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ISRN Organic Chemistry
Volume 2012 (2012), Article ID 976178, 11 pages
Synthesis and Optoelectronic Characterization of Some Star-Shaped Oligomers with Benzene and Triphenylamine Cores
Electroactive Polymers Department, Institute of Macromolecular Chemistry "Petru Poni", 41A Gr. Ghica Voda Alley, 700487 Iasi, Romania
Received 27 April 2012; Accepted 13 June 2012
Academic Editors: F. V. Gonzalez and F. L. Van Delft
Copyright © 2012 Teofilia Ivan et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Six star-shaped oligomers containing triphenylamine (D1–D3) and benzene unit (D4–D6) as cores have been synthesized by Wittig condensation or Heck coupling reaction using aromatic aldehydes and triphenylphosphonium salts or aromatic halogenated compounds with vinyl triphenylamine. All oligomers have well-defined molecular structure and high purity. Characterization of the oligomers was made by FT-IR, 1H-NMR spectroscopy, UV-Vis, and fluorescence spectroscopy. The electrochemical behavior was studied by cyclic voltammetry (CV). The cyclic voltammograms have revealed that oligomers undergo quasireversible or irreversible redox processes. The irreversible process is associated with electrochemical polymerization of oligomers by dimerization of unsubstituted triphenylamine groups. Thermal characterization was accomplished by TGA and DSC methods and evidenced that all oligomers were stable materials until 250°C and have formed stable molecular glasses after first heating scan.
1. Introduction
Conjugated oligomers with linear, highly branched and dendrimer structures form an important class of electro- and photoactive materials, investigated both in academic and industrial laboratories [1–9]. These architectures have advantages to offer molecules with a well-defined form and structure, a high chemical purity, and degree of order, being characterized by a polydispersity degree of one. It is important to note that the purity of materials is vital for the long-term stability of optoelectronic devices. Dendrimers can be obtained using laborious step-by-step synthesis in a convergent or divergent methodology [10]. The advantage of using small conjugated compounds is based on the possibility of tuning their photophysical properties by changing the chemical structure, for example, by introduction of side substituents, end-capping groups, insertion of certain specific functional groups, and by changing the oligomer length. Moreover, conjugated oligomers are used as model compounds for conducting polymers since their monodispersity, defectless structure, and better supramolecular organization in the solid state facilitate their experimental and theoretical investigations. The real interests for conjugated oligomers emerge also from interesting application such as active components in organic electronic or electrochemical devices, such as organic light emitting diodes (OLEDs) [11–15], photovoltaic cells [16, 17], optical power limiting [18], and field-effect transistors [19]. One of the important challenging goals of the conjugated oligomer chemistry is to develop new π-conjugated structures to investigate their photophysical and chemical properties, as well as to understand the structure-property relationship within such structures.
Triphenylamine (TPA) oligomers have been widely investigated for almost two decades because these compounds have shown excellent solubility, thermal and electrochemical stability, electron donating ability, and optoelectronic properties [9, 20]. They have been used most widely as the hole-transporting layer in EL devices, due to their amorphous film-forming ability and their high carrier mobility. They also can act as efficient dyes for sensitized solar cells [21]. Heck and Wittig reactions were extensively utilized to build the vinylene bond in each phenylenevinylene conjugation unit. The triphenylamine derivatives connected by the C–C double bond can be synthesized by Wittig and Heck reactions without air-sensitive catalyst or high temperatures and prolonged reaction time, and the structure similar to the p-phenylene moiety has the interesting photochemical and photophysical properties. In this paper, we report the synthesis, characterization, and photophysical properties of six representative conjugated star oligomers having trisubstituted 1,3,5-benzene and 4,4′,4′′-triphenylamine as the cores. The first five oligomers can be considered conjugated dendrimers of first generation while the sixth oligomer is a dendrimer of second generation. They have high fluorescence quantum yield, which indicats that these oligomers are candidates for the application in OLED as light emitting or photovoltaic materials. Relationship between chemical structure and optoelectronic properties of these compounds was investigated by spectral methods, such as UV-Vis and fluorescence spectroscopy, Cyclic Voltammetry, and thermal methods.
2. Experimental
2.1. Materials and Instruments
1,3,5-tris (bromomethyl) benzene (97%, mp = 94–99°C), triphenylamine (98%), sodium t-butoxide (t-C4H9ONa), triethylamine, palladium (II) acetate, and tri (o-tolyl) phosphine were purchased from Aldrich and used as received. Dioxane and tetrahydrofuran (THF) were dried on sodium wire and distilled under nitrogen just before use. 4-Formyl triphenylamine [22] and 4,4′,4′′-triformyl triphenylamine [23–25] were obtained by formylation of TPA according to the reported methods. 4-Formyl-N,N′-bis(4-bromophenyl) aniline [26], tris (4-iodophenyl) amine [27] and vinyl triphenylamine [28] were synthesized and purified according to the literature procedures. Triphenylphosphonium salts were also obtained in a series of chemical reactions in our laboratory, using the starting compounds: 1,3,5-tris (bromomethyl) benzene, N,N-dimethylaniline, and anthracene. 1,3,5-Tris (methylene-triphenyl phosphonium bromide) benzene was prepared as described in literature [29]. 4-(N,N-Dimethylamino)benzyl(triphenyl)phosphonium iodine was synthesized according to the reported procedure [30]. 9-Anthrymethyl triphenylphosphonium chloride was synthesized starting from anthracene by three steps: formylation [31], followed by reduction to 9-anthrylmethanol [32], exchange the –OH with chlorine using SOCl2 as reagent [31], and finally, reaction with PPh3 [29].
The FT-IR spectra were recorded in KBr pellets on a DIGILAB-FTS 2000 spectrometer. UV-Vis and fluorescence measurements were carried out in solution using spectrophotometric grade solvents, on a Specord 200 spectrophotometer and Perkin Elmer LS 55 apparatus, respectively. 1H-NMR spectra were recorded at room temperature on a Bruker Avance DRX-400 spectrometer (400 MHz) as solutions in CDCl3, and chemical shifts are reported in ppm and referenced to TMS as internal standard. The cyclic voltammograms (CV) were recorded using a Bioanalytical System, Potentiostat-Galvanostat (BAS 100B/W) system. The electrochemical cell was equipped with three electrodes: a working electrode (Pt, mm) or ITO-coated glass (platinum plate) with cm2, an auxiliary electrode (platinum wire), and a reference electrode (consisted of a silver wire coated with AgCl). Before experiments, ITO-coated glass electrode was sonicated in a mixture of detergent and methanol for 5 min and then rinsed with a large amount of doubly distilled water. The reference electrode (Ag/AgCl) was calibrated at the beginning of the experiments by running the CV of ferrocene as the internal standard in an identical cell without any compound in the system ( V versus Ag/AgCl). Prior to each experiment, electrolyte solutions were deoxygenated by passing dry argon gas for 10 min. All measurements were performed at room temperature (25°C) under argon atmosphere. Melting points were determined with Electrothermal MEL-TEMPR apparatus. Thermal gravimetric analyses (TGA) were performed by means of a STA 449 F1 Jupiter device, in N2 atmosphere, with a flow of 40 mL/min, and a heating speed of 10 K/min (30–900°C range). DSC measurements were performed with a Mettler DSC-12E apparatus, in nitrogen.
2.2. Synthesis of Arylenevinylene Oligomers by Wittig Method
Compounds D1, D2, D4, and D5, containing triphenylamine or benzene as cores, were synthesized by Wittig condensation starting from triphenylamine aldehydes with corresponding triphenylphosphonium salts (Figure 1). Aldehydes and phosphonium derivatives were dissolved in dry THF (10 mL) at 0°C and a base was added, and the reaction mixture was warmed to room temperature and stirred under N2 overnight. The reaction mixture was poured into water, filtered, and dried. The products were purified by column chromatography using dichloromethane/hexane (1/10). They were obtained as yellow powders with strong green-yellow fluorescence in diluted solution.
D1: to a solution of tris (4-formylphenyl) amine (0.15 g, 0.45 mmol) and 9-anthrymethyl triphenylphosphonium chloride (0.69 g, 1.4 mmol) in 10 mL THF, t-BuONa (0.17 g, 1.82 mmol) in 20 mL of dry THF was dropwise added to the resulting solution maintained at 0°C, then the reaction mixture was warmed to room temperature and stirred under N2 overnight. The reaction mixture was poured into water, filtered, and dried. The crude product was purified by flash column chromatography using dichloromethane/hexane (1 : 10) to give 0.21 g compound D1 (54.3%) as a yellow solid. Mp: 271-272°C.
FT-IR (cm−1, KBr): 3044–2923 (=C–H), 1597 (C=C), 1440, 1322 (C–N stretching vibration), 1176, 1016, 971 (out-of-plane bending vibration of trans –CH=CH–), 731, 508.
1H-NMR (CDCl3): 8.42–8.40 (t, 9H), 8.04–8.01 (m, 6H), 7.91–7.87 (d, 3H vinyl), 7.66–7.64 (d, 6H), 7.50–7.25 (m, 12 H), 7.32–7.25 (d, 6H), 6.98–6.94 (d, 3H vinyl).
Elemental analysis, %: Calculated for C66H45N (852.09 amu): C, 93.04; H, 5.32; N, 1.64. Found: C, 92.79; H, 5.42; N, 1.50.
D2: Tris (4-formylphenyl) amine (0.2 g, 0.60 mmol) and 4-(N,N-dimethylamino) benzyl (triphenyl) phosphonium iodine (0.98 g, 1.8 mmol) were dissolved in 10 mL of dry THF and t-BuONa (0.3 g, 3.12 mmol) in 20 mL of dry THF was added under cooling. The color solution changes, initially was mauve and finally changed to darkred. The reaction mixture was warmed to room temperature and stirred overnight under N2. The reaction mixture was poured into water, filtered, and dried. The crude product was purified by flash column chromatography using dichloromethane and hexane (1 : 10 v/v ratio). Yield = 0.245 g (59.5%) of D2 as a yellow solid. Mp: 140–144°C.
FT-IR (cm−1, KBr): 3440–3397 (N–H), 3020–2797 (=C–H), 1606 (C=C, conjugated phenyl groups), 1353, 1321 (C–N stretching vibration), 962 (out-of-plane bending vibration of trans –CH=CH–), 826, 543.
1H-NMR (CDCl3): 7.41–7.35 (m, 12H), 7.08–7.06 (d, 6H), 6.98–6.86 (m, 6H), 6.73 (d, 6H, vinyl), 2.99 (s, 18H, –CH3).
Elemental analysis, %: Calculated for C48H48N4 (680.935 amu) C, 84.67; H, 7.10; N, 8.23. Found: C, 83.25; H, 7.02; N, 8.11.
D4: 1,3,5-Tris (methylene-triphenyl phosphonium bromide) benzene (0.75 g, 0.65 mmol) and 4-formyl triphenylamine (0.53 g, 1.95 mmol) were dissolved in 10 mL of dry THF; t-BuONa (0.18 g, 1.95 mmol) in 20 mL of dry THF was added dropwise slowly to the resulting solution at 0°C, then the reaction mixture was warmed to room temperature and stirred overnight under N2. The reaction mixture was poured into water, filtered, and dried. The crude product was purified by flash column chromatography using dichloromethane/hexane as eluent, yield: 0.23 g (41.1%) of compound D4 as yellow solid. Mp: 191°C.
FT-IR (cm−1, KBr): 3438, 3034–2852 (=C–H), 1587 (C=C, conjugated phenyl groups), 1506, 1490, 1278, 1075, 1028, 960 (out-of-plane bending vibration of trans –CH=CH–), 753, 696.
1H-NMR (CDCl3): 7.49 (s, 3H), 7.42–7.38 (6H), 7.28–7.21 (m, 12H), 7.13–7.11 (m, 12H), 7.06–7.01 (m, 18H).
Elemental analysis, %: Calculated for C66H51N3 (886.15 amu) C, 89.46; H, 5.80; N, 4.74. Found: C, 88.18; H, 5.46; N, 4.38.
D5: A solution of 4-formyl-N,N′-bis (4-bromophenyl) aniline (0.56 g, 1.31 mmol) and 1,3,5-tris (methylene-triphenyl) phosphoniumbromide) benzene (0.5, 0.43 mmol) was dissolved in 10 mL of dry THF. The resulting solution was dropwise slowly added to 0.12 g (1.31 mmol) of t-BuONa in 20 mL of dry THF at 0°C, then the reaction mixture was warmed to room temperature and stirred overnight under N2. The mixture reaction was poured into water, filtered, and dried. The crude product was obtained as a yellow solid, yield: 0.26 g (44.1%). Mp: 142-143°C.
