text: DSpace Collection: http://dspace.cityu.edu.hk:80/handle/2031/728 2017-05-18T09:46:10Z 2017-05-18T09:46:10Z Group 4 Complexes Bearing Chelating σ-Aryl, σ-Alkenyl and Alkyl Ancillary Ligands: Synthesis, Spectroscopic Characterization and Olefin Polymerization Catalysis Liu, Cham Chuen (劉湛全) http://dspace.cityu.edu.hk:80/handle/2031/8651 2016-12-05T10:02:34Z 2015-01-01T00:00:00Z Title: Group 4 Complexes Bearing Chelating σ-Aryl, σ-Alkenyl and Alkyl Ancillary Ligands: Synthesis, Spectroscopic Characterization and Olefin Polymerization Catalysis Authors: Liu, Cham Chuen (劉湛全) Abstract: Chapter 1 gives an introduction to group 4 catalysts for olefin polymerization, and a brief review of recent developments in post-metallocene catalysts. Chapter 2 describes general experimental procedures. Group 4 post-metallocene complexes supported by tridentate pyridine-2-phenolate-6-(σ-aryl) [O,N,C(σ-aryl)] ligands, containing methyl substituent(s) on the σ-aryl group, are described in Chapter 3. The principal aim is to investigate the steric and electronic effects upon chemical and catalytic reactivity. The synthesized complexes have been characterized by multinuclear NMR spectroscopy, and η2-coordination of benzyl groups is indicated for all titanium and zirconium complexes. Moreover, the impact of the "py-adjacent" substituent (σ-aryl substituent adjacent to pyridyl ring) upon the C(σ-aryl) atom was indicated by 13C NMR spectroscopy and X-ray crystallography. The polymerization properties of the [O,N,C(σ-aryl)] catalysts have been studied. Interestingly, one of the catalysts produced polyethylene with narrow molecular weight distribution (Mn = 1.3 × 105, Mw/Mn = 2.1), implying single-site character. Theoretical calculations have been performed to consider energy-minimized calculated (Gaussian) structures of selected catalytic species. In Chapter 4, ligands with a more flexible chelating-[O,N] moiety have been developed, and a series of group 4 post-metallocene complexes bearing [OCH2N,C(σ-aryl)] ligands has been synthesized and characterized by multinuclear NMR spectroscopy. Unlike [O,N,C(σ-aryl)] complexes which display C2v symmetry, these complexes adopt C1 symmetry. Variable-temperature 1H NMR experiments suggest a fluxional process concerning the seven-membered [OCH2N] ring, and the associated activation barrier was calculated. The polymerization properties of [OCH2N,C(σ-aryl)] catalysts have been examined. However, these catalysts are less active compared with [O,N,C(σ-aryl)] analogues. A [O(methoxide),N,C] system bearing a five-membered [O,N] chelate ring was also developed. The catalytic capabilities of these complexes have been tested, but all are inactive for ethylene polymerization. The synthesis, spectroscopic characterization and olefin polymerization behavior of a series of group 4 catalysts bearing aryl-substituted chelating C(sp3)-donor ligands are described in Chapter 5. The [O,N,C(alkyl)] complexes adopt C1 symmetry, which is confirmed by solution NMR spectroscopy and X-ray crystal structures. Interestingly, metalation between M(CH2Ph)4 and the (bis-pyridyl)-substituted ligand gives [O,N,N] products, which are structurally different from [O,N,C(alkyl)] complexes. The [O,N,N] complexes are of C2v symmetry, and interesting resonance structures have been proposed based on spectroscopic observations. The polymerization properties of [O,N,C(alkyl)] catalysts have been studied. Notably, excellent catalytic activities (up to 5127 g mmol1 h1) was observed in conjunction with [Ph3C][B(C6F5)4]/iBu3Al at 22 oC. DFT calculations have been performed to gain insight into catalytic behavior. The development of chelating σ-alkenyl ligands to support group 4 post-metallocene complexes are described in Chapter 6. Mononuclear complexes bearing a σ-cyclohexenyl moiety, and unusual dimeric complexes featuring a novel μ-η3:η3 bonding mode for the C4-bridging "butadienoid" moiety, have been synthesized and characterized by multinuclear NMR spectroscopy. The binuclear complexes, which are readily formed by dimerization processes, are of C2 symmetry. Careful examination of the chemical shifts of the carbon and proton NMR resonances for the C4-bridge suggests that contributions from the proposed resonance structures may vary for different binuclear complexes and metal centers. UV-vis absorption studies have been performed in order to probe the charge transfer nature of these complexes, and infrared spectroscopy was employed to study the bonding of the C4-bridging moiety. Investigations into their catalytic characteristics in ethylene polymerization have been undertaken in conjunction with MAO or [Ph3C][B(C6F5)4]. Notes: CityU Call Number: QD474.L576 2015e; Includes bibliographical references.; Thesis (Ph.D.)