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Polymers 2013, 5(1), 112-127; doi:10.3390/polym5010112
Published: 29 January 2013
Abstract: A series of polypeptoid homopolymers bearing short (C1–C5) side chains of degrees of polymerization of 10–100 are studied with respect to thermal stability, glass transition and melting points. Thermogravimetric analysis of polypeptoids suggests stability to >200 °C. The study of the glass transition temperatures by differential scanning calorimetry revealed two dependencies. On the one hand an extension of the side chain by constant degree of polymerization decrease the glass transition temperatures (Tg) and on the other hand a raise of the degree of polymerization by constant side chain length leads to an increase of the Tg to a constant value. Melting points were observed for polypeptoids with a side chain comprising not less than three methyl carbon atoms. X-ray diffraction of polysarcosine and poly(N-ethylglycine) corroborates the observed lack of melting points and thus, their amorphous nature. Diffractograms of the other investigated polypeptoids imply that crystalline domains exist in the polymer powder.
1. Introduction
At the beginning of the 20th century Leuchs [1,2,3] discovered by chance a synthesis of α-amino acid N-carboxy anhydrides (NCAs), also known as Leuchs anhydrides. Subsequently, this class of molecules would be applied for the ring-opening polymerization to obtain synthetic polypeptides. Since the early 1950s many publications have dealt with mechanistic studies on the ring-opening polymerization of NCAs [4,5,6,7,8,9,10,11]. In the course of this, the class of N-substituted glycine N-carboxy anhydrides (NNCAs), represented solely by sarcosine-NCA (N-methylglycine-NCA), served predominantly to investigate the influence of amide proton on the polymerization. Other members of the resulting class of polymer (polypeptoids) were virtually unknown to polymer chemists until very recently. Sisido et al. only briefly mentioned poly(n-propylglycine) and poly(ethylglycine), without providing any characterization [12,13,14]. This limited interest in this polymer family may be attributed to an early report by Wessely et al., in which it was suggested that NNCAs are exceedingly sensitive to hydrolysis [5].
In the meantime, Sisido et al. [15], Okada et al. [16] and Kricheldorf et al. [17] demonstrated that the polymerization of sarcosine-NCA could be controlled more readily as compared to regular amino acid NCAs. More recently, Zhang and co-workers found that N-substituted NCAs could be polymerized yielding cyclic polypeptoids with excellent yield in a well-controlled manner [18,19,20,21].
The living character of the nucleophilic ring-opening polymerization (NuLROP) of NNCAs other than Sar-NCA was shown by Luxenhofer and co-workers [22]. In particular, the successful preparation of a pentablock quinquiespolymer highlighted the unique character of the NNCA NuLROP [23]. Moreover, efficient polymer analogue modification [24,25] and thermo-responsiveness [26,27] of polypeptoids was described.
The fact that polypeptoids can be prepared to yield highly defined linear or cyclic oligomer/polymers via step-wise solid phase synthesis or living ring-opening polymerization makes this class of polymer rather unique, as outlined in a recent review by Zhang et al. [28].
As this polymer class is rather new, little is known about the materials properties. Interestingly, Segalman studied a series of short sequence-specific polypeptoids (obtained by solid phase synthesis) in their crystallization and melting behavior [29]. As expected, melting points are lower than those of polypeptides (attributed to the lack of intermolecular H-bonding) and the crystallization behavior is strongly affected by the polymer side chain.
Here, we present a systematic study of the thermal stability, glass transition and melting points of polypeptoids bearing short (C1–C5) side chains of degrees of polymerization of 10–100. X-Ray diffraction studies confirm that polysarcosine and poly(N-ethylglycine) are amorphous solids while longer side chain yield semicrystalline materials.
2. Experimental Section
2.1. Materials
All the solvents and substances for the preparation of monomers and polymers were purchased from Aldrich or Acros and were used as received unless otherwise stated. Benzonitrile (BN) was dried by refluxing over P2O5, benzylamine over BaO and petrolether over CaH2 under dry argon atmosphere and subsequent distillation prior to use. Water levels were determined using a C20 compact coulometer (Mettler-Toledo, Giessen, Germany). In general, solvents were used at water levels <30 ppm. The monomers were handled preferably in a glovebox (UNIlab, MBraun, Garching, Germany).
2.2. Methods
Gel permeation chromatography (GPC) was performed on a PL-GPC-120 (Polymer Laboratories) running under WinGPC software (PSS, Mainz, Germany) with two consecutive Gram columns (100 and 1000 Å) with N,N-dimethylacetaminde (DMAc) (5 g/L LiBr, 70 °C, 1 mL/min) as eluent and calibrated against PMMA standards (PSS, Mainz, Germany).
NMR spectra were recorded on a Bruker DRX 500 at room temperature (295 K). The spectra were calibrated using the solvent signals (D2O 4.79 ppm, MeOD-d3 3.31 ppm, DMSO-d6 2.50, MeCN-d3 1.94 ppm).
Matrix assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectra were recorded on a Bruker Biflex IV (Bruker Daltonics, Bremen, Germany) using a N2 laser (λ = 337 nm). All spectra were recorded in positive reflector mode. The ions were accelerated using a potential of 19 kV and reflected using a voltage of 20 kV. Detection was typically set from 350 m/z to 10000 m/z with a matrix suppression of typically 350–1000 m/z. After parameter optimization for each measurement, the instrument was calibrated with Peptide Calibration Standard II and/or Oligonucleotide Calibration Standard (Bruker), depending on the m/z range of the individual sample. Samples were prepared with sinapinic acid (3,5-dimethoxy-4-hydroxycinnamic acid, SA) as matrix using the dried–droplet spotting technique (0.5–1 µL). Exemplarily, samples (1 g/L) were dissolved in methanol (supplemented with 1% (v/v) trifluoroacetic acid (TFA)). The solution was mixed 1:1 (v/v) with 20 g/L SA MeOH/1% TFA. Laser power was set slightly above the threshold, typically at 50%. Gauss distributions were calculated using Equation (1), where µ is the degree of polymerization (DP) obtained from the signal with highest intensity (MP). The obtained probabilities are plotted against the calculated m/z at the respective DP and overlaid with the experimental MALDI-ToF mass spectra to estimate the molar mass (Mn, Mw) and the dispersity of the polymers (ÐM).
Thermogravimetric analysis was realized with a TG 50 modular unit and a TC 15 TA controller (Mettler-Toledo, Giessen, Germany).
DSC studies of the polypeptoids were conducted using a DSC 4 calorimeter (Perkin Elmer) under nitrogen. Powder samples sealed into the aluminum pans were first heated from 0 °C (except poly(N-butylglycine)25 and poly(N-pentylglycine)25 which started by −25 °C) to 250 °C at 5 K min−1, depending on the decomposition temperature of the sample, cooled to 0 °C by use of air cooling (~24 K min−1). Some additional measurements were conducted using a DSC 204 F1 Phoenix (Netzsch). Experimental data of glass transition temperature against the DP were fitted using Flory-Fox Equation (2).
With Mn as derived from 1H-NMR and parameters listed in Table 1.
X-ray diffraction measurements were performed on the powder diffractometer Stadi P from STOE using the Cu-Kα radiation wavelength (λ = 1.54 Å). Measuring range comprised 10 to 80 2θ.
|Table 1. Parameters used Flory-Fox equation to obtain fits.
|71,000 K·g/mol
|52,000 K·g/mol
|69,000 K·g/mol
|35,000 K·g/mol
2.3. Synthetic Procedures
2.3.1. Monomer Synthesis
Sarcosine-N-carboxyanhydride was synthesized in tetrahydrofuran (THF) in the presence of triphosgene as described previously [22].
N-Ethylglycine-, N-n-propylglycine-, N-n-butylglycine- and N-n-pentylglycine-NCA:
These monomers were obtained by a three-step synthesis from primary amines and glyoxylic acid using modified literature procedures [5,20] and was described previously [22,23].
2.3.2. Preparation of Polymers
Poly(sarcosine)25 P2.
Sar-NCA (0.265 g, 2.3 mmol) was weighed into reaction vessel dissolved in 2.3 mL of dry benzonitrile. After complete dissolution, the initiator benzylamine (10.0 µL, 0.09 mmol) was added ([M]0/[I]0 = 25). Outside of the glovebox the reaction mixture was stirred at room temperature under constant pressure (20 mbar) for 2 h. Afterwards, reaction mixture was precipitated into 40 mL diethyl ether and isolated polysarcosine was dried under reduced pressure. After two precipitation steps polysarcosine was dissolved in water and subsequently freeze-dried (0.135 g, 83%).
GPC (DMAc): Mn = 1.3 kg/mol (ÐM = Mw/Mn = 1.31).
1H NMR (500 MHz; D2O): δ = 2.97 (66 H, br, CH3–), 4.29 (46 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.35 ppm (5 H, br, C6H5–).
All other polymers were synthesized accordingly.
Poly(sarcosine)10 P1.
1H NMR (500 MHz; D2O): δ = 2.99 (23 H, br, CH3–), 4.28 (17 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.33 ppm (5 H, br, C6H5–).
Poly(sarcosine)50 P3.
GPC (DMAc): Mn = 4.0 kg/mol (ÐM = Mw/Mn = 1.09).
1H NMR (500 MHz; D2O): δ = 2.96 (135 H, br, CH3–), 4.28 (90 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.32 ppm (5 H, br, C6H5–).
Poly(sarcosine)100 P4.
GPC (DMAc): Mn = 8.9 kg/mol (ÐM = Mw/Mn = 1.05).
1H NMR (500 MHz; D2O): δ = 2.95 (219 H, br, CH3–), 4.28 (146 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.33 ppm (5 H, br, C6H5–).
Poly(N-ethylglycine)10 P5.
1H NMR (500 MHz; D2O): δ = 1.14 (32 H, br, CH3–), 3.37 (19 H, br, CH3–CH2–), 4.25 (23 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.32 ppm (5 H, br, C6H5–).
Poly(N-ethylglycine)25 P6.
GPC (DMAc): Mn = 1.0 kg/mol (ÐM = Mw/Mn = 1.65).
1H NMR (500 MHz; D2O): δ = 1.14 (70 H, br, CH3–), 3.38 (45 H, br, CH3–CH2–), 4.26 (48 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.32 ppm (5 H, br, C6H5–).
Poly(N-ethylglycine)50 P7.
GPC (DMAc): Mn = 3.3 kg/mol (ÐM = Mw/Mn = 1.27).
1H NMR (500 MHz; D2O): δ = 1.14 (116 H, br, CH3–), 3.38 (73 H, br, CH3–CH2–), 4.22 (74 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.32 ppm (5 H, br, C6H5–).
Poly(N-ethylglycine)100 P8.
GPC (DMAc): Mn = 6.8 kg/mol (ÐM = Mw/Mn = 1.22).
1H NMR (500 MHz; D2O): δ = 1.14 (252 H, br, CH3–), 3.38 (164 H, br, CH3–CH2–), 4.25 (170 H, br, –CH2-CO- and C6H5–CH2–NH–), 7.32 ppm (5 H, br, C6H5–).
Poly(N-npropylglycine)10 P9.
GPC (DMAc): Mn = 0.6 kg/mol (ÐM = Mw/Mn = 1.58).
1H NMR (500 MHz; MeOD-d3): δ = 0.92 (38 H, br, CH3–), 1.60 (25 H, br, CH3–CH2–), 3.33 (n.d., br, CH3–CH2–CH2–), 4.25 (25 H, br, –CH2–CO– and C6H5–CH–NH–), 7.25 ppm (5 H, br, C6H5–).
Poly(N-npropylglycine)25 P10.
GPC (DMAc): Mn = 1.6 kg/mol (ÐM = Mw/Mn = 1.32).
1H NMR (500 MHz; MeOD-d3): δ = 0.92 (66 H, br, CH3–), 1.60 (45 H, br, CH3–CH2–), 3.32 (n.d., br, CH3–CH2–CH2–), 4.25 (43 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.25 ppm (5 H, br, C6H5–).
Poly(N-npropylglycine)50 P11.
GPC (DMAc): Mn = 5.0 kg/mol (ÐM = Mw/Mn = 1.22).
1H NMR (500 MHz; MeCN-d3): δ = 0.86 (50 H, br, CH3–), 1.52 (37 H, br, CH3–CH2–), 3.23 (32 H, br, CH3–CH2–CH2–), 4.10 (39 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.28 ppm (5 H, br, C6H5–).
Poly(N-npropylglycine)100 P12.
GPC (DMAc): Mn = 7.5 kg/mol (ÐM = Mw/Mn = 1.15).
1H NMR (500 MHz; MeOD-d3): δ = 0.92 (222 H, br, CH3–), 1.62 (149 H, br, CH3–CH2–), 3.33 (n.d., br, CH3–CH2–CH2–), 4.27 (146 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.26 ppm (5 H, br, C6H5–).
Poly(N-nbutylglycine)10 P13.
GPC (DMAc): Mn = 0.9 kg/mol (ÐM = Mw/Mn = 1.55).
1H NMR (500 MHz; TFA (DMSO-d6)): δ = 0.87 (33 H, br, CH3–), 1.30 (23 H, br, CH3–CH2–), 1.61 (22 H, br, CH3–CH2–CH2–), 3.33 (22 H, br, CH3–(CH2)2–CH2–), 4.38 (25 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.17 ppm (5 H, br, C6H5–).
Poly(N-nbutylglycine)25 P14.
GPC (DMAc): Mn = 1.9 kg/mol (ÐM = Mw/Mn = 1.27).
1H NMR (500 MHz; TFA (DMSO-d6)): δ = 0.86 (60 H, br, CH3–), 1.43 (82 H, br, CH3–CH2–CH2–), 3.34 (40 H, br, CH3–(CH2)2–CH2–), 4.32 (39 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.16 ppm (5 H, br, C6H5–).
Poly(N-nbutylglycine)50 P15.
GPC (DMAc): Mn = 3.2 kg/mol (ÐM = Mw/Mn = 1.40).
1H NMR (500 MHz; TFA (DMSO-d6)): δ = 0.87 (113 H, br, CH3–), 1.31 (77 H, br, CH3–CH2–), 1.62 (75 H, br, CH3–CH2–CH2–), 3.36 (76 H, br, CH3–(CH2)2– CH2–), 4.39 (80 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.16 ppm (5 H, br, C6H5–).
Poly(N-nbutylglycine)100 P16.
GPC (DMAc): Mn = 4.2 kg/mol (ÐM = Mw/Mn = 1.16).
1H NMR (500 MHz; TFA (DMSO-d6)): δ = 0.87 (172 H, br, CH3–), 1.30 (122 H, br, CH3–CH2–), 1.62 (115 H, br, CH3–CH2–CH2–), 3.36 (117 H, br, CH3–(CH2)2–CH2–), 4.34 (125 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.16 ppm (5 H, br, C6H5–).
Poly(N-npentylglycine)10 P17.
GPC (DMAc): Mn = 0.9 kg/mol (ÐM = Mw/Mn = 1.38).
1H NMR (500 MHz; TFA (DMSO-d6)): δ = 0.82 (30 H, br, CH3–), 1.27 (41 H, br, CH3–CH2–CH2–), 1.64 H (20 H, br, CH3–(CH2)2–CH2–), 3.35 (20 H, br, CH3–(CH2)3–CH2–), 4.39 (25 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.16 ppm (5 H, br, C6H5–).
Poly(N-npentylglycine)25 P18.
GPC (DMAc): Mn = 2.1 kg/mol (ÐM = Mw/Mn = 1.20).
1H NMR (500 MHz; TFA (DMSO-d6)): δ = 0.83 (51 H, br, CH3–), 1.27 (67 H, br, CH3–CH2–CH2–), 1.64 (34 H, br, CH3–(CH2)2–CH2–), 3.33 (34 H, br, CH3–(CH2)3–CH2–), 4.45 (36 H, br, –CH2–CO– and C6H5–CH2–NH–), 7.16 ppm (5 H, br, C6H5–).
Poly(N-npentylglycine)50 P19.
1H NMR (500 MHz; TFA (DMSO-d6)): δ = 0.82 (111 H, br, CH3–), 1.27 (149 H, br, CH3–CH2–CH2–), 1.65 (73 H, br, CH3–(CH2)2–CH2–), 3.36 (75 H, br, CH3–(CH2)3–CH2–), 4.45 (79 H, br, CH2–CO– and C6H5–CH2–NH–), 7.16 ppm (5 H, br, C6H5–).
Poly(N-npentylglycine)100 P20.
1H NMR (500 MHz; TFA (DMSO-d6)): δ = 0.82 (190 H, br, CH3–), 1.27 (258 H, br, CH3–CH2–CH2–), 1.65 (127 H, br, CH3–(CH2)2–CH2–), 3.36 (130 H, br, CH3–(CH2)3–CH2–), 4.45 (140 H, br, CH2–CO– and C6H5–CH2–NH–), 7.16 ppm (5 H, br, C6H5–).
3. Results and Discussion
Polypeptoids with different degrees of polymerization (DP) and varying side-chain length comprising 1 to 5 carbon atoms were successfully synthesized (Scheme 1).