FT-IR (cm−1, KBr): 3447, 3028–2852 (=C–H), 1581 (C=C, conjugated phenyl groups), 1507, 1485, 1312, 1285, 1272, 1176, 1007, 961 (out-of-plane bending vibration of trans –CH=CH–), 819, 710, 508.
1H-NMR (CDCl3): 7.51 (s, 3H), 7.37–7.35 (18 H), 6.98–6.96 (18H), 6.91–6.87 (6H).
2.3. Synthesis of Arylenevinylene Oligomers by Heck Reaction
Oligomers D3 and D6 were synthesized by Heck coupling reaction of halogenated aromatic compounds with 4-vinyl triphenylamine. The mixture of compounds and catalyst palladium (II) acetate and tri (o-tolyl) phosphine in anhydrous dioxane/triethylamine mixture was stirred 24 h at 80–90°C under argon. The reaction mixture was poured into methanol, filtered, and dried. The resulting compounds were obtained as yellow powders.
D3: A round-bottomed flask (25 mL) oven dried and cooled under N2 atmosphere was introduced: tris (4-iodophenyl) amine (0.5 g, 0.80 mmol), 4-vinyltriphenylamine (0.65 g, 2.4 mmol), Pd(OAc)2 (0.04 mmol), and tri (o-tolyl phosphine) (0.2 mmol) in 10 mL dioxane and 5 mL triethylamine. The reaction mixture was heated to 80–90°C overnight. The solution was poured into methanol the precipitate was filtered, washed with methanol, water and dried. The crude product is obtained as yellow solid (0.476 g). Yield = 56.6% of D3. Mp=257-258°C.
FT-IR (cm−1, KBr): 3026–2851 (=C–H), 1581, 1591 (C=C, conjugated phenyl groups), 1508, 1314, 1280, 959 (out-of-plane bending vibration of trans –CH=CH–), 752, 695 (C–H phenyl rings).
1H-NMR (CDCl3): 7.62–7.60 (3H, vinyl), 7.49–7.41 (t, 6H), 7.32–7.29 (m, 12H), 7.07–7.05 (d, 6H), 7.03–7.01 (m, 24H), 6.97–6.93 (d, 6H), 6.83–6.81 (3H, vinyl).
13C-NMR, CDCl3 100 MHz: 147.77, 147.49, 147.11, 147.03, 146.35, 146.00, 138.25, 138.12, 132.75, 132.34, 131.59, 129.19, 127.19, 126.40, 125.83, 124.26, 123.78, 122.56, 77.33–77.69 (from CDCl3).
D6: Compound D5 (0.05 g, 0.04 mmol), 4-vinyltriphenylamine (0.08 g, 0.28 mmol), palladium (II) acetate (0.002 mmol), and tri (o-tolyl phosphine) (0.01 mmol) were stirred in dioxane (10 mL) and triethylamine (5 mL) and heated and stirred overnight at 80–90°C under argon. The reaction mixture was poured in methanol, filtered, washed, and dried. The resulting compound was obtained as a yellow solid with yield = 58.1% (0.036 g). Mp: 240°C.
FT-IR (cm−1, KBr): 3435, 3026–2852 (=C–H), 1583 (C=C, conjugated phenyl groups), 1507, 1484, 1312, 1283, 1071, 1007, 961 (out-of-plane bending vibration of trans–CH=CH–), 696, 508.
1H-NMR (CDCl3): 7.51 (s, 3H), 7.44–7.42 (d, 6H), 7.39–7.35 (m, 24H Ph and vinyl), 7.31–7.22 (m, 24H), 7.20–7.03 (m, 48H), 6.98-6.92 (m, 30H Ph and vinyl), 6.92–6.87 (6H).
3. Results and Discussion
Six star-shaped oligomers, D1–D6, with arylenevinylene structure have been synthesized by condensation of triphenylamine aldehydes with triphenylphosphonium salts and by Heck coupling reaction between aromatic halogenated compounds and 4-vinyl triphenylamine. The synthetic pathways and chemical structures of compounds are given in Figure 1.It had to be mentioned that syntheses of D2 [33] and D3 [34, 35], using another synthetic routes, were reported but only nonlinear optical properties were studied.
The FT-IR and 1H-NMR spectra in CDCl3 have confirmed the expected oligomer structures (see Experimental). The FT-IR spectra have shown the characteristic bands of the chromophore groups: 2923–3020 cm−1 attributed to aromatic (νC–H); 1581–1606 cm−1 assigned to the phenyl rings (νC=C). All oligomers have transarylenevinylene structure which is also confirmed by characteristic IR absorption peak at 959–971 cm−1 corresponding to the out-of-plane bending vibration of HC=CH.
3.1. Photophysical Properties
The UV-Vis absorption and photoluminescence spectra of oligomers are shown in Figures 2 and 3. All absorption spectra consist of two distinct absorption regions with maxima at 250–325 nm and 370–406 nm without any vibronic features. The first maximum is assigned to π-π* transition in aromatic rings while the second maximum is due to π-π* in all conjugated molecule. Figure 2 presents the absorption and photoluminescence spectra of the D1, D2, and D3 oligomers, recorded in chloroform.
All three oligomers have a triphenylamine ramification node, three vinylene conjugated spacers and three anthracene, triphenylamine or p-N,N-dimethyl benzene as peripheral groups. The absorption spectrum shape of D1 is characteristic for substituted vinyl anthracene (three groups) [36], while the absorption of triphenylamine core is covered. The absorption spectrum of 9-vinylanthracene (in CHCl3) has two absorption regions with vibronic structure (260 nm and 355, 372, and 390 nm) being bathochromically shifted compared with anthracene. The bathochrome shift of absorption spectrum of D1 in comparison with vinylanthracenes is assigned to contribution of TPA core that by nitrogen central atom does not interrupt the conjugation between the three branches. The absorption spectrum of D3 shows a maximum absorption at 406 nm. 4,4-Bis (diphenylamino) stilbene, model compound of a branch, exhibits a maximum absorption peak at 370 nm (in CHCl3 solution) [37]. The strong bathochrome shift of of D3 (36 nm) in comparison with 4,4-bis (diphenylamino) stilbene model could be explained by participation of nitrogen central atom to conjugation, the conjugation between the three branches being uninterrupted. The absorption curves of D2 and D3 are very similar showing two absorption maxima at ~325 nm and 404 nm for D2, and 308, 330 nm and 406 nm for D3. The absorption maximum of D3 is bathochromatically shifted, related to D2, phenyl groups having a stronger donor effect in comparison with methyl ones.
Diluted solutions of oligomers in CHCl3 are characterized by a yellowish-green fluorescence. The emission spectra show a bathochromic shift in the order: D1 > D3 > D2 (Table 1) and this may be explained by increasing of conjugation length in oligomers. A dependence of fluorescence of D1, D2, and D3 upon excitation wavelengths was not observed. The absorption data of all oligomers are summarized in Table 1.
Figure 3 shows absorption and photoluminescence spectra of the oligomers having 1,3,5-trisubstituted benzene ring as core (D4, D5, D6), in chloroform solution. All oligomers display two absorption peaks in the range of 302–316 nm and 374–376 nm, respectively. The first absorption peak situated in the low wavelength region, 302–316 nm, was attributed to the triphenylamine moiety. The second absorption peak at 374–376 nm was ascribed to the TPA-vinylene-modified benzene unit. As compared with D1–D3 oligomers, the of D4–D6 is blue-shifted; the metha substituted benzene core interrupts the conjugation between the three branches.
A red-shifting of the absorption maxima was observed in the series D4 < D5 < D6 due to the increasing in the same order of the effective conjugation length of the branches. For D5, bromine atoms have an electron withdrawing effect and is lower than unsubstituted D4. Compounds D4 and D6 are dendrimers of first, and respectively, second generation. With increasing of the generation of dendrimers, the effective conjugation increases [38].
Figure 3(b) illustrated the PL spectra of oligomers in dilute chloroform solutions. For the emission spectra in dilute chloroform solutions, D4, D5, and D6 display similar behaviors. The red-shift of the emission peak of D6 from that of D4 and D5 show that there is obvious π-π* delocalization and a significant increase of the effective conjugation length with the increase of the generation of dendrimers. A comparison of UV and PL spectra of D3 and D4 oligomers shows that triphenylamine is a better conjugation node than benzene core.
3.2. Electrochemical Properties
The electrochemical characteristics of the star-shaped molecules were investigated by cyclic voltammetry. Generally, increasing the chain length and number of electroactive sites involves a higher electronic delocalization which may cause differences in redox behavior of the derivatives. Cyclic voltammograms of compounds have been determined in CH2Cl2 with tetrabutylammonium tetrafluoroborate as electrolyte. All measurements were carried out at room temperature and argon atmosphere. Representative cyclic voltammograms are shown in Figure 4.
In general, all molecules undergo a quasireversible redox process arising from triphenylamine central unit followed by a series of quasireversible or irreversible oxidations originating from bridged aromatic peripheral moieties.
Figure 4(a) shows the CV of D1. The first scan (dotted line) revealed four oxidation peaks and one reduction peak. First oxidation peak, occurring at V, is caused by the formation of the TPA cation radical. The further oxidation process revealed three anodic peaks at V, V, and V. These peaks can be attributed to the oxidation of the n-π conjugated system between triphenylamine and anthracene units at the ends. On the reverse scanning, one reduction peak can be observed located at V, which is very broad. The intensity of these peaks decreases with increasing the number of scans but no polymeric film was obtained on Pt plate electrode by recording a repetitive CVs scanning. The CVs of D2 are presented in Figure 4(b) and are characterized by two oxidation peaks at V, V and two reduction peaks at V and V. The second oxidation peak () is attributed to the strong conjugated electron-donating moiety (N,N-dimethylaniline). During the repetitive scanning of CVs of compound D2, the first oxidation () decreases with increasing the number of scans and the potential value for the second oxidation () is shifted in the positive direction. The current intensity decreases by increasing the number of scans. A very thin film of polymer with rainbow color is deposited on Pt plate electrode after repetitive CVs scanning, which is insoluble in methylene chloride and acetone.
In Figure 4(c), the CVs of compound D3 in methylene chloride solution, obtained during the successive scans between 0.0 and 1,5 V versus Ag/AgCl, are presented. The CV shows three oxidation peaks at V, V, and V and two reduction peaks at V and V. The oxidation peaks are associated with the loss of an electron from the atomic central nitrogen of TPA moieties, leading to the formation of cation-radicals. Intensity of these peaks increases with increasing the number of scans. Thus, a green thin film of polymer on Pt plate electrode was deposited by repetitive CVs scans.
Compound D4 undergoes quasireversible process exhibits two oxidation peaks at V, V and two reduction peaks at V and V. The oxidation peaks are assigned to the formation of cation-radicals of triphenylamine at the ends. The first oxidation peak () disappears with increasing the number of scans; the same thing happened with the reduction peak (). In both cases, the intensity of the current increases with the number of scans; this indicated that a new electroactive structure is formed during the repetitive CV scans. Thus, a green-red colored polymer film is formed and deposited on the Pt plate electrode surface, which is insoluble in methylene chloride and acetone.
The dendrimer D6 exhibits three oxidation peaks at V, V, and V and two reduction peaks at V and V. The three oxidation peaks correspond to the formation of cation-radicals of triphenylamine units (internal and peripheral units) that are formed during the process. Recording the CVs by running a higher number of scans was observed that a third oxidation peak () is shifted in the positive direction. By scanning in the opposite direction the value of reduction peak one () is shifted in negative direction with increasing the number of scans. The intensity of the peak current increased regularly during the successive scans (Figure 5(b)). Finally, a green-yellow polymer film deposited on the Pt plate electrode surface was obtained.
The anodic oxidation of triphenylamine and its derivatives was extensively studied starting from 1966 [39–42]. As a conclusion of these studies, TPA-based oligomers fall in the category of multistep processes involving electrochemical-chemical-electrochemical (ECE) reactions. In the first step, a cation radical is formed (TPA∙+) by oxidation and this is not stable and dimerizes to tetraphenylbenzidine. If all phenyl groups of TPA derivative are tri-para-substituted, the only reaction is the reversible one-electron transfer. In our case, oligomers contain TPA as internal and/or peripheral group. Therefore, only cation-radicals of peripheral TPA are unstable and could dimerize to form tetraphenylbenzidine derivatives, and all processes can be continued until polymer films are deposited on electrode surface.