--City University of Hong Kong, 2015.; 1 online resource (xiv, 382 p.) : ill. (some col.) 2015-01-01T00:00:00Z Fluorescent probes for thiol and hydrogen sulfide detection in living cells Zhang, Huatang (張華堂) http://dspace.cityu.edu.hk:80/handle/2031/8599 2016-11-09T03:41:09Z 2015-01-01T00:00:00Z Title: Fluorescent probes for thiol and hydrogen sulfide detection in living cells Authors: Zhang, Huatang (張華堂) Abstract: Small molecule thiols, including cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), play crucial roles in maintaining cellular redox environment and mitigating damages from free radicals and toxins. Recent research has showed that hydrogen sulfide (H2S) can be produced from sulfur-containing biomolecules such as Hcy and Cys. H2S has been linked to a series of diseases, including Alzheimer's disease, Down's syndrome, diabetes and liver cirrhosis. Consequently, development of highly sensitive and selective fluorescent probes for detecting thiols and H2S is intensely sought after because of their critical roles in physiological and pathological processes. After introducing the background on fluorescence, fluorescent probes for thiol and H2S detection were summarized in chapter 1. In chapter 2, a new fluorescent probe was developed for selective detection of thiols based on 1,4-Michael addition reaction of α,β-unsaturated acyl sulfonamide. The probe has good water solubility and reacts with thiols under aqueous conditions without using organic solvents and additional catalysts. More importantly, the probe could selectively detect thiols rather than other strong nucleophiles such as amines. We also proved that the probe could be applied to detect thiols in living cells. The probe was subsequently applied to detect intracellular thiols. In chapter 3, we proposed a novel strategy, namely, a fluorescent probe installed with dual-reactive and dual-quenching groups, for rational design of highly selective and sensitive fluorescent thiol probe. The principle of the strategy is as follow: 1) based on the dual-quenching effects, the fluorescence of the probe can be maximally inhibited, and the turn-on response upon thiol activation is much larger which leads to high sensitivity of the probe towards thiols; 2) based on the dual-reactive groups, the selectivity of the probe towards thiols is greatly improved, because the thiol detection can only be obviously interfered by molecules that can react with both two different reactive units. As a proof-of-concept study, we prepared such a new fluorescent thiol probe installed with dual-reactive and dual-quenching groups. The experimental results indicated that sensitivity of the probe towards thiols was significantly improved by dual-quenching effects, whereas selectivity of the probe was also greatly enhanced by installation of dual-reactive groups. Chapter 4 provides a novel and remarkably probe 4F-2CN, (tetrafluoroterephthalonitrile), which was discovered to be an efficient fluorescent probe for detecting thiol under physiological condition. Interestingly, fluorescent probe for detecting thiol under physiological condition. Interestingly, reacts with Hcy/GSH and generates blue fluorescence. Bioimaging experiments proved that Cys and Hcy/GSH can be selectively detected using two distinct mission channels. Addition of CTAB (cetyl trimethylammonium bromide) was observed to alter the fluorescent color of the reaction product of 4F-2CN and Hcy (from blue to green), but no alteration of fluorescent color occurred for Cys and GSH. Therefore the three commonly occurring thiols (Cys/Hcy/GSH) can be discriminated through the combined use of 4F-2CN and CTAB. Furthermore, with the use of CTAB, Cys, Hcy and GSH can be selectively detected using two distinct emission channels. In addition, the reaction product of 4F-2CN and Cys exhibits two-photon property, offering potentially useful tools for tissue imaging studies. Chapter 5 reports a novel fluorescent probe for detecting H2S based on iminocoumarin benzothiazole scaffold. The probe utilizes a H2S-induced cascade reaction consisting three consecutive steps: reduction, elimination and cyclization. The probe is highly sensitive and displayed around 80-fold increment in fluorescence signal after reacting with H2S under