Characterization of the obtained polypeptoids was performed using 1H NMR spectroscopy, GPC and MALDI-ToF mass spectrometry (Table 2). The polymers P19 and P20 (poly(N-pentylglycine)) were insoluble in the used solvents (DMAc, MeOH), therefore the characterization by GPC and MALDI-ToF MS was not possible. Furthermore, the molar mass of P1 and P5 was too small for the GPC measurement under the given conditions.
|Table 2. Analytical data of synthesized polypeptoids.
|Polymer a
|Mn b [kg/mol]
|ÐM b
|Mn c [kg/mol]
|ÐM c
|Mn d [kg/mol]
|DP d
|yield [%]
|0.6 e
|7 e
|1.7 e
|22 e
|3.8 e
|52 e
|5.3 e
|73 e
|>99 i
|1.0 e
|10.5 e
|2.1 e
|23 e
|3.9 e
|45 e
|7.2 e
|83 e
|>99 i
|1.4 f
|13 f
|2.3 f
|22 f
|4.1 g
|40 g
|7.4 f
|74 f
|1.4 h
|11 h
|2.2 h
|18.5 h
|4.4 h
|38 h
|6.8 h
|59 h
|>99 i
|1.5 h
|11 h
|2.3 h
|17 h
|4.9 h
|38 h
|>99 i
|8.4 h
|65 h
|>99 i
a As determined from [M]0/[I]0; b As determined by gel permeation chromatography; c As calculated from Gauss distribution fitted to MALDI-ToF mass spectra; d As determined by end-group analysis from 1H NMR spectroscopy (signal intensity of aromatic protons of benzylamine-initiator vs main-chain and side-chain signal intensity); e Determined in D2O; f Determined in MeOD; g Determined in MeCN; h Determined in TFA-d1 with DMSO-d6 as external lock; i Traces of solvents could be contained in the polymers.
A comparison of the obtained molar masses with the theoretical masses calculated from [M]0/[I]0 using the example of P(N-PrGly) with different degrees of polymerization shows an increasing discrepancy with an increasing DP (Figure 1). This has been reported before by others and us [17,22,25]. To date, we lack a satisfactory explanation. Nevertheless, the experimentally determined degrees of polymerization generally follow the expected trend.
The thermal properties of the different polypeptoids have been investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) (Table 3).
|Table 3. Summary of the DSC and TGA studies.
|Tg [°C]
|Tm [°C]
|Tc [°C]b
|Td [°C]c
|215 (2nd Tm = 63 °C)
|225 (2nd Tm = 70 °C)
|145 (2nd Tm = 56 °C)
|176 (2nd Tm = 49 °C)
|190 (2nd Tm = 70 °C)
|207 (2nd Tm = 67 °C)
a As determined from [M]0/[I]0; b crystallization temperature; c decomposition temperature.
The TGA thermograms of all polypeptoid samples, except P1, reveal decomposition temperature thresholds over 200 °C, which is in accordance with earlier reports for several other polypeptoids with long-chain substituents [29]. In Figure 2, an assortment of TGA thermograms is displayed. On the one hand, polypeptoid samples with a increasing side chain length were compared (Figure 2a), on the other hand the influence of the DP based on different P(N-PrGly) samples is depicted (Figure 2b). The influence of the substituent on the decomposition temperature is relatively little; in contrast, with an increasing DP, a shift to higher decomposition temperatures is noticeable.
The decomposition temperature of polysarcosine is comparable with the sarcosine decomposition temperature of 212.5 °C. To the best of our knowledge, no decomposition temperatures have been published for the other corresponding N-substituted glycines.
Rosales et al. reported that poly(N-isopentylglycine), poly(N-hexylglycine) and other polypeptoids with longer side chains were stable up to 260 °C. In our case, the on-set temperatures were significantly lower than 260 °C. Unfortunately, a more detailed comparison with literature is not possible as no detailed decomposition values or thermograms were given [29].
DSC studies were carried out below the decomposition temperatures to determine glass transition temperature (Tg) and melting points (Tm). The glass transition temperature as a function of the number of C-atoms in the side chain and of different degrees of polymerization was investigated (Figure 3). Different polypeptoid samples with the same DP, but increasing number of C-atoms in the side chain possess, as expected, decreasing glass transition temperatures (Figure 3a). Comparison of the Tg's of P4 (Tg = 143 °C) and P20 (Tg = 5 °C) exhibit a difference of 138 °C. In the literature a Tg = 117 °C for polysarcosine with a DP of 103 can be found [30].
Notably, the Tg value of P1 does not fit in the observed trend. This may be attributed in part to the low decomposition on-set temperature. Possibly, the decomposition of the polymer starts in the first heating cycle, the consequence being that the glass transition was drastically decreased (Figure 4). However, the determined Tg from the first heating cycle is already very low.
The decrease of the Tg by increasing side chain length is associated with extended flexibility of the backbone. Such decrease is expected and has also been studied in some detail for poly(2-oxazoline)s, constitutional isomers of polypeptoids [31]. Moreover, another trend is recognizable in Figure 3b. As is well known, an increase of the DP leads to an increase of the Tg [32,33]. An increase of the chain length decreases the flexibility of the polymer chains, the consequence being that the Tg increase to a constant value. In addition, the chain ends may act as plasticizers [34]. As the relative amount of polymer chain ends decreases with increase in chain length, the Tg reaches a plateau. For PSar, P(N-EtGly) and P(N-PrGly) this plateau appears to be reached at approx. DP = 50.
It should be noted that for unknown reasons P(N-BuGly) did not yield values for Tg for DPs other than 25 in this study. We are currently investigating this issue in more detail, as it may be that small residual of solvent is responsible for this. Some DSC response curves are depicted in Figure 5. We observed melting points for polypeptoids with a side chain comprising not less than three methyl carbon atoms. That implies that PSar and P(N-EtGly) are amorphous solids. Our data corroborates earlier reports by Okada et al. [30]. However, P(N-PrGly), P(N-BuGly) P(N-BuGly) and exhibit crystalline domains in the solid structure.
The obtained values for Tm of the polypeptoids follow the same trend as the glass transition temperature, i.e., with increasing chain length the Tm increases towards a plateau (Figure 6a). Interestingly, polymer Tm values at a fixed DP are highest for the P(N-BuGly). The value we report here for P(N-BuGly) again corroborate and supplement values reported by Rosales et al. Moreover, Tm values for P(N-PenGly) align roughly with literature values for poly(N-hexylglycine) and poly(N-octylglycine), although it must be noted that for those samples, a the smaller DP of 15 was reported (Figure 6b) [29]. In addition, these samples were monodispers.
The first and second heating DSC thermogram of P(N-PenGly)25 (P18) are shown in Figure 5d). The first heating thermogram exhibits two signals (in the range of 50 °C and 175 °C) which can be assigned to melting points. Interestingly, while for the other degrees of polymerization (P17, P19, P20) the lower temperature Tm persists in the second heating cycle no signal was detected at 50 °C therein for P18. In lieu thereof a buckle in the curve can be observed. Zhang et al. observed two melting points for the polypeptoid with a decyl substituent at the nitrogen and attributed this phenomenon to crystalline packing of the side chains and the main chains [35]. Accordingly, we also attribute the observed signals to crystalline packing of the side chains, but after the cooling cycle no melting point is observed in the second heating cycle. Repetition of the measurement revealed clearly smaller signals for the melting point in the range of 50 °C (data not shown). However, the melting point existed in the second heating curve as well.
The DSC thermogram of P(N-PrGly) shows an exothermic peak in the range of 143–155 °C, which can indicates a cold-crystallization process (Figure 5b). This peak describes the transition from amorphous solid to crystalline solid.
It should be noted that we observed a number of problems with repeatability of DSC measurements for some samples. In a number of cases, it appears that decomposition/discoloration started briefly after the glass transition temperature although TGA thermograms give no indication of a change in sample mass. The presence of flat and/or asymmetric peaks, decreasing Tg and Tm and discoloring of the samples after the measurement (yellow-brown), do hint towards changes in the polymer structure during these measurements. As may be expected, the problem with DSC measurement reproducibility was particularly pronounced for samples of low molar mass. We attribute this to more pronounced end-group effects for short polymer chains.
Crystallinity of polymer powders was also assessed using X-ray diffraction (Figure 7). Diffractograms of PSar and P(N-EtGly) show no sharp signals. This observation correspond amorphous solids and corroborates the observed lack of melting points by DSC. In contrast the diffractograms of the other three polymers (P(N-PrGly) (P11), P(N-BuGly) (P14) and P(N-PenGly) (P18) exhibit a sharp signal in a range of 20° 2θ, which is evidence for crystalline domains in the polymer powder. Rosales et al. detected a reflection in this range for all investigated peptoids and attributed this observation to the spacing between polymer chains (d = 4.5 Å) based on previously investigations [29,36]. Furthermore, P(N-PenGly) exhibits a reflection in the range of 25° 2θ. Zhang et al. investigated cyclic poly(N-decylglycine) with WAXS and attributed a reflection in the same range to the distance between adjacent repeating units (d = 3.6 Å) [35].
4. Conclusions
We have investigated a series of polypeptoid homopolymers bearing short (C1–C5) side chains of DP = 10–100 regarding thermal stability, glass transition and melting points. First, we synthesized polypeptoids by nucleophilic living ring-opening polymerization and characterized the obtained polymers with 1H NMR spectroscopy, MALDI-ToF mass spectrometry and gel permeation chromatography. Afterwards, thermal properties of the different polypeptoids have been investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry. TGA thermograms reveal decomposition temperature thresholds over 200 °C. Side chain length and DP affect the decomposition temperatures differently. The influence of the side chain is relatively little. However, an increasing DP leads to a shift to higher decomposition temperatures.
Furthermore, dependences of the glass transition temperature were investigated regarding side chain length and degree of polymerization. The obtained values confirm expected trends for Tg values and corroborate values reported earlier where available. In summary, an increasing side chain length leads to a decrease the Tg while an increase of the DP increases the Tg to a constant value. Similar observations occurred for the melting points, i.e., melting points increase to a constant value by increasing DP. However, three carbon atoms in the side chain are necessary to obtain semi-crystalline materials. Moreover, poly(N-butylglycine) and poly(N-pentylglycine) of degrees of polymerization of 50–100 exhibit two melting points which are attributed to crystalline packing of the side chains and the main chains.
X-ray diffraction measurements confirm crystalline domains in the polymer powder for polypeptoids with more than two carbon atoms in the side chain.
This publication is based on work supported by Award No. KUK-F1-029-32, made by King Abdullah University of Science and Technology (KAUST) and the Fonds der Chemischen Industrie (awarded to R.L.). We would like to acknowledge technical support by Matthias Kluge (TU Dresden) for TGA and DSC measurements. We kindly acknowledge technical support with XRD measurements by Anja Bensch (Prof. Michael Ruck, Inorganic Chemistry II at TU Dresden) The authors thank Julian Wagenhöfer for helpful discussions about XRD diffractograms. We also acknowledge Prof. Rainer Jordan (TU Dresden) for support and access to equipment. This publication was funded by the German Research Foundation (DFG) and the University of Wuerzburg in the funding programme Open Access Publishing.
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Great Decor in a Flash Without a Lot of Cash
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Spit Spot Frame
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Showcase your best friend in this adorable Spit Spot Frame. Made to look like faux animal spots, this cute frame is perfect for displaying a precious photo of your little puppy or kitten. You can even personalize the frame by adding their name or other words of adornment. This Spit Spot Frame makes a great gift for any animal lover, and is a sweet way to show off a precious pet either at home or in the office.
- One wooden frame, available from a craft shop
- Acrylic paint in the following six colors: mother-of-pearl rose pink; sweet memories (bright pink); plum; powder blue; grey and white
- Two 2cm wide wooden words for this project, the words Love and Joy were used
- Fine paintbrush
- Artline 210 Fineliner Pen
- Plaid Royal Coat Dimensional Magic
- Clear-drying craft glue
- Quick-drying clear matt spray varnish
- Pencil
- Fine sanding paper
- Dry cloth to dust the frame
Sandpaper the whole frame thoroughly. Dust well with a dry cloth before continuing with the next step.
Remove the glass and back covering. Paint the frame with the mother-of-pearl rose pink acrylic paint.
Allow to dry and apply a second coat.
Use a pencil to draw animal print spots on the front of the frame.
Paint the spots, using the remaining five acrylic paints, and allow to dry thoroughly.
Once dry, use the Artliner pen to encircle each spot and allow to dry thoroughly.
Paint the words with the sweet memories acrylic paint and allow to dry thoroughly.
Add the Dimensional Magic to the top of the words and allow to dry for several hours.
Add one coat with the quick-drying clear matt spray varnish and allow to dry thoroughly.
Add Dimensional Magic to the front of the frame and allow to dry for at least 3 hours. Tip: Use a toothpick to pop any air bubbles that might appear.
- Glue the words in place and allow to dry thoroughly.
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Gold Braided Multi Coral Ribbon Bracelet
designer's notes
Fringe Benefits! Vintge Vixens, this one's for you! An intricately interwoven mix of vintage ribbons is set off with a serving of spectacular rhinestone shiners! Finally, a wave of fringed ribbon fans from the bracelet's cusp! After all, beauty is in the eye of the bedazzled!
color: Multi-Coral Gold Braided Multi Coral Ribbon Bracelet Crystal; U.S.A; style# 330796301