According to the correlation which can be done, between HOMO and LUMO energy levels and redox potentials, the value of the energy levels can be calculated from CVs using the on-set values of the oxidation and reduction peaks. The on-set values are estimated from the intersection of the two tangents drawn at the rising oxidation (or reduction) current and the background current in the CVs. The electrochemical data are summarized in Table 2.
Thermal properties of D1–D4 and D6 were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TG curves revealed that oligomers were thermally stable materials and the onset decomposition temperatures occurred above 250°C under nitrogen. According to DSC analysis, all compounds remained in amorphous glass state after first heating scan because triphenylamine units have a noncoplanar conformation that hindered the crystallization process.
4. Conclusion
In conclusion, we have synthesized six-conjugated arylenevinylene oligomers containing triphenylamine and benzene as core by Wittig and Heck polycondensation methods. The oligomers showed very good solubility in common organic solvents due to the star conformation. All conjugated oligomers exhibit interesting optical properties (absorption and emission) and they also have high fluorescence, which indicate that they are good candidates for the application in OLED as light emitting materials. Cyclic voltammetry was carried out in order to obtain information about the electrochemical stability and the redox process of oligomers. By increasing the π-conjugation length, which implies a higher electronic delocalization, the redox behavior of the compounds is changed. It was observed that oligomers containing peripheral TPA groups are able to be electrochemically polymerized by dimerization, when thin polymer films were deposited on working electrode.
The authors thank the Romanian National Authority for Scientific Research (UEFISCDI) for financial support (Grant PN-II-ID-PCE-2011-3-0274, Contract 148/2011).
- T. A. Skotheim and J. R. Reynolds, Handbook of Conducting Polymers, CRC Press, New York, NY, USA, 3rd edition, 2007.
- A. G. MacDiarmid, "Synthetic metals: a novel role for organic polymers (Nobel lecture)," Angewandte Chemie, International Edition, vol. 40, pp. 2581–2590, 2001. View at Google Scholar
- A. J. Heeger, "Semiconducting and metallic polymers: the fourth generation of polymeric materials (Nobel lecture)," Angewandte Chemie, International Edition, vol. 40, pp. 2591–2611, 2001. View at Google Scholar
- J. Heinze, "Electronically conducting polymers," Topics in Current Chemistry, vol. 152, pp. 1–47, 1990. View at Publisher · View at Google Scholar
- S. J. Higgins, "Conjugated polymers incorporating pendant functional groups-synthesis and characterization," Chemical Society Reviews, vol. 26, no. 4, pp. 247–257, 1997. View at Publisher · View at Google Scholar
- T. Noda, H. Ogawa, N. Noma, and Y. Shirota, "Organic light-emitting diodes using a novel family of amorphous molecular materials containing an oligothiophene moiety as colour-tunable emitting materials," Journal of Materials Chemistry, vol. 9, no. 9, pp. 2177–2181, 1999. View at Publisher · View at Google Scholar · View at Scopus
- T. Otsubo, Y. Aso, and K. Takimiya, "Functional oligothiophenes as advanced molecular electronic materials," Journal of Materials Chemistry, vol. 12, no. 9, pp. 2565–2575, 2002. View at Publisher · View at Google Scholar · View at Scopus
- H. Nakanishi, Y. Aso, and T. Otsubo, "The longest class of oligothiophenes," Synthetic Metals, vol. 101, no. 1–3, pp. 604–605, 1999. View at Google Scholar · View at Scopus
- D. Sek, E. Grabiec, H. Janeczek et al., "Structure-properties relationship of linear and star-shaped imines with triphenylamine moieties as hole-transporting materials," Optical Materials, vol. 32, no. 11, pp. 1514–1525, 2010. View at Publisher · View at Google Scholar · View at Scopus
- D. A. Tomalia, A. M. Naylor, and W. A. Goddard, "Starbust dendrimers: molecular-level control of size, shape, surface chemistry, topology, and flexibility from atoms to macroscopic matter," Angewandte Chemie, International Edition, vol. 29, no. 2, pp. 138–175, 1990. View at Google Scholar · View at Scopus
- A. Kraft, A. C. Grimsdale, and A. B. Holmes, "Electroluminescent conjugated polymers—seeing polymers in a new light," Angewandte Chemie, International Edition, vol. 37, no. 4, pp. 402–428, 1998. View at Google Scholar · View at Scopus
- B. W. D'Andrade and S. R. Forrest, "White organic light-emitting devices for solid-state lighting," Advanced Materials, vol. 16, no. 18, pp. 1585–1595, 2004. View at Publisher · View at Google Scholar · View at Scopus
- S. A. Jenekhe, "Excited-state complexes of conjugated polymers," Advanced Materials, vol. 7, no. 3, pp. 309–311, 1995. View at Google Scholar · View at Scopus
- J. S. Miller, "Conducting polymers—materials of commerce," Advanced Materials, vol. 5, no. 9, pp. 671–676, 1993. View at Google Scholar · View at Scopus
- R. L. Carroll and C. B. Gorman, "The genesis of molecular electronics," Angewandte Chemie, International Edition, vol. 41, no. 23, pp. 4378–4400, 2002. View at Google Scholar
- G. Yu, J. Gao, J. C. Hummelen, F. Wudl, and A. J. Heeger, "Polymer photovoltaic cells: enhanced efficiencies via a network of internal donor-acceptor heterojunctions," Science, vol. 270, no. 5243, pp. 1789–1791, 1995. View at Google Scholar · View at Scopus
- Y. J. Cheng, S. H. Yang, and C. S. Hsu, "Synthesis of conjugated polymers for organic solar cell applications," Chemical Reviews, vol. 109, no. 11, pp. 5868–5923, 2009. View at Publisher · View at Google Scholar · View at Scopus
- J. D. Bhawalkar, G. S. He, and P. N. Prasad, "Nonlinear multiphoton processes in organic and polymeric materials," Reports on Progress in Physics, vol. 59, no. 9, pp. 1041–1070, 1996. View at Publisher · View at Google Scholar · View at Scopus
- J. H. Schon, A. Dodabalapur, C. Kloc, and B. Batlogg, "A light-emitting field-effect transistor," Science, vol. 290, no. 5493, pp. 963–965, 2000. View at Publisher · View at Google Scholar · View at Scopus
- J. Louie, J. F. Hartwig, and A. F. Fry, "Discrete high molecular weight triarylamine dendrimers prepared by palladium-catalyzed amination," Journal of the American Chemical Society, vol. 119, no. 48, pp. 11695–11696, 1997. View at Publisher · View at Google Scholar · View at Scopus
- B. O'Regan and M. Grätzel, "A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films," Nature, vol. 353, no. 6346, pp. 737–740, 1991. View at Google Scholar · View at Scopus
- M. Zheng, F. Bai, and D. J. Zhu, "New light emitting materials: alternating copolymers with hole transport and emitting chromophores," Journal of Applied Polymer Science, vol. 74, no. 14, pp. 3351–3358, 1999. View at Google Scholar
- G. Lai, X. R. Bu, J. Santos, and E. A. Mintz, "Reinvestigation of the Vilsmeier-Haack formylation of triphenylamine," Synlett, vol. 1997, no. 11, pp. 1275–1276, 1997. View at Google Scholar · View at Scopus
- T. Mallegol, S. Gmouh, M. A. A. Meziane, M. Blanchard-Desce, and O. Mongin, "Practical and efficient synthesis of tris(4-formylphenyl)amine, a key building block in materials chemistry," Synthesis, no. 11, pp. 1771–1774, 2005. View at Publisher · View at Google Scholar · View at Scopus
- M. Grigoras and L. Stafie, "Synthesis and characterization of linear, branched and hyperbranched triphenylamine-based polyazomethines," Designed Monomers and Polymers, vol. 12, no. 2, pp. 177–196, 2009. View at Publisher · View at Google Scholar · View at Scopus
- L. Vacareanu and M. Grigoras, "Synthesis and electrochemical characterization of new linear conjugated arylamine copolymers," High Performance Polymers, vol. 23, no. 2, pp. 112–124, 2011. View at Publisher · View at Google Scholar · View at Scopus
- Y. Kuwabara, H. Ogawa, H. Inada, and Y. Shirota, "Thermally stable multilayered organic electroluminescent devices using novel starburst molecules, 4,4′,4″-tri(N-carbazolyl)triphenylamine (TCTA) and 4,4′,4″-tris(3-methylphenylphenyl-amino)triphenylamine (m-MTDATA), as hole-transport materials," Advanced Materials, vol. 6, no. 9, pp. 677–679, 1994. View at Google Scholar · View at Scopus
- K. M. Yeh, C. C. Lee, and Y. Chen, "Poly(4-vinyltriphenylamine): optical, electrochemical properties and its new application as a host material of green phosphorescent Ir(ppy)3 dopant," Synthetic Metals, vol. 158, no. 14, pp. 565–571, 2008. View at Publisher · View at Google Scholar · View at Scopus
- H. Saito, S. Ukai, S. Iwatsuki, T. Itoh, and M. Kubo, "Synthesis of soluble poly(arylenevinylene)s carrying various heterocycles as arylene units," Macromolecules, vol. 28, no. 24, pp. 8363–8367, 1995. View at Google Scholar · View at Scopus
- X. Zhang, X. Yu, Y. Sun et al., "Synthesis and nonlinear optical properties of two new two-photon initiators: triphenylamine derivatives," Optical Materials, vol. 28, no. 12, pp. 1366–1371, 2006. View at Publisher · View at Google Scholar · View at Scopus
- E. Campaigne and W. L. Archer, "The use of dimethylformamide as a formylation reagent," Journal of the American Chemical Society, vol. 75, no. 4, pp. 989–991, 1953. View at Google Scholar · View at Scopus
- F. H. C. Stewart, "The Preparation of some surface active alcohols containing the anthracene nucleus," Australian Journal of Chemistry, vol. 13, no. 4, pp. 478–487, 1960. View at Publisher · View at Google Scholar
- R. Sander, V. Stuempflen, J. H. Wendorff, and A. Greiner, "Synthesis, properties, and guest-host systems of triphenylamine-based oligo(arylenevinylene)s: advanced materials for LED applications," Macromolecules, vol. 29, no. 24, pp. 7705–7708, 1996. View at Publisher · View at Google Scholar · View at Scopus
- X. Zhang, X. Yu, J. Yao, and M. Jiang, "Synthesis and nonlinear optical properties of two three-branched two-photon polymerization initiators," Synthetic Metals, vol. 158, no. 21–24, pp. 964–968, 2008. View at Publisher · View at Google Scholar · View at Scopus
- M. J. Plater and T. Jackson, "Polyaromatic amines. Part 3: synthesis of poly(diarylamino)styrenes and related compounds," Tetrahedron, vol. 59, no. 25, pp. 4673–4685, 2003. View at Publisher · View at Google Scholar · View at Scopus
- A. Heller, "Organic liquid scintillators. VI. Substituted distyrylbenzenes: scintillation properties and spectra of absorption and fluorescence," The Journal of Chemical Physics, vol. 40, no. 10, pp. 2839–2850, 1964. View at Google Scholar · View at Scopus
- H. Y. Wang, G. Chen, X. P. Xu, H. Chen, and S. J. Ji, "The synthesis and photophysical properties of novel poly(diarylamino) styrenes," Dyes and Pigments, vol. 88, no. 3, pp. 358–365, 2011. View at Publisher · View at Google Scholar · View at Scopus
- Y. Jiang, J. Y. Wang, Y. Ma, Y. X. Cui, Q. F. Zhou, and J. Pei, "Large rigid blue-emitting π-conjugated stilbenoid-based dendrimers: synthesis and properties," Organic Letters, vol. 8, no. 19, pp. 4287–4290, 2006. View at Publisher · View at Google Scholar · View at Scopus
- E. T. Seo, R. F. Nelson, J. M. Fritsch, L. S. Marcoux, D. W. Leedy, and R. N. Adams, "Anodic oxidation pathways of aromatic amines. Electrochemical and electron paramagnetic resonance studies," Journal of the American Chemical Society, vol. 88, no. 15, pp. 3498–3503, 1966. View at Google Scholar · View at Scopus
- S. C. Creason, J. Wheeler, and R. F. Nelson, "Electrochemical and spectroscopic studies of cation radicals. I. Coupling rates of 4-substituted triphenylaminium ions," Journal of Organic Chemistry, vol. 37, no. 26, pp. 4440–4446, 1972. View at Google Scholar · View at Scopus
- K. Y. Chiu, T. X. Su, J. H. Li, T. H. Lin, G. S. Liou, and S. H. Cheng, "Novel trends of electrochemical oxidation of amino-substituted triphenylamine derivatives," Journal of Electroanalytical Chemistry, vol. 575, no. 1, pp. 95–101, 2005. View at Publisher · View at Google Scholar · View at Scopus
- L. Vacareanu and M. Grigoras, "Electrochemical characterization of arylene vinylene oligomers containing triphenylamine and carbazole units," Journal of Applied Electrochemistry, vol. 40, no. 11, pp. 1967–1975, 2010. View at Publisher · View at Google Scholar · View at Scopus