physiological condition. The probe also showed excellent selectivity towards H2S over other biologically relevant species including ROS, RSS and RNS. It displayed 32-fold of selectivity for H2S compared to that of other reactive sulphur species. Furthermore, the probe has been applied for imaging H2S in living cells. Cell imaging experiments demonstrated that the probe is cell-permeable and can be used to monitor the alteration of H2S concentration in living cells. Chapter 6 has developed a fluorescent probe based on rhodamin 110 to detect H2S in aqueous buffer at physiological pH. Because of the dual azide quenching effect, the probe exhibited high sensitivity for H2S detection. The fluorescence intensity increases by approximately 120-fold when H2S is added. The detection limit can be as low as 1.12×10-7 M. The probe is highly selective to H2S over other biologically relevant species. It displays 32-fold selectivity over reactive sulfur species. The probe also has good cell-permeability and can be used for live-cell imaging of H2S. Notes: CityU Call Number: QH324.9.F4 Z45 2015; xxix, 186 pages : illustrations 30 cm; Thesis (Ph.D.)--City University of Hong Kong, 2015.; Includes bibliographical references. 2015-01-01T00:00:00Z Assessment of endocrine disrupting hormones, alkylphenol ethoxylates and phthalic acid esters in the aquatic environment of the Pearl River Delta, China Wu, Qian (吳茜) http://dspace.cityu.edu.hk:80/handle/2031/8598 2016-11-09T03:41:07Z 2015-01-01T00:00:00Z Title: Assessment of endocrine disrupting hormones, alkylphenol ethoxylates and phthalic acid esters in the aquatic environment of the Pearl River Delta, China Authors: Wu, Qian (吳茜) Abstract: Endocrine disrupting chemicals (EDCs) are heterogeneous groups of chemicals that can interfere with endocrine function in organisms at low concentrations and are considered "contaminants of emerging concern". Among the identified EDCs, hormones, alkylphenol ethoxylates (APEOs) and phthalic acid esters (PAEs) have attracted high research interests in recent years because of their high production and toxicity. Steroid hormones can disrupt the endocrine function of organisms at low levels (down to ng/L) in the aquatic environment. APEOs are mainly used as nonionic durability of plastic material. They have been proven to cause reproductive damage, metabolic disorders and some are carcinogens. Considering their prevalent application nd toxic effects, 4-Nonylphenol (NP) has been listed as a priority hazardous substance in the European Union (EU) and bis (2-ethylhexyl) phthalate (DEHP), benzyl butyl phthalate (BBP), and di-n-butyl phthalate (DNBP) are permanently banned above 0.1% in toys and childcare products in the EU, United States (US), Australia, and China. China has undergone a rapid industrialization process over the past several decades and become the second largest chemical producer after the US. The Pearl River Delta (PRD) region is situated in the southern part of China and it is one of the most urbanized areas of China, where manufacturing industries are flourishing. The occurrence of some EDCs in this region has been reported at relatively high levels in recent years. However, most of the studies mainly focused on a limited number of groups of EDCs in certain environmental matrices. The sources, behaviour, fate and environmental risk of multiple priority groups of EDCs in the PRD are not yet clear. It is necessary to conduct a comprehensive evaluation of the source, occurrence, behaviour and fate of multi-groups of EDCs of high concern in this region. The objectives of this study are 1) to develop a method for simultaneous determination of multiple groups of EDCs in various environmental matrices, including sewage, sludge, seawater and river water and sediment to investigate their occurrence, distribution and fate in the PRD, 2) to examine the removal efficiencies of representative sewage treatment facilities, which are considered one of the major sources of EDCs for the aquatic environment, and calculate the daily mass balance of target EDCs in the sewage treatment plants (STPs), 3) to identify their sources and fate in different abiotic samples in the PRD, 4) to study and compare the levels of target EDCs in different highly developed regions including the PRD, Yellow River Delta (YRD) and Tokyo Bay (TB), 5) to conduct a preliminary risk assessment of the oestrogenic effect of the 12 most potent and abundant EDCs in STP influent, effluent, seawater, river water, and sediment of the