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Bobby Lenarduzzi RSS
Whitecaps name SFU's Alan Koch head coach of USL Pro club
Coaching a university team in Canada is among the more secure gigs in the fickle world of sport. The pension's not bad, either. Leaving is a tough decision. So it says something about Alan Koch that he's given up his … Continue reading
SFU's Koch among candidates for Whitecaps' USL Pro job
The Whitecaps' search for a USL Pro head coach could well end with a local hire. Alan Koch, bench boss of Simon Fraser University's men's team, is among the leading candidates, sources say. Koch, a 39-year-old native of Durban, South … Continue reading
Whitecaps expected to announce USL PRO franchise to play out of UBC
The Whitecaps are set to join the growing list of MLS clubs investing in their own USL PRO franchises. The Caps will make "a special announcement" at the University of B.C. on Friday "regarding the club's development program." Caps president … Continue reading
Whitecaps: Froese, Bustos sign MLS deals
Whitecaps residency midfielders Kianz Froese and Marco Bustos, both 18, have signed MLS deals, according to multiple sources. The club is expected to announce the signings this week, which times well with their push for a USL Pro franchise somewhere … Continue reading
Three New Westminster groups declare support for Whitecaps' USL PRO plan
The New Westminster Chamber of Commerce, Queen's Park Residents' Association and Royal City Youth Soccer Club have backed the Whitecaps' plan to bring USL Pro soccer to New Westminster in 2015. The three organizations held a joint press conference in … Continue reading
Camilo's agent breaks his silence
Camilo Sanvezzo's agent, Lucas Teixeira, has broken his long silence on the Golden Boot winner's messy exit from Vancouver and MLS. In an interview with Away From the Numbers (The Province made several attempts to get Teixeira on the … Continue reading
Is Camilo on his way back to the Vancouver Whitecaps?
Is Camilo Sanvezzo set to return to the Vancouver Whitecaps? It's a real possibility, according to Peter Schaad, who is the Caps' play-by-play voice for TEAM Radio and also does work for TSN, the MLS rights holders in Canada. In … Continue reading
Camilo pictured at Queretaro FC practice
Camilo Sanvezzo continues to defy the Whitecaps, who insist he remains their player. The 25-year-old Brazilian striker was pictured Thursday jogging around the Queretaro FC training field in full uniform. He showed up in Mexico over the weekend and shocked … Continue reading
Lenarduzzi on Camilo's appearance in Queretaro colours
Camilo Sanvezzo, the Whitecaps player of the year, is in Mexico where he's donned the shirt of Liga MX side Queretaro FC. Whitecaps president Bobby Lenarduzzi spoke to media on Monday afternoon at the club's Gastown offices. Here's the transcript:… Continue reading
Whitecaps bid for Bob Bradley falls short
The Vancouver Whitecaps have fallen short in their bid to land former U.S. and Egypt coach Bob Bradley, sources have told the Province. Barring a last-minute about-face, Bradley is expected to take a job in Europe. He's been linked … Continue reading