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As the Marie Claire team haggles with publicists and argues with each other about who will grace our April cover (hint: the person I am rooting for has NEVER appeared on our cover before) I thought I'd share with you some of the best magazine covers in South Africa of all time.
Original DRUM magazine covers from the 40s, 50s and 60s are considered collector's items these days – so if you can root one out of your granny's attic you could find yourself minted.
Joburg-based readers should make an effort to get to the BaileySeippel Gallery (Arts On Main, 260 Fox St, CBD from today till Sunday 7 February) to see a selection of limited edition Drum Magazine A1 size, archival pigment prints. The covers on display come from a collection in the archives at BAHA (Bailey's African History Archive) and are an opportunity to see images, from that time, that are otherwise not yet easily available to the public.
Lori Cohen

subset: commoncrawl


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Cord was named for his uncle Corder Vineyard. He was born in a log house, that was located in the Wash Bottom, behind Glen Moore's house on East Piney Road. Little is known of his life, other than the fact he was a 'country boy', and he evidently was influenced by his father who had fought under Andrew Jackson in the Indian Wars, since he entered Company H, 11th Regiment of Tennessee Infantry, Army, CSA, 1 May 1861, under the command of CPT Thedford (later Col), COL G.W. Gordon, Lt Col Long, MAJ P.V. Weems, CPT F.P. Tidwell (Company Cdr). He was wounded by a shot to the right shoulder blade. The shot split on the scapular bone mist passing in the lungs. The other trussing down the muscle of the back near the spine. The Regimental Surgeon W.B. Maney, when he examined him after Cord was wounded stated it was his opinion that a mortal wound had been received, and he did not amputate the right arm. Dr. Maney later reaffirmed his opinion in a sworn statement date 26 September 1892. J.K. Clifton & B.A. Clifton, along with C. Slayden, M.D., witnessed Cord's Disability Application of 29 August 1892. J.K. & B.A. Clifton were in the same battle with Cord, since J.K. stated he carried him from the battle field, and B.A. Clifton stated he was present when Cord was shot and was the first man to brush the flies off of him. Both of the Cliftons stated that they had known Cord ever since they were paroled, and that he has not been able to do manual labor at any time and he was a good soldier. C.T. Weems is buried in the Weems' Cemetery, located on the hill above his old farm, just off of East Piney Road. COL Thedford is buried in the Woodard Cemetery, which is located on a hill behind the Yates, and just a short distance from where he lived out his last years on East Piney Road.
Cord learned a sign to give railroad conductors from one of his army buddies, and after he had recovered from his wounds, he traveled each fall to visit relatives located in Rome, Georgia; Oklahoma; and other places. He never did tell where he traveled, he would simply state, "all of the folks of doing fine."
Fought in Indian Wars under General Andrew Jackson. Came to Dickson County Tennessee for part he fought in Indian Wars in Florida in 1838.
The story was told by Cousin Mintie that Tup was out hunting one day, and was attacked by Indians. He was able to hold them off for a while, but was at the point of being killed, when another hunter happened by and together they bested the Indians. The rescuing hunter then gave the Indian scalps to Tup. Cousin Mintie said she remembered playing with those scalps and some old confederate money, when she was just a child.
Another story of Tup was that he went to the garden to pick some turnips for dinner. While he was at the garden some neighbor men came by and said they were going to fight the Indians with Andy Jackson. Tup left with them, and one year to the day returned through the garden, picked a mess of turnips, and went back to the house. Upon entering the house, he placed the turnips on the table, and his wife picked them up and washed and cooked them -- but, she never did ask where he had been or what he had been doing!
Tup was evidently a rough frontier man, since he drank and played cards. Grandpa Cord (C.T.) Weems was a religious man and did not approve of such, so he seldom visited his father, and highly disapproved of his children going there.
[NI0027] Birth date of Philisia Weems and James Howell Weems was recorded in Family Bible of James Yates. Mary Carson Weems was the first wife of Jackson Morgan Yates.
Nancy Ann Frances Jones was the daughter of Isaac Newton Jones, who was the son of Izme Jones, who in turn was the son of Issac Newton Jones. Although My grandfather and his two sisters stood to inherit part of their grandfather's farm, they were told by Lawyer Black that they had filed too late, and therefor would not receive anything.
Nancy was a school teacher, and was also somewhat of a prankster. It was told that when Aunt France (Yates) Weems was laying corpse in the "old Weems Mansion" , Nancy, who bore a close resemblance to Aunt France, sneaked out of the kitchen side of the house, went around to the stairs and up to the loft room to get a bed sheet. She then put the sheet around her face and went up to the kitchen window, where the other ladies were still washing dishes. She threw such a fright into them, and they created such a comotion, that the men sitting in the other side of the house with the deceased ran over to check. In the process of leaving the room, one of the men grabbed a shotgun, and upon seeing my great grandmother, took a shot as she went running East into the cornfield. I never heard whether or not she was hit, but she did manage to get the sheet back to the room and then she reappeared in the turmoil inquiring about what had taken place.
Evidently Dalton and Eunora took after their mother. Both of them were pranksters, and when visiting each other at family reunions, I remember they would look at each other and start giggling, and individually they would pick at the grandchildren.
Although James Yates died in 1880, it was not until the year 1884 that his heirs completed, as indicated on pages 133 thru 136 of Book T, Dickson County Registrars Office: "For the consideration of Thirty Dollars, to each one of the heirs, in hand paid, we have this day bargained, sold, and do hereby transfer and convey unto G.C. Redden, his heirs and assigns forever, all our undivided interest in a tract of land lying in the State of Tennessee, Dickson County, District No2, known as the James Yates farm, and subject to the widows dower, bounded on the North by Tim Petty, and East by him, on the South by Loftis, and West Horner. To have and to hold the said undivided interest in said land to said G.C. Redden, his heirs and assigns forever, we bind ourselves, our heirs, and representative to warrant and defend the title to the same undivided interest the lawful claims of persons whatever this the 18th day of July 1884.
Signed : Aidy Donagan (his mark), M. Yates , J. M. Yates, T.A. Yates (her mark)
John M. Yates, Mary J. Yates (her mark), J.H. Yates, Annie Yates, Isaac O. Yates, E.J. Yates, B. H. Yates, W.M. Yates, S.V. Yates, Suffrona Holland (her mark), Nancy Holland (her mark), C.R. Yates, R.P. Nall, Jas. W. Nall, Witnessed by: A. Myatt (Notary), E. Y. Andrews, A.C. Donagan, Aadoline Donagan.
The original house, which James built in the 1820's, was still standing in the 1970's. The Family Graveyard is located south of the house, and was kept up by Aunt Ola Kimbro's son, Carl. James, his wives and younger children, and Charles Riley (C.R.) Yates, are buried there. Isom and Dicey were buried in a graveyard just past the family plots, and their grandson Sherman had just died , when I started to do the family geneology in 1969. Gail Yates.
Known to family members as 'Aunt France', she was crippled and sat in a rocking chair which had been equipped with casters for her to move around.
Nancy Ann Frances Jones Yates was said to have strongly favored Aunt France.
At Chillicothe, Missouri, Uncle Britt mustered out of the 4th Provisional Regiment, Missouri Militia, he had entered during the Civil War as a drummer, or musician . He was going home to Kentucky, after he mustered out. After walking all day in the hot sun, and missing the ferry, he decided that the Mississippi River was low enough for him to swim across. After walking upriver for a short distance, he ducked behind some bushes, stripped off his clothes, tied them in a bundle, placed them on his head, and then swam across the Mississippi River just above Memphis, Tennessee. He then put his clothes back on and walked home to Pilot Oak, Kentucky, or to his brother James Henry Yates' house.
Uncle Britt owned a cabinet shop at Pilot Oak, KY, for several years, and made quilt boxes of walnut boards, and those were held together with wooden pegs.
He was a dead shot, since he hit anything he aimed at to shoot. Uncle Aubrey Luther held Uncle Britt as a hero. My father said Uncle Britt could jump in the air, click his heels three times, and take off at a run, and that was when he was in either his 60's or 70's. He said all of the young people were soft . Uncle Britt moved to Poplar Bluff, Missouri, from Kentucky, and lived there until his death.
Marriage records of Dickson County Tennessee show he married Daminty Pistol. I have not been able to find other records to verify who S.V. was.
When Jethro was about 12 years old, he hired out to work for an older couple that did not have any children. Their farm was located either around Newport or Jonesboro, Tennessee. He was to be paid one dollar per month, in addition to his room and board. At the end of that year, he had done such a fine job for them, that they paid him an extra dollar, making a total of thirteen dollars for the year of work. Now for the year of 1795, that was good payment, but it was also the only year that the State of Franklin was in existence. That thirteen dollars was in paper money, and it belonged to the Bank of the State of Franklin. Jethro carried that money with him the rest of his life, and he would state that it was one of the most valuable lessons that he ever learned. Jethro moved to Dickson County Tennessee in about 1836, and worked with a man names Spencer in a gunpowder mill located on Nails Creek, just off of Highway 46 in Dickson. Jethro smoked a corncob pipe, and it is believed that since the bowl would flip around as he was smoking the burning tobacco fell out and set off an explosion that killed him in October 1851. Jethro was uneducated, since he could not write; however, his prior planning of transferring land and slaves to his children was recorded on 23 March 1846.
