. Tranter, J. Che
Page 119 and 120:
[64] A. Szabo, N. Kunzle, T. Mallat
Page 121 and 122:
[128] J.D. Aiken III, R.G. Finke, J
Page 123 and 124:
[189] K. Umezawa, T. Ito, M. Asada,
Page 125:
I declare that the current Ph.D. th
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