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Neil Young Cancels European Tour Dates
With a man down due to injury, Neil Young and Crazy Horse have been forced to cancel a series of summer tour dates.
With a man down due to injury, Neil Young and Crazy Horse have been forced to cancel a series of summer tour dates.
It's been about nine months since Neil Young released an album, which is an eternity for the prolific legend. Thankfully, that drought will soon be over.
Ever the restless wanderer, Neil Young spent much of the 80s exploring different musical avenues. It's only natural that one path would eventually take him back to the past, which is what happened on 'Everybody's Rockin,'' released on July 27, 1983.
Neil Young will once again lead Farm Aid, the annual benefit concert that supports American farmers. The 2013 edition of the daylong festival will take place on Sept. 21 in Saratoga Springs, NY.
Poverty afflicts so many people that it can feel like it's impossible to make a difference -- but like any huge problem, the most effective solutions involve the efforts of many, and that's where programs like the Global Citizen Tickets Initiative come in.
When Neil Young performed 'Rockin in the Free World' for the first time on February 21, 1989, in Seattle, the song was just hours old. In fact, Crazy Horse guitarist Frank 'Poncho' Sampedro claimed that most of the band didn't even know the song when they first played it.
In an extensive interview with Rolling Stone, Crazy Horse guitarist Frank 'Poncho' Sampedro expresses some concerns that Crazy Horse's current tour with Neil Young may be their last.
Neil Young was already having a pretty lousy decade when 'This Note's for You' was released on April 11, 1988. It didn't start out that awful, with the folksy 'Hawks & Doves' and the Crazy Horse album 'Re-ac-tor' in 1980 and 1981, respectively.
Neil Young is back on the road again -- but instead of working with Crazy Horse or Buffalo Springfield, he's tooling around in his handmade fuel-efficient hybrid vehicle, called the Lincvolt. He's even blogging about the journey, which has included stops at California's Joshua Tree National Park and the Imperial Sand Dunes.
On March 20, 1968, a genuine rock and roll all star bust went down. At the home of then girlfriend of Stephen Stills, nestled in the legendary Topanga Canyon of California, members of Buffalo Springfield were getting a little out of hand.
It's almost always impossible to predict just what Neil Young is going do next -- but for once, we might have a small clue. The elusive, iconoclastic rock legend has been on tour with Crazy Horse in Australia, and according to a new report, he filmed one of the dates Down Under for a forthcoming concert film.
Wanting to do his part to help the victims of Hurricane Sandy, Neil Young has announced that, on Dec. 6, he and Crazy Horse will play a benefit concert at the Borgata Hotel Casino and Spa in Atlantic City, N.J.