"For the love and affection I entertain for Rosey McGhee my daughter, I do hereby give, transfer, and convey to her a negro girl by the name of Dicey, in the County of Dickson, Tennessee, District No 2, to have and to hold the same to the said Rosey McGhee, her heirs, and assigns forever. I covenant and agree for myself and heirs to warrant and defend the title to the said Negro Girl to the said Rosey McGhee, her heirs and assigns against the lawful claims of all persons, whtsoever, this 25th day of March 1846. Jethro (X) Yates (his mark). Witnessed by James and William Thedford.
"For the love and affection I entertain for Fanning Yates, my son, I do hereby give and transfer and convey to him a Negro Girl, by the name of Gilley, in the County of Dickson, Tennessee, District No 2, to have and to hold the same to the said Fanning Yates, his heirs and assigns forever. I do covenant and agree for myself and heirs to Warrant and defend the title to the said Negro Girl
to the said Fanning Yates, his heirs and assigns against the lawul claims of all persons whatever, this 25th day of March 1846. Jethro (X) Yates (his mark)
Witnessed by James and William Thedford.
"For the love and affection I entertain for James Yates, my son, I do hereby give, transfer, and convey to him two Negroes, one named Isum, the other named Martha, in the County of Dickson, Tennessee, District No 2, to have and to hold the same to the same James Yates, his heirs and assigns forever. I
covenant and agree for myself and heirs to warrant and defend the title to the said negro to the said James Yates his heirs and assigns, against the lawful claims of all persons whatever, this 25th day of March 1846. Jethro (X) Yates
(his mark), Witnessed by James and William Thedford.
"For the love and affection I entertain for my son John Yates, I do hereby give and transfer and convey to him a certain part of my tract of land in Dickson County Tennessee, District No. 2, containing by estimation one hundred acres and bounded as follows, to wit: Beginning at a stake in the East boundary line of John T. Cliftons old tract of land, runs South with said Cliftons line 61 3/4 poles passing an Elm, the South West Corner of a fifty acre tract deeded to Wiley Myatt by Kendrick Myatt, thence with a marked line south, supposed to be 50 poles to a Red Oak, thence East 34 poles to a Black Walnut,thence North one pole to a hickory, thence East one hundred and forty five poles and 3/4 to a White Oak, thence North supposed to be one hundred and fifteen poles to a Black Walnut, Thence West one hundred 30 1/2 poles to the Beginning, to have and to hold the same to the said John Yates, his heirs and assigns forever, I covenant and agree for myself and heirs to warrant and forever defend the title to the said tract of land to the said John Yates, his heirs and assigns against the lawful claims of all persons whatever, this the 15th day of June 1846. JETHRO(his mark) YATES
Test: Mosses Tidwell
J.C. Rye STATE OF TENNESSEE, Dickson County, Personally appeared before me Thomas McNeilly, Jethro Yates with whom I am personally acquainted and who acknowledged that he executed the foregoing deed for the purposes this in contained, Witness my hand at office this 15th June 1846 THOMAS McNEILLY
STATE OF TENNESSEE: Registers office June 19th 1846. 3 O'Clock P.M. then was the foregoing deed of Gift with the clerks certificate thereon received and noted in Note Book A, page 28, and Recorded June 19th 1846 in Book I page 114 & 115. Henry A. Bibb, Register
For the love and affection I entertain for Fanning Yates, I do hereby give, transfer, and convey to him a part of my tract of land in Dickson County Tennessee District No 2 containing by estimation Fifty acres and bounded as follows, to wit: Beginning on a Whit Oak running North fifty five poles to a White Oak, Thence West one hundred forty five 1/3 poles to a Hickory. Thence South fifty five poles to a Red Oak. Thence East one hundred and forty five 1/3 poles to the Beginning to have and to hold the same to the said Fanning Yates, his heirs to warrant and forever defend the title to the said tract of land to the said Fanning Yates, his heirs and assigns against the lawful claims of all persons whatsoever this the 15th day of June 1846.
TEST: Moses Tidwell JETHRO (his mark) YATES
J.C. Rye
STATE OF TENNESSEE DICKSON COUNTY Personally appeared before me Thomas McNeilly, Clerk of the County Court of said County, Jethro Yates with whom I am personally acquainted and who acknowledged that he executed the foregoing deed for the purposes therein contained Witness my hand at office this 15th June 1846. Thomas McNeilly
DICKSON COUNTY Registers Office June 19th 1846 3 O'Clock P.M. then was the foregoing deed of gift with the Clerks Certificate thereon executed, recorded, and noted in Note Book A page 2 and Recorded June 19th 1846 in Book I page 115 Henry A. Bibb Regs
April 6, 1846
State of Kentucky, Graves County
Dear Father, Friends, and connections
We are in tolerable health at present, hoping these few lines may find you all enjoying the good blessings. James, I don't know how he is just now. He lives over in district 75, and I have no letter just now from him. Dear father, I want you to summon up your recollection as well as you possibly can about the money that you paid Jonathan Johnson--------------------------and the 50cents ------
lines missing -- Bid your part and the 20$ was for payment for all of which he paid away to Nappier, he said when he came back he told me all about it, and told me he would credit my note that he held against me for John's land for 35$ (he never gave me no credit. And unless you will go before the Magistrate of that county and make oath of the money I shall have it to loose and pay again by the law of this county. I want you if you please to do it and send your deposition here in a letter as soon as possible. I would be very glad to come and see you all if it were in my power but James is gone and there is no way to do anything at all. Jonathans family is gone to Arkansas and have left John Henry here to get along as he can, We desire to be remembered to you all inquiring friends, so no more at present remembering yours J.A. Henry H. Cole and Fannie
Major Jethro Yates, I want you to fix this matter amediately and yours sir will state the deposition and send it in a letter. I shall think it very hard to pay that money twice and take care of John at last.
Major Jethro was Buried at the intersection of Nails Creek Road and Iron Hill Road, which is just east of Highway 46 in Dickson, if you turn south on it from Interstate Highway 40
Miscellaneous NOTES:
Henry Cole married Frances Johnson in Dickson County, 21 Apr 1841
Henry H. Cole married Milly Yates 18 Jan 1817 NC Bondsman Shadrack Cole witness B.A. Barham
Mary Yates married Sterling Beesley 07 Oct 1797 (Sister of Jethro ?) witness J(im) Rice (lived on Hurricane Creek in TN) Bondsman Henry Beesley Bond #000151500
Thomas Yates m. Martha Nickins 20 Sep 1820 Bondsman Jethro Yates (?) Bond #000052843
Matthew Yates m. Elizabeth Baucom 20 Mar 1807 Bondsman Alsey Yates witness William Hill Bond #000159551
NOTE: The first story, above, was handed down through the generations, but is thougth to be actual, since I personally saw and counted the money that was in a leather wallet, along with considerable Confederate money, located at the home of Bertha Redden, on South Main Street in Dickson. Gail Yates.
Major Jethro did not come to Dickson County until circa 1830-40, since he is shown in the 1830 census of Guilford County North Carolina with William, Charley, and Hardy Yates.
[NI0123] John arrived in Dickson Co, about 1851, which coincided with the death of Jethro his father. Jethro wrote his will, and recorded it in Dickson Co, TN. in about March 1846. He named Fanning, Rosey, James, and John as his heirs, so when he died in Oct 1851, his heirs would probably have taken possession of their inheritance.
[NI0126] Fanning Yates was shot by bushwhackers on what is now Highway 96, at the intersection with Turnbull Road. His grave was located where the dam is now for the Turnbull Lake, which caused them to remove the grave to the Gentry Cemetery. The Cemetery is located above the Turnbull Road.
Rosey was given a slave by her father in 1846.
She married O'Kelley McGhee, and they owned a large farm located on old Highway 70S just North of Waverly, Humphreys County, Tennessee. The house and large log barn was situated on the hill across the highway from a limestone operation. The graveyard was located south and east of the barn on top of a hill.
[NI0147] Check for Fannie & Henry Cole. They knew Jethro, Fanning's father, and wrote a letter to him from Kentucky in 1846. Also, John M. Yates, of Wingo , Kentucky, had a son John, who moved to Success, Arkansas. Uncle Brit joked about John having to move to Arkansas to be Succ
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There are fewer and fewer full-service FBOs, the kind that offer charter, maintenance and even a flying school in addition to fuel and aircraft storage. And those that survive usually aren't found at one of the airports serving a major metropolitan area such as New York City. Panorama Flight Service is one of that rare breed, and in April the FBO celebrated its 50th year in business at Westchester County Airport in White Plains, N.Y. To mark the anniversary, Panorama held an open house that drew more than 1,500 people from the local area. "We picked up 10 students, half a dozen real prospects for ownership and probably a couple of good prospects for jet charter," said Panorama president Gene Condreras.
Condreras' stepfather Ted Healy and his father, Ted Sr., started the company in 1958 as a sightseeing operation offering rides over New York City's "asphalt jungle." Under the younger Healy's guidance this grew into a large charter and maintenance business, and the FBO was opened in 1981. In 2002 Panorama completed a 10,800-sq-ft FBO/office terminal on a 21-acre site at Westchester County Airport. The facility includes a 20,000-sq-ft main hangar, two 3,500-sq-ft clear-span hangars and 32 T-hangars. Condreras has worked for Panorama in almost every capacity since he started there more than 25 years ago, and although he has had an enormous influence over Panorama's success, he attributes the company's growth to Panorama's 70 employees. "It's all about being a good listener," he said, "hearing what's important to the customer and being fair and honest. It's not rocket science."