PRD, and then to evaluate their potential risk to aquatic organisms. A solid phase extraction (SPE) cleanup procedure followed by application of ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) was developed for simultaneous detection of 33 target EDCs (Estrone (E1), 17α-estradiol (17α-E2), 17β-estradiol (E2), estriol (E3), 17a-ethynylestradiol (EE2), diethylstilbestrol (DES), norethindrone (NRT), progesterone (PGR), equilin (EQ), equilenin (EN), testosterone (TTR), bisphenol A progesterone (PGR), equilin (EQ), equilenin (EN), testosterone (TTR), bisphenol A 4-tert-octylphenol-di-ethoxylate (4-t-OP2EO), NP, 4-nonylphenol-mono-ethoxylate (NP1EO), 4-nonylphenol-di-ethoxylate (NP2EO), 4-n-nonylphenol (4-n-NP), 4-n-nonylphenol-mono-ethoxylate (4-n-NP1EO), BBP, dimethyl phthalate (DMP), diethyl phthalate (DEP), DNBP, di-isobutyl phthalate (DIBP), dicyclohexyl phthalate (DCHP), di-n-hexyl phthalate (DNHP), di-n-octyl phthalate (DNOP), DEHP, dibenzyl phthalate (DBzP), diphenol phthalate (DPP), diphenoliso-phthalate (DIPP), and benzyl benzoate (BzBz)), and was successfully applied for the analysis of different environmental samples. The lower detection limits of the current method for aqueous and solid matrices are 0.01-2.5 ng/L and 0.01-25 ng/g, respectively. The relative recoveries ranged from 70% - 120% with relative standard deviation less than 15% in most matrices, complying with the requirements for environmental sample analysis. Hong Kong is an international metropolis located in the PRD, and traditional and advanced sewage treatment facilities can be found here for treating the sewage generated by the high population. Sewage and sludge samples were collected from four STPs covering not only the conventional preliminary, primary, and secondary treatments, but also tertiary and some advanced treatment facilities. E1, NP2EO, and DEP were dominant for each group in the influent samples with concentrations ranging from 11-33, 747-3945 and 445-4635 ng/L, respectively. Conversely, PGR, NP1EO and DEHP were most abundant in dewatered sludge. The preliminary creening, primary sedimentation and disinfection approaches achieved the lowest removal efficiencies (< 30%) for most chemicals, while activated sludge showed greater than an 80% removal rate to more than two-thirds of compounds and the removal rate of reverse osmosis was greater than 99% for most pollutants. Mass balance results suggested that steroid hormones are usually removed by biological prefer to be adsorbed in the sludge phase. The estradiol equivalent quotient based risk assessment indicated that secondary and higher STP treatments can distinctly decrease the oestrogenic effect of effluent released into the environment and the levels of EDCs in seawater from Victoria Harbour (VH) have a low to medium risk in terms of oestrogenic effect on aquatic organisms. In the PRD river and seawater samples, E1 was frequently detected (82%) at concentrations ranging from 0.08-2.4 ng/L, while synthetic estrogens were below the detection limit. NP and its short-chain ethoxylates account for more than 80% of total target phenols, though their concentrations (2.5-390 ng/L) were lower than the levels in some European countries. APEO pollution along the western coast of Shenzhen and Hong Kong is obviously higher than the eastern coast, which could be impacted by the riverine input of the Pearl River (PR). Concentrations of DMP in river water were significantly higher than those in coastal seawater samples. In contrast, the distribution pattern of DIBP was the opposite. In the YRD and TB, the overall concentrations of target EDCs were lower than that in the PRD, which was inferred to be attributed to the lower discharge amount and better waste treatment facilities in these regions. Improved STPs could reduce the direct discharge of pollutants from both industrial and domestic sources into the aquatic environment. The composition profiles and concentrations of the target compounds between the surface and bottom water were comparable, indicating the rapid vertical diffusion of these pollutants. PR flowing across Guangzhou and Dongguan and VH in Hong Kong showed a relatively higher hazard potential than other sampling sites in the PRD region. In order to estimate the worst-case scenario, a species-based risk assessment was also conducted and fish vitellogenin inducement was the most sensitive endpoint for hormones. The currently detected concentrations of E2, NP, and BPA in the PRD region were lower than the EU