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|Home Decor
"My customer's joy and success is my motivation!"
Cali Chic Patterns (CaliChicPatterns) was inspired from my desire to design and make knit and crochet blankets to comfort "little miracles" and ...
"My customer's joy and success is my motivation!"
Cali Chic Patterns (CaliChicPatterns) was inspired from my desire to design and make knit and crochet blankets to comfort "little miracles" and satisfy knitters/ crocheters looking for attractive and istinctive designs.
Moreover, I wanted to introduce patterns that contain "detail" yet remain simple and easy to understand so fun and successful creation would be the experience, every time.
Growing up in Japan, I've studied and practiced knitting, crocheting and quilting since I was a teen. It's truly my passion. However, I was challenged here in the US where typical patterns do not have symbol charts or diagrams to visually show where the stitches go. I was disappointed by this but undaunted, I learned how to read and write patterns in US Terms.
Soon my desire was to share my own designs with my style of detailed simplicity, keeping patterns clean and simple but providing detail necessary for everyone, regardless of experience, to have success. For example, providing a blanket edging connection guide, so often omitted in blanket patterns with complex edging designs!
And that's just what I did.... Cali Chic Patterns is the expression of that desire.
I hope my distinctive creations please you and you experience only success and joy making them yourself for your own family or as a gift for a special friend.
THANK YOU so much for taking time to learn about me and Cali Chic Patterns.
♥ Kyoko
♥ Knitting pattern #27 for adorable Cali Kids toddler to teen blanket with crochet trim and cute heart or crown motif. Pattern provided makes a blanket "approximately" 34 x 28 inches (86.4 x 71.1 cm)., depending on yarn thickness and tightness of knit and crochet preference. It will make a welcome baby shower gift for new moms, or a favorite blanket within the family for your toddler.
♥ Sizing makes it a full blanket for a toddler or a generous size baby blanket as well. Pattern includes all yarn details, tools required and helpful photos plus diagrams..
♥ This pattern is written in standard US terms AND includes international Knitting and Crochet "SYMBOL CHARTS" of the blanket and trim so you can easily SEE what to do and where!
Symbol Diagrams are also very helpful for those from OUTSIDE THE UNITED STATES, unfamiliar with the English terms, to still follow how to make this beautiful blanket!
♥ SHIPPING IS FREE since product is a PDF electronic document that is available for INSTANT DOWNLOAD as soon as payment clears.
♥ This pattern is copyright protected and cannot be changed, sold, or reproduced in any way. You cannot sell the pattern but you are free to sell any items you make from using this pattern.
♥ Text and Photos are Copyright (c) 2013 by Cali Chic Patterns, all rights reserved.
♥ By purchasing this pattern you agree to the terms above.
4x4 in / 10x10 cm:
18 sts / 24 rows knitting
13.2 sc / 16 rows crochet
591 yards of Worsted weight