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Draft Update: Taylor Hall
Although most Oiler fans seem to be leaning toward Tyler Seguin as the #1 choice in this summer's entry draft, Taylor Hall is most certainly in the conversation. A recent tsn article had some nice quotes from the kid, including this gem:
- "Whether I go one or two, it doesn't matter to me," he explained. "But hopefully through these playoffs I'll be able to show Edmonton that I'm their guy and I can go number one."
I know that these kids are trained to say the right thing, but it is still nice to hear an elite talent mention the Oilers in a positive fashion.


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Codemasters have sent out emails to all their users informing them of a hacking incident that happened on June 3rd.
In the email they reveal that unauthorised entry was gained to the Codemasters.com website and this was shut down as soon as it was detected but have revealed that both their Estore and CodeM services were compromised as well as the codemasters.com website and the DiRT 3 VIP code redemption page.
According to the company, hackers were able to access Customer names and addresses, email addresses, telephone numbers, encrypted passwords and order history via the Estore, however no credit card information was accessible as they use a 3rd party for payments.
For CodeM users, they believe hackers were able to access Members' names, usernames, screen names, email addresses, date of birth, encrypted passwords, newsletter preferences, any biographies entered by users, details of last site activity, IP addresses and Xbox Live Gamertags.
As with any hacking incident, they suggest users change any passwords associated with other Codemasters accounts and on other sites and to be vigilant when receiving calls and emails from people claiming to be from Codemasters.
Codemasters have redirected all site traffic to their facebook page and announced a new site will be coming later this year.


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Internet giant Google is coming to Maldon armed with advice for businesses.
Maldon MP John Whittingdale has secured a Google Juice Bar for the town, which will see Google representatives give free digital consultations in a bid to help local firms make the most of the web.
Business are encouraged to contact Maldon District Council on 01621 854477 to sign up for the event, set to take place from 10am until 2pm on Friday at the council offices in Princes Road.


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Dave Challenges Andy To The Extreme Burger Challenge At Swifty's In Utica
I've challenged our very own Andy Cash to Swifty's of world famous Extreme Burger Challenge here in Utica. Why? Because what are friends for?
According to Swifty's, here's what Andy and I are in store for:
3 of our 1/2 lb signature burgers stacked on top of each other: Jack Burger, Cowboy Burger and Swifty's Buffalo burger (burger deep fried and smothered in hot sauce). Finish eating the entire burger PLUS side of fries/gravy in 30 minutes and win Swifty's Swag, bragging rights and an induction to the Swiftys Wall of Fame!"
I've been training for this moment my whole life.
We will have a video uploaded this weekend with the results.


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BUT if we were to accept your idea as a hypothetical we are still faced with this: there is a difference between making your money back, making profit and making big bucks profit.
Now I'm not sure which one CG would fall underneath for Mattel because...well frankly none of us have the books for Mattel's finances. But hypothetical....in a typical business model the only way a company could go on to produce such another giant product would be with the financial momentum after making "big bucks profit."
Personally....I wish this is the case because I would love a Snake MT
CHECK OUT MY BRAND NEW WEBSITE for my Akil and Saltfish comic strip, more to come soon!
I've got everything that I need, right in front of me! Life's a happy song people!
Fear is faith in failure
Now obviously things have changed because back then the line was untested and the market response was unknown. However the same basic principal exists as you pointed out- present sales and profit predict future product
Comparing retail to sub doesn't really work. If Mattel ever brings MOTU to retail, for a movie release or whatever, you can expect exactly this approach, loads of goofy colored missile firing he-men. It's not just Hasbro, this is what pretty much every toy company with a big retail presence does, flood the market with the big names to draw in the kids and parents. One need only look at the Mattel DC retail lines for an idea of what you'd get. Despite the cruddy distribution, I still don't think anything of Mattels retail boys lines compares to anything Hasbro is putting out. Even Hasbros 5 poa figures look better than most of Mattels similar products. Aside from the 4H, Mattels sculpters just don't seem comparable to me.
UNLESS you want to consider the Marvel Universe 3.75 as a 'reboot' of the secret Wars toys... That's kind of how they started... Still, I have had a LOT more quality control issues with THOSE then I do with MOTUC...
Soooo yeah, I'm happy with how Mattel runs it (mostly... I STILL hate the sub only philosophy...) but saying Hasbro would do it better... I see no evidence of that.
While I don't think Hasbro would be able to do better, I do believe you'd be able to walk into a store and probably find multiple lines, both collector and kid focused, or the remnants of them anyway, and you'd probably have a new tv series as well to accompany a line for whatever that show is. And would goofy colored missile firing He-Man really be so bad if it were bringing some fresh blood into the Masters of the Universe? Sure distribution is spotty, but how is ordering a set of & figures off of BBTS much different than subbing up and receiving a figure every month? Now personally, I have no desire to see Hasbro take over the He-Man license, nor would it ever happen, but there's no denying that Mattel could do more with it than they are. A niche line like this is not the best option when it comes to long term exposure of a brand. How much more might we get and for less, if there was some cheapy kiddie line on the side helping to pay for the bigger stuff? Say what you will about the transformers movies and toys, but it's because of those that we get great figures like Deluxe Waspinator and Voyager Rhinox and countless others from the Classics Generations series. If the Joe movies and lines had done better, I've no doubt we'd see a ton more of the classic stuff from that line as well. If we're lucky enough that this line is still going whenever the Masters film finally happens, I have no doubt you might start hearing that a Snake Mountain is possible after all.
And they didn't do a GREAT job of bringing in the new blood...
I don't doubt they would have TRIED a new series or something... but Hasbro doesn't seem to stick with them much. GI Joe keeps trying, but they abandon each direction pretty fast.
We'd see something like this if you did tha:
MICHAEL BAY PRESENTS: A MICHAEL BAY production. In a world where an evil corporation has taken over New York, there is only one hope: THE MASTERS OF THE UNIVERSE: THE RISE OF HE-MAN, starring CHANNING TATUM as Adam, a down on his luck New York bartender who finds the magical wise-cracking POWER SWORD (voiced by Kevin Hart) after a meteor crashes into his back yard. Granting him mysterious techno powers through a nano-grafted POWER-SUIT (tm), Adam becomes He-Man, heroic vigilante. With help from the mysterious love interest TEELA played by RIHANNA, Adam must defeat the evil GRAYSKULL CORPORATION and it's alien CEO SKELETOR (MARK WAHLBERG) . Coming this Fall to a theatre near you.
Last edited by SonOfHeMan; June 12, 2014 at 09:48pm.
200x did bring in new blood. Do you think everyone single member of this board are only vintage and filmation fans? I'm willing to bet there's a good amount of members here that for them 200x was their first encounter with He-Man and made them fans. And while I can't argue that ridiculous variants helped do in the 200x line, it was more the ridiculous amount they were packing per case in comparison to new characters as opposed to their existence in general. Don't forget, back in the vintage days, things like Thunderpunch He-Man and Dragon Blaster Skeletor were some of those "goofy variants". The trick is to balance it out and not pack them 3 per case every case and toss in a Teela as an afterthought. As for that Michael Bay movie, regardless of the quality, if it made a ton of money, you can bet the Classics stuff we could get would be greatly expanded as a result. I don't see how that's not a win win situation, regardless of the quality of the film itself. Trans fans got a giant transformable Metroplex last year, you can bet that wouldn't have happened without the boost in revenue from the films. The same could happen for MOTUC, and items like Snake Mountain.
The same as all the modern retail lines do.
The things that killed the 200x line... are the SAME things that they complain about on the Marvel Universe websites right now.
Honestly, I have a hard time ever encouraging BAD media or 'Expansion for the sake of expansion'
Eventually something becomes unrecognizable and its simply not the same property anymore.
I consider Bayformers (despite hating that term...) to be on par with New Adventures. Similar names... similar tropes... completely unrecognizable in appearance or attitude or lore. Just saying YEAH... but they made another show!!! DOESN'T really excite me too much if I don't LIKE the media or the direction.
And the way new media has a way of taking over and pushing out the 'core' entities... and becoming the 'real' version... I don't know. I just can't buy into it.
I collect Marvel universe quite enthusiasticly, and frequent several boards for that particular line, and character variants never really comes up as a complaint, most I've spoken to see it as a necessary evil, retail wants the big names, it's how we get the Deaths Heads and Whirlwinds. The case pack outs however, and including Iron Man version X at 3 per case in wave one, and then again in wave 2, seems to be the thing that causes frustration, and it's what creates the back log. There's a balancing act there, and it's tricky. Include too many C listers per case and you end up with just as much of a clog as if you packed a ton of Iron Men. in my neck of the woods we're drowning in Black Knights and Auroras right now, both great figures, but over saturated unfortunately. If MOTUC was retail, you'd have the chances of even the hard core, highly sought after figures becoming peg warmers. If you had a case of 4 He-Mans and 4 Shadow Weavers and 4 Two Bads for example, and a store got in a couple cases, you'd have them sitting after a while, regardless of how well done the figures are.
As for new media, I'm not trying to convince you that new media is great, but if having that new media existing and being successful could make a Classics Snake Mountain possible, wouldn't it be worth it? A cruddy product we can ignore, so that we can get something we do want? Seems like a good trade off to me. And for every cruddy bayformers, you occasionally get a gem, like Beast Wars or Transformers Animated.
When the new Marvel Infinte line was announced with the bleeding Edge Iron Man and the Captain America we JUST got and Wasp was (I think) one per case... the board I was on just lit UP.... Everyone couldn't fathom the idea of the immediate rereleases and accused Hasbro of trying to kill the lien!!!
And There's always the issue with Marvel 3.75 competing with itself with 3 movie lines, a spiderman line and general line all putting out the same character at the same time... but that's a different complaint
Reminds me of 200x. We had new media... and while we got one variant of He-man with his tradional iron cross harness... we didn't get a classic looking Grayskull... we got the 200x grayskull. Which I didn't bother buying...
It's possible we would get some new things that were inspired by the vintage stuff... but new media tends to overwhelm the old. it gets pushed hard at the customers to the exclusion of most everything else.
Transformers does a LITTLE better. We still see the occasional G1 influenced thing, but most of it is either Movie or 'TF Prime' stuff.
I kinda like the game show host Castle Grayskull... "Skeletor! YOU are not WELCOME here!......A New CAAAR!!!"
Now, I'm not saying their slowness freaking folks out was OK for DR to do, or any thing of the sort - it's DR. But, the folks that actually had them cancelled because of the "wrong card updated" issue was isolated to only those folks who called during the year to change the cards, because DR hadn't trained them that the card number was baked into the original orders, and changing it elsewhere wasn't changing a thing. Totally their fault, again, though - not defending that, just being realistic as to the only folks that would have actually been affected.
Regardless, this is all moot - because (see below) they took cancellations well into the production process and until only a few months before release because of the broken promises that they made. They used the "hey we are offering refunds!" as the mantra excuse when folks pointed out their dissatisfaction at the changes. So if they called or emailed to cancel, or just let their cards lapse, Mattel still would have made the same amount of Castles and would have been stuck with the same number of them largely by their own doing.
He has made himself the face of the brand. Paul, Joe, and Bob aren't trying to style themselves with "celebrity" status and soak up the limelight but pretend the shadow he casts is someone elses fault. His choice to be that "visible" person. There are a myriad of reasons he brings it on himself, mostly because his foot seems to naturally want to slide into his mouth and he often makes minor things turn into big controversies just by opening his mouth more, but that's all been well-documented and isn't worth going blow by blow and repeating here.
Did a search on this thread for 'cancel CC' and got 359 hits. Some for the idea, some against it in the way that Forum conversations go. But they go back LONG before the DR mess up almost as far back as the Castle announcement.
Things like this....
Still it happens every time there is a sub drive that people think this is clever, and then the mods come on to try to nip that kind of talk in the bud.
I believe Scott said that Mattel did check with individuals ordering multiple castles to ensure they were legit. Not sure what they did, but I don't think they just took orders for 5000 castles at face value.
I serve up lots of hot, fresh action figure reviews on Action Figure Barbecue!
"We have a Ram-Man"
Personally, I admire him specifically for making himself the face of the brand- Not for "celebrity status" but so Paul, Joe, and Bob can do their jobs without being witched at & demoralized from every corner of the internet. This whole one-on-one online interaction between company and customer has been an interesting new frontier to see played out over the years. Taking the heat and criticism for issues regarding product seems part of that job and he shoulders it pretty well in my opinion. Both for issues that are the company's fault and those that aren't. There may be other examples out there, but this is one of the first times I've seen this kind of business paradigm. It has both it's advantages and flaws to be sure but speaking only for myself, I think it's been a worthy experiment so far.He has made himself the face of the brand. Paul, Joe, and Bob aren't trying to style themselves with "celebrity" status and soak up the limelight but pretend the shadow he casts is someone elses fault. His choice to be that "visible" person. There are a myriad of reasons he brings it on himself, mostly because his foot seems to naturally want to slide into his mouth and he often makes minor things turn into big controversies just by opening his mouth more, but that's all been well-documented and isn't worth going blow by blow and repeating here.
I call this opinion because unless you are gifted with infinite wisdom which allows you to transcend your own opinions and biases to see things from a different perspective than you cannot ground anything which you said in truth. Here is the plain simple fact: You see a media advertisement, you interpret it and you respond. The second part is where everyone gets in trouble because its the interpretation which is subjective and therefore not a valid indicator of reality. And as much as you or anyone else can deny, it's science and I'd be more than happy to PM you any articles or supporting documentation if you care to challenge this because not only have I read them, I actively study them within my profession.
So the internet and all of it's ongoing commentary which you call "documentation" is realistically a huge melting pot of personal interpretations and opinions. Which is FINE, that's what forums are for. They bring people together to discuss topics. But it is no way, shape or form a body of evidence which can be used to glorify to vilify somebody because they are still just opinions.
And until someone is given the magical power of seeing reality for it's objective nature and provide us with facts and not their opinions or interpretations of what is happening and how we should judge TG, then we have to come to the simple conclusion that we don't have any clue about Mattel's inner workings, TG's occupational or personal decisions or anything basically.
Looks like Matty still has 918 in stock.
I imagine if snake mountain is a go,that will drain the total quite a bit.
Comedian on the matty forums.
Maybe if they offer a bundle with a little discount.
Contact BadVermin for all your customs and repaints.
Hey, without digging through 186 pages, is there a way to plug this one chain with a plug that came with the castle castle somewhere? I just bought one from Matty collector, and I'm trying to assemble it.