guideline values, which are 1, 330 and 1600 ng/L, respectively. The occurrence and fate of EDCs in the PRD sediment indicated different patterns with water samples. The concentrations of progestogen and androgen ranged from 0.10 to 5.4 ng/g (dw). Estrogen concentrations ranged from 0.16 to 7.6 ng/g (dw). NP is more persistent than its ethoxylate analogues, accounting for the top percentage among APEOs. DEHP was dominant in the PAE group (92%), as pollutants with relatively higher logKoc values preferred to accumulate in the sediment phase. The overall sediment concentration is equal or lower than other studies conducted elsewhere. Pollutant distribution has a decreasing gradient from northwest to southeast within the study areas. The concentrations of NPEOs, BPA, and DEHP in the PR were one order of magnitude higher than that in the West River (WR), PR estuary, and coastal area of Hong Kong. The intensive shipping activity in the western part of Hong Kong waters was inferred to be associated with the higher APEO concentration in this area. The risk assessment on benthic species at various trophic levels demonstrated that in the worst case scenario, NP, 4-t-OP, BPA, and DEHP are at high risk and they may pose adverse effects on the growth and reproduction of benthic organisms. It has been reported that mud snail embryo development is highly sensitive to alkylphenols. The concentration of NP detected in 36.7% of coastal sediment samples and 65.3% of the PR sediment samples were higher than the EU threshold value, which could pose a high risk to benthic organisms. Overall, the current study has provided a comprehensive investigation of the occurrence, source, distribution and fate of three groups of EDCs of high concern in the PRD. STPs are important in the reduction of direct waste discharge of EDCs. Secondary treatment or higher degree of treatment method is able to lower the levels of most EDCs significantly. Sludge should be cautiously treated in consideration of the adsorption of large amounts of lipophilic EDCs. The PR is more severely polluted than other study sites, although the situation has been improving by upgrading the wastewater treatment facilities since 2008. The overall oestrogenic effect in the study area water has a low to medium risk to aquatic organisms. Notes: CityU Call Number: RA1224.2 .W8 2015; xxv, 279 pages : illustrations (some color) 30 cm; Thesis (Ph.D.)--City University of Hong Kong, 2015.; Includes bibliographical references (pages 217-279) 2015-01-01T00:00:00Z Kinetics and mechanisms of some redox reactions of nitridoruthenium(VI) and nitridoosmium(VI) complexes bearing a salen ligand in aqueous solutions Wang, Qian (王倩) http://dspace.cityu.edu.hk:80/handle/2031/8597 2016-11-09T03:41:04Z 2015-01-01T00:00:00Z Title: Kinetics and mechanisms of some redox reactions of nitridoruthenium(VI) and nitridoosmium(VI) complexes bearing a salen ligand in aqueous solutions Authors: Wang, Qian (王倩) Abstract: The chemistry of metal nitrido complexes has received much attention in recent years. This thesis describes the kinetics and mechanisms of the reactions of [Ru(N)(salchda)(MeOH)]+ and [Os(N)(salchda)(H2O)]+ (salchda = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion) with L-ascorbic acid, sulfite, hydroxide and L-cysteine in aqueous media. The oxidation of L-ascorbic acid (H2A) by [RuVI(N)(salchda)(MeOH)]+ (RuVIN) has been studied in aqueous acidic solutions from pH range of 1 to 6 under argon atmosphere. The reaction has the following stoichiometry: 2RuVIN + 3H2A → 2[RuIII(NH2-HA)]+ + A. The pseudo-first-order rate constant, kobs, depends linearly on the concentration of H2A. The second-order rate constants, k2 are dependent on [H+] according to the relationship k2 = (ka[H+] + kbKa) / ([H+] + Ka), where ka and kb are the rate constants for the oxidation of H2A and HA-, respectively. At 298.0 K and I = 0.1 M, ka = (6.47 ± 6.25) × 101 M-1 s-1, kb = (4.84 ± 0.10) × 103 M-1 s-1 and Ka = (4.23 ± 0.40) × 10-5. Kinetic studies have also been carried out in D2O. The solvent kinetic isotope effects are 3.32 and 0.98 for ka and kb, respectively. Mechanisms involving HAT/N-rebound at low pH (≤ 2) and nucleophilic attack at the nitrido at high pH (≥ 5) are proposed. The kinetics of oxidation of sulfite (SIV, SO32- + HSO3-) by [RuVI(N)(salchda)(MeOH)]+ (RuVIN) and [OsVI(N)(salchda)(H2O)]+ (OsVIN) have been studied in aqueous solutions. For the oxidation of SIV by RuVIN, the rate law is -d[RuVIN]/dt = k2[RuVIN][SIV]. The second-order