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The Emergence of the Renaissance in Black Literature
T he first stirrings of black literary activity that would foreshadow the Harlem Renaissance were evident in the years immediately before and shortly after World War I. During this period several black writers began publishing work that differed significantly from either the Chesnutt or the Dunbar traditions in black literature. These writers came from extremely diverse backgrounds and worked independently of one another in widely scattered areas of the country. Like Chesnutt and Dunbar, they published their initial work primarily in white magazines, and their initial literary contacts were generally with white writers and editors. They were not yet part of a literary movement, but their experiences and the direction that they took in their art served as an important prelude to the Harlem Renaissance. And, in the mid-1920s most of these writers, together with other young blacks, would meet in Harlem and be proclaimed as the founders of the new black literary movement.
The first of the new writers to publish was James Weldon Johnson. Johnson is especially important because, more than any other writer, he was a transitional figure whose early work was in the Dunbar tradition but who later became a significant poet and critic of the Renaissance. Chronologically Johnson, who was born in 1871, belonged to the generation of Dunbar and Chesnutt, and his first published work, a dialect piece patterned after Dunbar's popular poetry, was accepted in 1899 by Century


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About Patti Davis / Patti Davis Biography
About Patti Davis / Who is Patti Davis ?
Patti Davis's Character horoscope
Patti Davis is a very practical person and equally capable. Patti Davis is very tidy by nature, Patti Davis love order and are methodical. It is even possible that these qualities are too highly developed in Patti Davis and it may be that while attending to minute details, Patti Davis lose some of the larger opportunities of life.Patti Davis is sensitive and generous. Were Patti Davis to hear of a case of want or somebody in dire distress, it is unthinkable that Patti Davis would pass by and not hold out a helping hand.Patti Davis is a hesitant person. Though Patti Davis have the qualities for making Patti Davis's way in the world and it is within Patti Davis's powers to climb high up the ladder of success, the necessary qualities to carry Patti Davis through and while Patti Davis is wondering some more pushing but less well-equipped person steps into Patti Davis's place. Therefore do not think much of Patti Davis's mythical limitations. Take it for granted that Patti Davis will succeed and Patti Davis will.Patti Davis is calculative and realistic. Patti Davis always want to achieve something. There is some deep desire burning in Patti Davis's heart to achieve something. This makes Patti Davis restless at times. However, Patti Davis will always have proud on Patti Davis's achievements.
Patti Davis's Happiness and Fulfillment horoscope
Patti Davis will often meet with disappointments and expect more, for Patti Davis tend to worry so much that the very things Patti Davis is afraid of usually happen. Very shy, Patti Davis have great difficulty in communicating feelings and emotions. If Patti Davis will clear Patti Davis's head of all worldly matters for a small period each day and sit in meditation, Patti Davis will feel much peace and realise that things are not as bad as they seem.
Patti Davis's Life Style horoscope
Patti Davis's friends serve as motivational factors in Patti Davis's life. Patti Davis need their support and encouragement. Patti Davis can thus achieve Patti Davis's goals by directing yourself in areas where Patti Davis's friends see Patti Davis's progress.
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Nineoverten.com has put up a review of Pacific Rim, an iOS brawler based on the movie of the same title directed by Guillermo del Toro.
From the review: The guys at Reliance Games have build a decent brawler that complements the big-screen spectacle as well as appeal to hardcore fans of the movie. 4/5


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August 3, 2011
Photo by Derrick Mahone
Jonesboro junior Cameron Sutton will be counted on to play on both sides of the ball for the Cardinals this season. He will play both wide receiver and quarterback on offense and cornerback on defense.
Stories this photo appears in:
Maturing Jonesboro looks to make playoff run
Jonesboro coach Tim Floyd doesn't believe his squad needs a major overhaul in its attempt to make a run for the state playoffs.
Use the comment form below to begin a discussion about this content.


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Throwing Copper is the second album by American alternative rock band Live, released on April 19, 1994 on former MCA Records subsidiary Radioactive Records. It was produced by Jerry Harrison of Talking Heads and was recorded at Pachyderm Recording Studio. To date, the album has sold over eight million copies in the United States.
Description provided by Wikipedia under Creative Commons Attribution CC-BY-SA 4.0


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Getting Smart About Smart Meter Analytics
Posted by: Metering International
January 4, 2015
The Missing Link to Satisfying Customers, Enhancing Operations, and Running a Better Utility Business
By Larsh Johnson, CTO, Siemens Smart Grid Software Solutions
New market forces, including environmental concerns and government regulations, combined with outdated and proprietary infrastructure, have propelled the utility industry to a tipping point which is driving a monumental change across the U.S. and around the world. Utilities are now deploying vast networks of Advanced Metering Infrastructure (AMI), commonly called smart meters.
4 Comments
albertoJune 9, 2014 at 6:44 pm
Imlementation of advanced metering technology and customized enhancements will enable to EPM to transform the way the company conducts business and interacts with customers
thirumanamcheri santhanam gopalanDecember 20, 2014 at 7:09 am
Yes, the implemntation of advanced metering technology will enable all the electricity utilities as well as its customers to enjoy lot of advantages such as monitoring the inter grids, its up date status, billing & esy collection of payments from the customers,saving of administrtive expenses etc, keeping the customers informed of the latest situation on the powerfront , augmentation of power through alternative energy sources such as solar power, wind energy etc by involving the customers etc.. innumerable advantages can be obtained using the AMI/AMR/ technologies .
kolmemdsahebDecember 20, 2014 at 12:20 pm
Metering international provided useful information
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You are using an outdated browser. Please upgrade your browser to improve your ReverbNation experience.
Go to www.soundclick.com/jessjbeatz if you looking for some new production/beats for your album or mixtape. Best beats on the net!
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Even if you not looking for tracks, I'll give you 20% of every referral you send me. I believe in looking out for those who look out for me. –Jess J
www.soundclick.com/jessjbeatz or www.reverbnation.com/jessjbeatz


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Appointments & Offices
Check insurance plans, locations and make an appointment
Is Amy Swift accepting new patients?
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Expert Advice on Teaching
Welcome to our Expert Advice section. We're working hard to fill this page up with articles by experienced teachers, and interviews with leaders in the education field.
If you're interested in working with us on this (interested in writing articles, conducting interviews, or being interviewed), please send us an email.
- Becoming a Teacher in Your Second Career
by Sarah Landrum on May 21,2015
Find out the best way to achieve your dreams and become a teacher in your second career. What you need to know to make the best decision possible.
- What is the Difference Between EdD and PhD in Education?
by Chelsea Dunning on May 12,2015
Learn the major differences between a Doctorate in Education (E.d.D) and a Ph.D. in Education. What you need to know to make the right decision for your future.
- What It Takes to Become a Principal
by Josh Coburn on August 13,2014
Learn what it takes to become a principal at the elementary, junior high, or high school level as well as what is expected of many principals regardless of what level they are the administrator over.
- The Need for Special Education Teachers
by Susan Melgren on March 14,2014
The U.S. has an increasing need for special education teachers. Consider making a difference in the field of education by becoming a special education teacher.
- An Introduction to the Common Core State Standards
by Susan Melgren on February 20,2014
Learn more about the history of the Common Core State Standards, who they affect, how they're being implemented, and some of the controversy surrounding them.
- Should You Pursue a Master's in Education?
by Alisha Hipwell
- Becoming a Teacher: Is Alternative Certification for You?
by Alisha Hipwell


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Both are lovely.
Welcome to the Quilting Board!
Both are lovely.
Ahhhhhh I have the mag and was admiring the quilt.....you`ve given me a great idea...thank you for sharing....your top is just so cute!!!!!
They are lovely!
Very pretty and you did a great job on your FMQ!
nice heart quilt
Adorable! Love them.
Country 1
very pretty!!!!
These are darling! I remember making paper Valentine baskets with my kids in this pattern. Fun to see it carried out in fabric!
KEEP CALM and CARRY ON!!
how sweet are these


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NETWORK, A National Catholic Social Justice Lobby, deplores the current inability of Congress to govern responsibly and for the common good. They have turned democracy on its head, with one extreme faction of one party in the House of Representatives able to subvert the will of the people and even most of the legislators. Read more
In response to today's
U.S. Census Bureau's release of 2012 poverty statistics, Sister Simone
Campbell, Executive Director of NETWORK, stated: "The poverty statistics
released today underscore once again the continuing grim reality that millions
in our nation struggle at the economic margins. We call on Congress to
immediately halt efforts to decimate programs that help people live lives of
dignity and promise." Read more
As the world community debates what can or should be done to alleviate that suffering, NETWORK stands strong in our belief that violence is not the solution as it only begets more violence. Read more
Sister Simone Campbell, NETWORK Executive Director, testified today before the House Budget Committee about government programs that address poverty. The committee is chaired by Representative Paul Ryan, whose 2012 budget proposals were criticized by NETWORK and NETWORK's "Nuns on the Bus" because they included heavy cuts to vital programs that help people at the economic margins. Read more
On Wednesday, July 31, Sister Simone Campbell*, NETWORK Executive Director, will testify before the House Budget Committee, which is chaired by Representative Paul Ryan. The hearing is entitled "The War on Poverty: A Progress Report," and she will talk about the vital role that government-funded programs play in partnership with church/private initiatives. Without them more children would be hungry and more hardworking families would suffer. Read more
President Obama was exactly right when he said that "this growing inequality is not just morally wrong, it's bad economics." It also does not reflect true American values. Read more
Today, Sister Simone Campbell and other members ofNETWORK's "Nuns on the Bus" campaign briefed Members of Congress, congressional staffers and guests on the urgency of passing immigration reform now. Read more
On Wednesday, July 24 at 1:30 PM, Sister Simone Campbell and other members of NETWORK's "Nuns on the Bus" campaign will brief Members of Congress, congressional staffers and guests on the need for quick action on immigration reform. All are welcome. Read more
Racism and violence continue to be two of the deepest stains on our nation. Each of us should take a moment to pray and reflect—but, only a moment. In our hearts, we already know that a moral nation does all it can to eradicate both. The time to act is now. Read more
Message: Pass Comprehensive Immigration Reform! Read more


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Make sure you check out the Nikita Floyd Show Friday at 10am when Nikita talks about the blame game in the snow fiasco in Atlanta; Black History month, and what we should be doing in February in preparation for the 2014 lawn and garden season. Nikita will also discuss healthy eating experiences and love inspiration-words that will blow your lovers mind for a week. The Nikita Floyd Show, Fridays at 10am on 1450 WOL and on the web at www.woldcnews.com
The Blame Game And Black History On The Nikita Floyd Show.
Comments: 0 | Leave A Comment
Tags: ATLANTA » Lawn and garden » Nikita Floyd


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Morgan R.
(1 review)
I have been a full time nanny and part time babysitter for a year and a half now. I have worked for a few families and have experience cooking and doing light housework for them when needed.
I find my time working with children to be some of the most memorable moments of my life. To have that satisfying sensation that you were helpful in some way.