text: 'D1 Ultimate-GT & Top Gear Finland Supercar Event' PHOTOGRAPHY: razzi.me Matte black 2011 LUMMA BMW X6M CLR X 650 M overview, start-up, small revs and lovely exhaust sound. This SUV beast also races down the track at full throttle and drag races against the Mercedes SLS AMG Roadster and Ferrari 458 Spider. Filmed at the 'D1 Ultimate-GT & Top Gear Finland Supercar Event'. Enjoy! Specs: modified 4.4L twin-turbo V8 650 hp (478 kW) 830 Nm (612 Ft-Lbs) Top speed 312 km/h (194 mph) 0-62 mph in 4.5 seconds www.ultimate-gt.com | http Location: Kiikala Airfield, Finland Watch in High Definition (1080p HD). RATE, COMMENT & SUBSCRIBE! Jamboolio's automotive PHOTOGRAPHY: razzi.me Follow Jamboolio on TWITTER: twitter.com


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DEVIL YOU KNOW - Capital Chaos TV Footage From San Francisco Show Available
June 18, 2014, 3 years ago
Devil You Know, the creative union of Howard Jones (ex-Killswitch Engage), Francesco Artusato (All Shall Perish) and John Sankey (Devolved), recently performed at the Regency Ballroom in San Francisco and Capital Chaos TV was on hand to catch the action:
Devil You Know recently released their album The Beauty Of Destruction on Nuclear Blast Entertainment in North America. The record came in at #45 on the US Billboard Top 200 Chart and at #3 on the Hard Rock Chart, in its first week of sales according to Nielson Soundscan."No matter how much work we've done in the past, or how much success any of us have had in our prior bands," state the boys from their current tour with Black Label Society and Down, "we are all excited how things have come together for Devil You Know on record, on the road and with a very strong first week sales! It is a true new beginning indeed!"
The Beauty Of Destruction was produced by Logan Mader (Five Finger Death Punch, Gojira) and mixed by none other than acclaimed producer/mixer Chris "Zeuss" Harris (Hatebreed, Chelsea Grin). Artwork was created by noted painter and illustrator Travis Smith (Opeth, Devin Townsend).
The Beauty Of Destruction tracklisting:"A New Beginning"
"My Own"
"Embracing The Torture"
"For The Dead And Broken"
"Seven Years Alone"
"It's Over"
"A Mind Insane"
"Crawl From The Dark"
"The Killer"
"I Am The Nothing"
"Shut It Down"
"As Bright As The Darkness"
"Sacrifice" (bonus track – vinyl LP only)
Album stream:
"Seven Years Alone" video:
"A New Beginning" lyric video:
Devil You Know is:
Howard Jones (Ex-Killswitch Engage, Blood Has Been Shed) - vocals
Francesco Artusato (All Shall Perish, The Francesco Artusato Project) - guitar
John Sankey (Devolved, Fear Factory, Divine Heresy) - drums
Ryan Wombacher (Bleeding Through) - bass
Roy Lev-Ari - guitar


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Toddlers & Preschoolers love "doing school" and creating projects of their very own.
Here is a simple, fun, and effective way to help younger children learn about colors.
Learning Colors Book for Toddlers & PreschoolersThis is so simple, just print and fold to make the color book.
Kids will identify the colors and color in the oval on each crayon with the corresponding color.
Then, kids can trace the color word to start working on those fine motor skills they are going to be needing in just a couple years!
More Color Activities for Kids
- Color Flashcards300+ Free Coloring Pages for Kids
- 27 COLORFUL Kids Activities
- My Color Book (different style than above)
Before you download your free pack you agree to the following:
- This set is for personal and classroom use only.
- This printable set may not be sold, hosted, reproduced, or stored on any other website or electronic retrieval system.
- Graphics Purchased and used with permission from ScrappinDoodles License #94836
- All downloadable material provided on this blog is copyright protected.


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Paris: The French government this week unveiled a smartphone app to alert users about possible terror attacks during the tournament. Called SAIP, the app was developed following the Bataclan attacks in November. It can send alerts to users' phones less than 15 minutes after an incident is confirmed, tailoring information to the user's specific geographical location.
Users can share alerts from the app directly on social media. Family and friends can also use the app to check up on their love ones during an attack.
French interior minister Bernard Cazeneuve said SAIP will "keep the public up to date with what we know." The app is available for free, in French and English, for Android and iOS phones.
The city of Paris initially spoke of the possibility of closing down fan zones, public areas where people can watch the matches on cinema-size screens, but after reassurance from the interior ministry, the city confirmed that fan zones will stay open.