rate constant, k2, is found to be pH dependent with k2 = (ka[H+] + kbKa)/([H+] + Ka), where ka and kb are the rate constants for the oxidation of HSO3- and SO32-, respectively. At 298.0 K and I = 1.0 M, ka = (1.63 ± 0.92) × 102 M-1 s-1 and kb = (6.17 ± 0.02) × 106 M-1 s-1, respectively. For OsVIN, the reaction has the following stoichiometry: [OsVI(N)]+ + SO32- + 2H+ → [OsIV(NH2SO3)]+. The rate law is -d[OsVIN]/dt = k2[OsVIN][SIV]. The dependence of k2 on [H+] shows a similar relationship with ruthenium(VI) nitrido where ka' and kb' were found to be (2.79 ± 0.97) × 10-1 M-1 s-1 and (1.14 ± 0.03) × 101 M-1 s-1 respectively at 298.0 K and I = 1.0 M. For both RuVIN and OsVIN, sulfite undergoes nucleophilic attack at the nitrido ligand to afford the sulfamato species, [RuIII(NH2SO3)(salchda)(OH2)] and [OsIV(NH2SO3)(salchda)(OH2)]+, respectively. Details of the reaction mechanism will be discussed. The reactions of RuVIN and OsVIN with hydroxide (OH-) have been studied in aqueous alkaline solutions. For RuVIN, the reaction has the following stoichiometry: RuVIN + 2OH- → RuIINO + H2O. The rate law is -d[RuVIN]/dt = k2[RuVIN][OH-]. It is proposed that OH- undergoes nucleophilic attack at the nitrido ligand to afford the nitrosyl species, RuII(NO)(salchda)(OH). For OsVIN, the reaction follows the rate law -d[OsVIN]/dt = k2[OsVIN][OH-]. The mechanism involves initial N∙∙∙N coupling of [OsVI(N)(L)(OH)], followed by N2 releasing and attacked by another OH- to form the peroxo species, Os(O2)(salchda). The oxidation of L-cysteine (Cys) by [RuVI(N)(salchda)(MeOH)]+ has been studied in anaerobic aqueous solutions over the pH range of 1.00-5.32. The electrophilic ruthenium nitrido species undergoes stepwise reactions with L-cysteine to produce the sulfilamido ([RuIV(NH)(Cys)(salchda)]+), sulfilamine ([RuIII(NH2)(Cys)(salchda)]+), and amine ([RuIII(NH3)(salchda)]+) complexes of ruthenium. At low pH (pH ≤ 4), only two phases were observed. However, three phases were observed at high pH (pH ≥ 4). The rate laws for all three phases are phases were observed at high pH (pH ≥ 4). The rate laws for all three phases are 0.09) × 105 M-1 s-1, k2' = (1.78 ± 0.21) × 102 M-1 s-1, and k2'' = (6.52 ± 0.30) × 101 M-1 s-1 at pH = 5.32, T = 298.0 K and I = 0.1 M for the first, second, and third phase respectively. The dependence of k2 on [H]+ indicated that both protonated (Cys-H+) nd neutral species (Cys) are involved in the reaction with the relationship k2 = (ka[H+] + kbKa) / ([H+] + Ka), where ka and kb are the rate constants for the oxidation of Cys-H+ and Cys, respectively. The reactivity of Cys is almost 103 times greater than that of Cys-H+. Kinetic studies have also been carried out in D2O. For the first phase, the solvent kinetic isotope effects (ka(H2O)/ka(D2O) are 2.03 and 1.74 at pH = 1.0 and 5.4, respectively. For the second phase, the solvent kinetic isotope effect (ka'(H2O)/ka'(D2O) is 2.52 at pH = 1.0. For the third phase, the solvent kinetic isotope effect (ka"(H2O)/ka"(D2O) is 2.27 at pH = 5.4. Hydrogen atom transfer (HAT) mechanisms are proposed at low pH. Notes: CityU Call Number: QD181.R9 W36 2015; ix, 210 pages : illustrations 30 cm; Thesis (Ph.D.)--City University of Hong Kong, 2015.; Includes bibliographical references (pages 194-210) 2015-01-01T00:00:00Z


text:
Poll: When do you think Joey and Elisa should get together? Vote Now!
Author has written 10 stories for Danny Phantom, Twilight, Misc. Books, Yu-Gi-Oh, and Bleach.
wuz up! peeps!
Hi! i'm Katrina. my friend Brandi and i share this account. thats why its peaceBABES
well im obsessed with twilight and shes obsessed with danny phantom sooo twilight stories are prob. mine som maybe hers. bu danny phantom stories are DEFINATLY hers. we cant spell worth a dang.
I'm a brunette and i'm a cutie,
mess with me i'll kick your booty.
redheads are smart.
blondes think they're cool.
well think again cuz brunettes RULE!
With his sense of humor...
He can cheer you up when your feeling down
With his booming laugh...
He can end an awkward silence
With his scary large muscels...
He can scare away anyone who wants to hurt you
That's why I love him
He's mine so back off!
For all you Grly Grls,
Try not to impersonate Barbie
funny quote:
"The statistics on sanity are that one out of every four Americans are suffering from some form of mental illness. Think of your three best friends. If they're okay, then it's you."
Another quote(Sad though):
"Saying goodbye is never easy; it doesnt matter how much time you have to say it."