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new choral composition contest deadline extended
Event Date: April 1, 2010
Posted: March 16, 2010
Views: 3205
Location: Illinois, USA
The Lutheran Youth Choir of North America, a national auditioned touring choir for high school youth formed in 2006, has initiated a new annual International Choral Composition Contest with a $500 First Prize. This year's entry deadline has been extended to April 1, 2010. All composers age 18 and older, from any country, who desire to contribute to the genre of excellent sacred music suitable for high-school-age singers are invited to apply. In addition to the cash award, the winning composition will be premiered by the choir on its annual summer tour. For more information, go to www.lutheranyouthchoir.org.


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Type: Posts; User: Shaxspear
Made lamb tagine the other day, and hot damn it was delicious.
Any other Japanese knife brand suggestions other than Miyabi or Takayuki?
I have a Weekend 1 3day available at face value. Won't have it until I pick it up from will call on the Thursday, but I'm not looking for money in advance. Just a lead on a buyer.
Girlfriend can't make it anymore. I'll be picking the passes up at will call on the Thursday. I'm not looking for payment before giving you the passes. Just looking to secure a buyer before getting...
Pneumos aren't uncommon for kids with that kind of build. Yes they can happen at any time. Some are minor and can resolve themselves, while others can cause tension pneumos and have the potential to...
De La Soul
Killer Mike
That's not always effective either.
Yeah a gram "should" kill almost everyone, but there are always exceptions. That's why my ideal cocktail would be Fent/ketamine to snow them long enough for the sux and kcl to do the job.
There is injectible fentanyl. It's in mcg though. Injecting them with that much wouldn't take that long. It would be a race between the respiratory depression and hypotension that would kill them.
Snow them Propofol/Fentanyl/Ketamine concoction so they have no chance of feeling anything.
Sux/Rocuronium to make them stop breathing/moving.
Potassium Chloride to make sure the job is done.
The only weekend I've never had to help someone out was Weekend 1 this year. It's hot and people make bad decisions.
Tell Shannon she's going to get shanked.
Almost half of my posts are in the NFL thread. I can see where the confusion comes in.
#5 in the weekend 2 shot sitting on the foot. I missed the weekend 1 shot by a minute.
I think I'm going to try to make it to one of them this year
You'll likely have to pay oversized baggage fees that will vary depending on the airline.
We were camped right across from the ADA camping last year and it was the perfect spot.
I will preface this by saying that I am a full blown meatatarian, but the Native Foods Cafe is a vegan restaurant with amazing food. We go there once or twice every year during Coachella.
I was told in the past that the first wristband to be scanned has to be with the camping pass.
I had a blast last year. If the lineup tickles my fancy again this year, I'll probably go again.
I could see Sanchez going to the Seahawks as a backup if nobody throws him a bone.
Gutted. I don't think there's another band I've seen as many times as GWAR. I don't own a single album, but they came to town every year and I would always try to go because they were that much fun.
Finally ended up receiving my kickstarter immersion circulator and gave it a spin tonight cooking everything with it.
Striploin cooked to...
Even with the new stadium it shouldn't be too hard. Just keep an eye on NFL ticket exchange or stubhub when the schedule gets released.
Skyscanner app
I happen to enjoy stupid music festivals. I would rather spend the money to do both weekends than do VIP for one. That and I was in France in September. Sadly my girlfriend wasn't keen on bringing a...
There are plenty of people like myself who have more than enough money and still refuse to spend it on a VIP pass. It's completely subjective if you think it's worth it. There are air conditioned...
Good luck and Godspeed. That shit is delicious.
Or you can just save yourself the money and find yourself a girlfriend who isn't a boring, stuck up priss.
Do you have multiple camping passes? The first year I did onsite camping with an 8 person tent and was lucky I had an awesome neighbour who let us encroach on their space because there wasn't enough...
Julysquatch > Maysquatch
The Seahawks need to be smart in the front office if they want to stay competitive in the long run. While they do have a couple of overpaid players, they have quite a few star players that are being...
Not once have I ever been bored by my team completely destroying an opponent.
Humor me.
Is this supposed to be you "breaking it down"? It would have made sense if I was someone asking a stupid question. If you don't want to admit you misinterpreted the context and you...
Feel free to break it down for me genius. Someone asked a question. I shared a common experience contrary to what's supposed to happen. PF for whatever reason quotes me and calls me a nimrod. I find...
Come again? PF called me a nimrod and you called us dipshits. Way to read, though.
Right. The board is full of assholes that troll new people with incorrect information on a regular basis, and yet I get called out for sharing an experience that appears to happen quite a bit.
I've never had my passes signed for. I've come home to them sitting in my mailbox the last 3 years.
**Edit but this is only the personal experience of a nimrod apparently**
Going to the Caribbean in January next year. We've already done Jamaica and St. Lucia. Where should we go next? Key deciding factors being beaches, food and snorkeling.
Frank Gore got a 6. I'm pretty sure he doesn't know how to tie his shoe.
It was 37
Be very careful and aware if you hit an ATM. We had to leave our resort to go get more money from an ATM at a bank down the road. The MINIMUM amount the machine would let us take out was $500. I'm...
Pretty much everywhere in Jamaica accepts USD, just make sure they're not shaking you down with a shitty exchange rate.
I'll give it a whirl sometime. What is the relevance of the skim milk powder?
I did the beef stock recipe from ChefSteps and it turned out really freaking good.


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Iranian animations to compete at Italy's Lenola filmfest
Two short Iranian animations are slated to take part in the 2012 Lenola Film Festival, competing with productions from around the globe. Alireza Chitai's Life Story of the Red Pencil and Nazanin Sobhani-Darbandi's Zero will be screened in the competition section of the Italian festival. Produced by Iran's Institute for Intellectual Development of Children and Young Adults (IIDCYA), the animations will compete with 16 other works from France, Croatia, Belgium, Spain, Mexico and Germany. The 15th edition of Lenola Film Festival will run from July 26 to 29, 2012, on the theme of 'To Choose.' The annual festival aims to express the enormous potential of short films and bring together the most important and significant artistic productions from Italy and around the world. TE/TE


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Height: 6-foot-8
Weight: 308 pounds
Class Year: 3V
Hometown: Cleveland, OH
No Videos Available.
The Latest: NFL Draft: Top 20 small-college prospects — 12/11/2008
One of the real tests for scouts and NFL scouting departments across the nation is their ability to locate small-school talent and uncover possible hidden gems throughout the draft process. Running back Rashad Jennings may be the best of the bunch this season.[details]
Joel Bell STATS
No Statistics Available.
Joel Bell College Videos
No Media Available.
No Bio Available.
Joel Bell Audibles
No Audibles Available.
Headlines from Rivals.com Network
NFL Draft: Top 20 small-college prospects — 12/11/2008, from Rivals.com College Football
NFL Draft: Seniors with something to prove — 10/8/2008, from Rivals.com College Football
Rivals.com is your source for: College Football | Football Recruiting | College Basketball | Basketball Recruiting | College Baseball | High School | College Merchandise
Site-specific editorial/photos �2012 Yahoo! Inc. All rights reserved. This website is an officially and independently operated source of news and information not affiliated with any school or team.
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Statistical information �2007 STATS LLC All Rights Reserved.