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GABRIELLA Bennett is turning back the clock to give Evening Times readers plenty of food for thought.
She's cooking up dishes from recipes which are more than 100 years old as part of a fascinating series on Glasgow's forgotten recipes which she is highlighting in weekly blogs on our website.
Gabriella said: "When the opportunity arose to bring back to life 100-year-old dishes as part of my new series of features - Glasgow's Forgotten Recipes - I bit the editor's hand off at the chance."
It's a challenge the 25-year-old digital journalist is more than willing to take on even though the dishes include brain cakes and fish mould - a far cry from the bananas, peanut butter and yoghurt she would eat as a child.
But the writer, who lives in the shadow of the shipyards at Scotstoun, is made of stern stuff.
She's reviewed some of Scotland's best restaurants over the years and even sampled rare culinary delights such as deconstructed pigs' ears and dollops of sweetcorn ice cream.
Gabriella said: "Athough I'd approach anything still alive with caution - but never say never - I'll try pretty much any weird and wonderful food going.
"Maybe my bravery is to be attributed to my age or maybe I'm just daft but my ability to give anything a go is to be put to the test.
"Did I mention that, as well as cooking the forgotten recipes and sourcing the ingredients which might prove a job in itself, I'll be sampling them too?
"I've had to borrow an old, care-worn copy of The Glasgow Cookery Book to act as my go-to guide,which was first published in 1910. A cursory flick through the book gave even a hardened foodie like myself a shock."
She added: "I'm hoping to find a butcher in the city who can sell me the ingredients needed to resurrect my recipes.
You can follow Gabriella's exploits and discover the family meals made in Glasgow before the First World War at www.eveningtimes.co.uk - if you have the stomach for it.
gordon.thomson@ eveningtimes.co.uk


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A simple weather widget for Geckoboard
This app uses the Yahoo Weather API to fetch current forecast info for your location then converts it into a format that works with Geckoboard's custom text widget.
Built by David Underwood in about 4 hours (including research).
Image by Pat Dalton. Used with permission.
HTML/CSS template by Chris Creed
Email: firstname.lastname@example.com
Blog: The Flying Developer
Twitter: @davefp


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There is a helpful post of Richard MacManus over at Read/Write Web that takes a balanced look at the topic of Bots and Content Creation / Aggregation.
It's a touchy subject for many bloggers who see some automated content creation systems (particularly those that aggregate RSS feeds) as a threat to their own livelihood.
Richard looks at a number of Content Creation systems and ends up taking some middle ground, liking some systems and being very wary of others. It's worth a read as this is a topic we're going to have to grapple with more and more in future. In fact in the past two days I've had emails from 4 different software makers announcing these sorts of packages. In all cases I promptly deleted them as I could see that they were being pretty blatantly marketed to spambloggers.
As Richard notes in his post – systems like these can actually be used in positive and helpful ways (he gives examples) – the problem is that they can also be used to rip off the content of others and to clutter the web. I guess it comes down to the individuals using them to make a call on how they'll approach their content creation.
What do you think about these systems?


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Get Answers to Bird Care Questions. Ask a Bird Specialist.
Most normal pet birds never need to have their beaks trimmed. Many people will mistake the superficial flaking of outer layers for overgrowth. If the beak is actually overgrowing, it could be the result of an injury or deformity, scaly face mites (Cnemodecoptes), or liver disease. One common cause of liver disease in parakeets is obesity, which can result from a combination of genetics, excessive eating of high fat seeds, and lack of exercise.
I would highly recommend that you take the bird to an avian veterinarian for a checkup to see if a cause of the beak overgrowth can be determined. It may be something simple and treatable like the mites, so that once addressed, the beak will not be a problem anymore. As a side note, the mite protectors and sprays you can purchase at the pet store do not work on this type of mite, and are unnecessary in my opinion.
If it is more complex problem, like fatty liver disease from obesity, the vet can talk to you about making gradual changes in the diet, such as offering pellets and dark green leafy vegetables in addition to the seed. The doctor can then safely trim the beak, and may be willing to show you how to do it yourself. Beak trimming requires great care, because if you get it too short, it will not only bleed profusely, but the pain may prevent the bird from eating for several days. Every species has a different normal length, and even if you try to cut the beak to look exactly like a normal parakeet's beak, you may get it too short. Sometimes when the beak grows out, the blood supply will also grow out further than expected.
Here are some sketches and photos of overgrown beaks so you can compare your bird's beak to determine if it is really abnormal:
If you do attempt to trim the beak yourself, the most important thing to know is you must avoid holding the bird too tightly, because if you compress his chest he may not be able to breathe. The next important point is that you should usually trim less than you think you should. He can do okay with a beak that is a little too long, but as I said before, too short can be extremely painful and even life threatening.
Please feel free to write back if you have further questions about this.


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Vaidyaratnam Kesaranjini Thailam: It checks premature greying of hair,dandruff,falling of hair etc.
Usage: Required quantity to applied over the head.For external application only.
Ingredients: Eclipta alba,Phyllanthus emblica,Glycyrrhiza glabra,Abrus precatorius,Embella ribes,Hibiscus rosa-sinensis,Sesame Oil,Milk,Cinnamomum camphora.
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You have to send us DD for the order amount to process the order. Note: We will process your order only on the receipt of payment. In case of Cheque, the order will be processed after the cheque clearance.
Buy Ayurvedic & herbal medicines online.Shop for ayurvedic product, herbal supplements and healthcare products. Swasthyashopee is an online store for all ayurvedic products, ayurvedic cosmetics. We cater most popular brands like Dabur, Baidyanath, Unjha, Emami, Zandu, Ranbaxy..
Disclaimer: All products & Logo copyrights owned by their respective companies / manufacturer.
The information presented at this page is not intended to replace the services of a health practitioner licensed in the diagnosis or treatment of illness or disease. Any application of the material in this text is at the readers discretion and sole responsibility. If you have a persistent medical condition or your symptoms are severe please consult a physician. Statements on this web site about health conditions and remedies have not been evaluated by the U.S. Food and Drug Administration.


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Thumbz is a photo sharing app for your Windows Phone that allows you to... well... share and get feedback on your photos. Once uploaded to the network, other members can vote up, down on your photo as well as leave a comment. You in turn can rate and comment on others photos as well. You can also use Thumbz as a informal public opinion poll if you include a question in the image description.
Thumbz does have a novelty feel to it but it also has the potential to be a decent photo sharing network. It just needs time and to see it's membership continue to grow.


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Date of birth: 28 August 1966
Nationality: Spanish
Playing career: San Sebastián CF, Castilla CF, UD Las Palmas, Real Madrid CF, CD Logroñés, FC Barcelona, Rayo Vallecano de Madrid, Spain
Coaching career: Rayo Vallecano de Madrid, Real Madrid Castilla, Spain Under-19s, Spain Under-20s, Spain Under-21s, FC Porto, Spain
• Lopetegui's promising goalkeeping performances for Real Sociedad de Fútbol's youth sides led to a move to Real Madrid. The Basque native progressed into the senior squad, but, starved of opportunities, switched to Logroñes, where he made 107 Spanish top-flight appearances over three seasons.
• Those displays earned a move to Barcelona but again he found playing time limited, prompting a transfer to Rayo Vallecano, where he featured 112 times until retirement in 2002. He earned one senior international cap and was part of Spain's 1994 FIFA World Cup squad.
• Started his coaching career in 2003/04, at second division Rayo, but the experience was short-lived – he was dismissed after ten games. After five years away from the bench he returned to active duty in 2008/09, with Real Madrid Castilla, ending the campaign in sixth place.
• In 2010 Lopetegui joined the Royal Spanish Football Federation (RFEF) and led the U19s to the European title two years later before reaching the quarter-finals of the FIFA U-20 World Cup in 2013. He had assumed control of the U21s in August 2012 and guided the holders to the 2013 UEFA European Under-21 Championship, winning the title in Israel.
• On 6 May 2014, he returned to club duties with Porto but failed to win any silverware with the club and left his post in January 2016. Appointed Vicente del Bosque's successor as Spain coach in July that year.
©UEFA.com 1998-2017. All rights reserved.


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Reviews - Craighaar Hotel4
1 Waterton Road, Aberdeen, AB21 9HS
Customer Reviews
Our reviews are from genuine LateRooms.com customers. We verify that the customer has stayed before leaving a review.
Very Good
91% would recommend it to a friend
Customer service
Food quality
Room quality
Excellent accommodation if visiting Newhills Bowling Club which is just across the road.
Craighaar Hotel
Nice friendly hotel perfect for a business trip.
Craighaar Hotel
Very good and would gladly stay again
Food and staff great,place to relax or travel into Aberdeen.
Long week-end stay
Stayed from friday until monday,The service was outstanding in all departments,so friendly and polite , even the cleaners were so helpful and nice,Great selection at breakfast time,would recommend the Hotel strongly.
stayed here while visiting family
I was pleasantly surprised when I saw the room, as had not stayed here before and it was a last minute booking.
I only had breakfast so do not know about other meals, but it was very good
I would definitely stay again and I would recommend the hotel. Prices are always expensive in Aberdeen. so I felt the rate in this hotel was very fair compared to others. I could not get the TV to work but I did not really want to see it anyway and it probably could have been sorted if I had asked.
Read More Less
Fantastic Hotel
Everything about this Hotel is top quality.
From the greeting in reception upon arrival to departing in the morning was first class. All the staff were very friendly and helpful. Excellent food, well cooked and tasted brilliant. Room standard, probably the best I have seen in terms of comfort and cleanliness. Very modern styling which is very attractive. All members of staff deserve top marks for providing a level of service over and above their job description. Thanks for a pleasant stay.
Read More Less
Excellent service
Room and bathroom clean decor very modern
Situated in flight path of Aberdeen Airport and although no flights after 10pm they do start early in morning and from about 6 am the various take off , landings etc can be clearly heard - no issue for me as on business trip but may distaract late sleepers,
Breakfast great and service prompt and pleasantly served
Room did not smell fresh
My room had a very stale smell of b.o 👎
Hopefully only a one off as it's usually a good hotel
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NewswireToday - /newswire/ -
Sarasota, FL, United States, 2011/12/13 - 1st Choice Service Experts, a division of 1st Choice Industries that delivers plumbing, HVAC, electric and handyman services, has hired Kevin Henault as HVAC Manager - 1stChoiceCorp.com.
1st Choice Service Experts, a division of 1st Choice Industries that delivers plumbing, HVAC, electric and handyman services to commercial clients throughout Florida and residential customers in Manatee, Sarasota and Charlotte counties, has hired Kevin Henault as HVAC Manager.
Henault has over a decade of experience in general maintenance and air conditioning service and repair. He holds an HVAC Class A Florida State License, and was owner of an air conditioning company for the past eight years. He graduated from Dean Vocational Trade School with a diploma in Electronics, and served four years as a U.S. Army medic.
Kevin has a solid background in general maintenance and HVAC service and repair, said 1st Choice Industries CEO Gary Simone. With our Service Experts division growing quickly, we will rely on his hands-on technical knowledge and leadership experience to bring our customers the prompt, reliable services they need to keep their homes and businesses up and running.
About 1st Choice Industries
Headquartered in Florida with satellite offices throughout the United States, 1st Choice Industries (1stChoiceCorp.com) is a premier provider of construction, facilities management and professional business solutions. Founded in 1983 in New Jersey, the company moved its corporate headquarters to Sarasota, Florida, in 2004. The company was recently awarded the 2011 Frank G. Berlin, Sr., Small Business Award by the Greater Sarasota Chamber of Commerce. 1st Choice Industries supports national clients across a broad range of industries, including retail, restaurant, hospitality, medical, banking and more.
Grapevine Communications is a full-service, award-winning advertising, marketing and public relations firm based in Sarasota, Florida, and serving clients nationwide. The firm was awarded the 2010 Frank G. Berlin, Sr., Small Business Award by the Greater Sarasota Chamber of Commerce.
Written by / Agency / Source: Grapevine Communications International, Inc.
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On 03/04/2008, Sean Davis <sdavis2(at)mail(dot)nih(dot)gov> wrote: > > You will still need to create all the columns for your table first. > Also, I think you'll want to look at the documentation for the copy > command, as what you give above should probably result in an error. > So columns cannot be automatically created. The documentation is poor, for example the 'explanation' of the use of |stdin should really explain that as an alternative
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