~Author unknown~
17 Things to do when you're in Walmart!
1. Set all the alarm clocks in Housewares to go off at 5-minute intervals.
2. Make a trail of tomato juice on the floor leading to the rest rooms.
3. Walk up to an employee and tell him/her in an official tone,
4. Go the Service Desk and ask to put a bag of M&M's on lay away.
5. Move a 'CAUTION - WET FLOOR' sign to a carpeted area.
6. Set up a tent in the camping department and tell other shoppers you'll invite them in if they'll bring pillows from the bedding department.
7. When a clerk asks if they can help you, begin to cry and ask,
8. Look right into the security camera & use it as a mirror, and pick your nose.
9. While handling guns in the hunting department, ask the clerk if he knows where the anti - depressants are.
10. Dart around the store suspiciously loudly humming the "Mission Impossible" theme.
11. In the auto department, practice your "Madonna look"
12. Hide in a clothing rack and when people browse through,
13. When an announcement comes over the loud speaker, assume the fetal position and scream..
14. Go into a fitting room and shut the door and wait a while and then yell, very loudly, "There is no toilet paper in here!
15. Grab a lot of bouncy balls and throw them down the aisle, shouting "Go, Pikachu, Go!"
16. Have a friend push you down the aisle in a shopping cart as you yell "THE REDNECKS ARE COMING! THE REDNECKS ARE COMING!"
17. Shout at the top of your lungs "VALDEMORT IS TAKING OVER!" and count how many people turn to look at you
When all else fails, read the directions.
Someone told me that it was illegal to kill someone just because they pissed you off...crap...
I'm not a tomboy, I'm just better than you.
I am who I am and I be who I be, you can kiss my ass if you don't like what you see.
I rather be hated for who I am, then loved for something I'm not.
Party hard, rock and roll. We're the class you can't control
I'm not clumsy, I just think faster than I move.
I'm not random, I just think quicker than you. Jealous?
What happens if you get scared half to death twice?
Does the noise in my head bother you?
When it rains at my party, we dance in the rain.
I can please only one person per day. Today is not your day. Tomorrow isn't looking good either.
I don't have an attitude problem. You have a perception problem.
The dinosaurs' extinction wasn't an accident. Barney came and they all committed suicide.
I understand that Scissors can beat Paper, and I get how Rock can beat Scissors, but there's no way Paper can beat Rock. Is Paper supposed to magically wrap around Rock leaving it immobile? If so, why can't paper do this to scissors? Screw scissors, why can't paper do this to people? Why aren't sheets of college ruled notebook paper constantly suffocating students as they attempt to take notes in class? I'll tell you why, because paper can't beat anybody, a rock would tear that crap up in two seconds. When I play rock/ paper/ scissors, I always choose rock. Then when somebody claims to have beaten me with their paper I can punch them in the face with my ready made fist and say, oh, I'm sorry, I thought paper would protect you.
Being mature is overrated.
I'm the kind of kid who will burst our laughing in the middle of a dead silence because of something that happened yesterday.
When I was younger, my parents encouraged me to walk and talk. Now, all they want me to do is sit down and shut up!
If you are obsessed with DANNY PHANTOM, copy and paste this onto your profile.
If your friends don't really like DANNY PHANTOM, but you don't care, copy and paste this onto your profile.
If you are obsessed with TWILIGHT, copy and paste this into your profile
If you are obsessed with fanfiction copy this into your profile
If people think you are mentally insane...copy and paste this onto your profile
If you have ever gotten so completely sidetracked in a conversation that you don't remember why you were talking in the first place, copy this into your profile.
If you have ever zoned out for more than five consecutive minutes, copy this into your profile.
If you have your own little world, copy and paste this into your profile.
If you've ever walked into a doorway that you could've clearly dodged, you just weren't paying close enough attention, copy and paste this on your profile.
Truthful Quotes and Statistics.
According to the latest figures, 43 percent of all statistics are utterly worthless.
Don't steal. The government hates the competition.
If at first you don't succeed, change the rules.
Tell the truth and run.
Smile! It makes them wonder what you're up to.
Friends come, and friends go, but enemies accumulate.
Truth is stranger than fiction, because fiction has to make sense..
Power corrupts. Absolute power is kind of neat.
Generally, generalizations are wrong.
Ye shall know the truth, and the truth shall make ye mad.
All things considered, insanity may be the only reasonable alternative.
If we knew what we were doing, it wouldn't be research.
Life is like a box of chocolates - it's full of nuts.
The Truth is out there. So what are you doing here?
If you can't beat them, join them. Then take over.
Whatever you are, be a good one.
You cannot shake hands with a clenched fist.
You can never underestimate the stupidity of the general public.
We are the people our parents warned us about.
Freedom is the right to be wrong, not the right to do wrong.