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When I got Jimmy Camp's new CD in the mail, my first thought was not, "Oh, how nice of Jimmy to think of me." It was, "Now I have some leverage to get him to let me print The Jimmy Camp Story."
Maybe it isn't uncommon for a rock musician to live on the streets of L.A. and San Francisco, to drink to excess, to take a lot of drugs, to rob people out of desperation, to get stabbed in a seedy hotel room, or to disappear for days while loved ones don't know whether you're dead or alive. But it is uncommon among Orange County's in-demand Republican political campaign managers. And that's what Camp is.
This morning, for example, he'll be working for Janet Nguyen, monitoring the supervisor race recount. He expects to spend the next two years working for Rudy Giuliani's California campaign. And while he and Mike Schroeder are on opposite sides of those races, they have worked together on many campaigns, among them the historic recall of a turncoat Republican who helped keep Willie Brown in power.
After amicablenegotiations about what I couldn't print - only one thing, basically - we met for breakfast yesterday at Watson's in Orange, a couple blocks from his house.
Camp was born in 1964 in Germany, where his father was stationed. The family moved back to the states and lived in Virginia and West Virginia. When he was 14, the family moved to Orange County, where his father attended a non-denominational divinity school. Jimmy went to the Melodyland (Christian) High School in Anaheim, but hung out with kids from Troy High in Fullerton, with whom he had more in common - namely, skateboarding and punk rock. One Troy student was Mike Ness, who would found Social Distortion.
Camp had started out playing Top 40-style rock guitar, "but in '78 I heard The Clash, and that was it." He became a full-on punker, playing in local clubs and writing songs. At 17, he left home for L.A. "I literally stood on Hollywood Boulevard playing guitar for money."
He moved to Huntington Beach and lived in one of the flophouse rooms above the Sugar Shack and became part of an increasingly debauched '80s scene on Main Street. (That's when I arrived in H.B. I'll bet Camp was one of the punks I'd think about making a permanent fixture in the pavement when they skated off the sidewalk and into my path.) On a typical night, Camp would play the Golden Bear then cross the street to Perq's. Drinking heavily and doing drugs, he'd get into fights with the punk-hating surfers. He remembers waking up after one fight to discover he had a smashed eye socket.
Musically, he was starting to fuse the sounds of The Clash, The Sex Pistols and The Ramones with the "roots" stuff his father had played, like Buddy Holly, Chuck Berry and Johnny Cash. In the late '80s, Camp left O.C. again and did the street-musician thing in San Francisco and Austin. One night in S.F., a junkie broke into his room in a welfare hotel and tried to steal his guitar. They fought and the tweaker slashed Camp's left hand. Unable to play guitar, he had his mother send him bus fare and he came home.
By 1988, he was ready to tone it down. He played in O.C. bands, but he'd stopped the drugs and cut back the booze. During this period, he scored a job working political phone banks for former O.C. Republican Chairwoman Lois Lundberg. He had no interest in politics. He'd never even voted. He took it strictly for the hours - the 5 p.m.- 9 p.m. shift let him play and party late and sleep all day. But something happened. He became a supervisor. Then Lundberg started farming him out to GOP campaigns around the state. He got hooked on politics.
"It's the sport of it. The adrenaline rush," he says. He went to closing down campaign offices as often as he closed down bars. And people like Schroeder, then chairman of the state Republican party, took notice.
"He's one of the great political gym rats," Schroeder says. "If you didn't stop him, he'd work deep into the night." And while unabashedly maintaining his rocker trappings - he still makes his raw, earthy music; he still has the tattoos he collected as a punker; you rarely see him in a suit.
"Some of the more conservative (politicos) are taken aback by the tattoos and leather jacket," Schroeder says, "but that goes away as soon as they realize how good he is at what he does."
Tomorrow: Camp's late-night work has a dark side; his new CD; the recount front, where he and Schroeder face off today.
Contact the writer: Mickadeit writes Mon.-Fri. Contact him at 714-796-4994 or firstname.lastname@example.com


text: Utah Surplus In Utah Coffers By Lynn Ware Peek • Sep 17, 2014 State officials say Utah finished the fiscal year with an extra $112 million to spend on one-time projects. Lynn Ware Peek has more. Duffin Builds State-wide Trails Non-profit By Lynn Ware Peek • May 1, 2014 alpinetrails.com A new non-profit group with experienced leadership at its helm has opened its doors. The new Trails Utah will help other communities promote trails and trail usage and will follow the Park City model. Lynn Ware Peek has more. Utah's AG Speaks For Ban On Same-sex Marriage By Associated Press • Apr 11, 2014 Utah Attorney General Sean Reyes spoke at a rally Friday in Salt Lake in favor of the same-sex marriage ban. Lynn Ware Peek has more. Federal Judges Split On Same-sex Marriage Ruling By Lynn Ware Peek • Apr 10, 2014 One day into the hearing on District Robert Shelby's ruling declaring Utah's same-sex marriage ban unconstitutional, judges on a Federal appeals court are divided and a ruling is not expected for several months. Lynn Ware Peek has more. Outgoing Mayor's Last Wish Becomes Moot - To His Delight By Lynn Ware Peek • Dec 23, 2013 Alex Butwinski Park City Mayor Dana Williams has now performed some 25 same-sex marriages at the Summit County Courthouse, as the ruling that declares Utah's ban on gay marriage is declared unconstitutional. Lynn Ware Peek has more. Same-sex Marriage Comes To Summit County By KPCW • Dec 23, 2013 Alex Butwinski UPDATE: Monday 12/23/2013, 12:35 PM After two appeals to stay the decision to allow same-sex marriage in Utah were denied in the federal appellate court, the case goes back to Judge Robert Shelby, who already said he won't offer a postponement of his original ruling because the arguments made Monday were the same ones he had already considered in his original ruling from Friday. Park City Mayor Dana Williams has now performed at least 28 same sex marriages in Summit County since 8 AM this morning. MONDAY, 12/23/2013, 9:45 AM Governor Herbert Honors Robert Redford By Leslie Thatcher • Nov 11, 2013 Leslie Thatcher Film actor, director and founder of the Sundance Institute Robert Redford was honored by the state of Utah Saturday, with November 9th being proclaimed as Robert Redford Day in Utah. KPCW's Leslie Thatcher has more. Shutdown Of The National Parks In Utah By Lynn Ware Peek • Oct 14, 2013 SALT LAKE CITY - Utah's five national parks were bustling with visitors over the weekend as parks re-opened at least for now. Lynn Ware Peek has more. Tourism Means Big Bucks By Leslie Thatcher • Sep 18, 2013 Tourism is big business in Utah and Summit County makes a big contribution to that. KPCW's Leslie Thatcher has more. Utah Schools To Receive Letter Grades By Lynn Ware Peek • Aug 21, 2013 Just like school kids receive an A, B, or C, in a new statewide scoring program, so too will the schools be given a letter grade. Lynn Ware Peek has more.


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Email AddressVerified
Phone Number▒▒▒▒▒▒▒▒▒▒▒ 17
Reviewed3 Reviews
About Me
- School
- Sydney University [1983]
- Work
- independent / retired
- Languages
- English, Español
- John's Airbnb Symbol
I'm a well travelled Australian, now long time Argentine resident, and like to welcome interesting people to come and enjoy my slice of paradise that is San Carlos de Bariloche.
In summer or winter, Bariloche is a perfect place to enjoy lakes, mountains, and scenery beyond belief.
Whether your a skier, canoeist or kayaker, into bike riding, hiking, mountaineering, climbing, swimming, scuba diving, or just sitting and chilling on the deck taking in the views, with a malbec in hand, we have it all here for you to enjoy.
I find it hard to leave - as will you !


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December 2, 2012
Baldwinsville senior running back Tyler Rouse, seen here in the Section III Class AA semifinal against Fayetteville-Manlius, was chosen the Gatorade New York State Player of the Year after a season where he gained 2,977 yards and scored 45 touchdowns. Rouse is the first Section III player honored with this award since Onondaga's Latavius Murray in 2007.
Stories this photo appears in:
Rouse garners State Player of the Year honor
B'ville runner first Section III honoree since 2007
Now the post-season accolades begin to pour in for Baldwinsville football standout Tyler Rouse. The senior running back, who led the Bees to the Section III Class AA final this fall, was just named the Gatorade Player of the Year in New York State, the first Section III player selected for that high honor in six years.
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