The difficulty is not so great as to die for a friend, as to find a friend worth dying for.
Belief gets in the way of learning.
If you try to fail and succeed, what have you done?
When angry, count to four. When very angry, swear.
Enjoy every minute of life. There's plenty of time to be dead.
And in the end, it's not the years in your life that count, it's the life in your years.
We don't live in the world of reality, we live in the world of how we percieve reality.
If God had intended Man to smoke, he would have set him on fire.
A single death is a tragedy. A million deaths is a statistic.
Have the courage to live. Anyone can die.
Education is important. School, however, is another matter.
When a finger points at the moon, the imbecile looks at the finger.
Fashion is a form of ugliness so intolerable that we have to change it every 2 months.
Cynics are made, not born.
Maybe this world is another planet's hell.
OMG! i'm so sad right now!
Brandi is moving and she will be in another school district!
FAKE FRIENDS: Never ask for food.
FAKE FRIENDS: Call your parents Mr/Mrs.
FAKE FRIENDS: Bail you out of jail and tell you what you did was wrong.
FAKE FRIENDS: Have never seen you cry.
FAKE FRIENDS: Borrow your stuff for a few days then give it back.
FAKE FRIENDS: Know a few things about you.
FAKE FRIENDS: Will leave you behind if that is what the crowd is doing.
FAKE FRIENDS: Would knock on your front door.
FAKE FRIENDS: Will talk bad to the person who talks bad about you.
FAKE FRIENDS: Would ignore this.
FAKE FRIENDS: Are for a while.
1. When there's only one other person in the elevator, tap them on the shoulder and then pretend it wasn't you. 2. Ask if you can push the button for other people, but intentionally push the wrong ones.
3. Hold the doors open and say you're waiting for a friend. After a while let the doors close and say, "Hi Greg. How's your day been?"
4. Drop something and wait until someone goes to pick it up and then scream, "That's mine!"
5. Bring a camera and take pictures of everyone in the elevator.
6. Move your desk into the elevator and whenever anyone gets on ask if they have an appointment.
7. Lay down a Twister mat and ask people if they would like to play.
8. Randomly ask, "Did you feel that?" When they look at you curiously, begin to explain your theory that a troll has made its way into the building, become more panicked by the minute.
9. Stand really close to someone, sniffing them occasionally. As they are getting off, tell them you "know of a medicine that can cure that?"
10. When the doors close, announce to the others in a voice of forced calm, "It's okay, don't panic, they open again!"
11. Grimace painfully while smacking your forehead and muttering, "Shut up, all of you, just shut up!"
12. Crack open your briefcase or purse and peer inside periodically while whispering, "Got enough air in there?"
13. Stand silently and motionless in the corner facing the wall, without getting off. If someone approaches you, turn around and try to bite them.
14. Stare at another pAs senger for a while and then announce in horror, "You're one of THEM!" and back away slowly.
15. Stare manically and grin at another pas senger for an extended amount of time before announcing, "I have new socks on."
16. Draw a little square on the floor with chalk and announce to the other pas sengers in an unnecessarily loud voice, "This is MY personal space!"
17.Make explosion noises when anyone presses a button
Yes, as yinz heard, i am moving to a new school district. In two and a half days(The half day is the day before thanksgiving break) So i will make the best of my remaining school days, and (And then cry the day before my last, i am serious, i ama gonna bawl.)
So, nothing else is of interest right now, so byes.
BANANA PHONE! HA.HA.HAHA! post this on your profile if you are extremely random
98 percent of the population would die if Johnny Depp said it wasn't cool to breathe. Copy this onto your profile if you would be one of the 2 percent that is laughing your ass off
If you have ever considered going to the dark side since they have cookies, copy this onto your profile.
All the good men in this world are either gay, taken, or fictional charaters. Copy if true
If you think that life without computers is useless then copy this to your profile
If you've ever talked to yourself, copy and paste this into your profile
If you talk to yourself and aren't afraid to admit it to anyone, copy and paste this in your profile
If you are always the last picked in gym class, and if you don't care, please copy and paste this into your profile.
If you think that being unique is cooler than being cool, copy and paste this into your profile.
"I'm bringing sexy back..." copy and paste this into your profile if you didn't even know sexy was gone
Okay...so there's this thing called retarded-ness and me and my freinds, well...We've gone pro.
I've got ADD and magic markers. Oh the fun I will have.
guns dont kill people, uh-uh, i kill people ch-ch with guns
If you are obsessed with Danny Phantom, copy this into your profile.If you are going into Danny Phantom withdrawl, copy and paste this into your profile.
If you have Phantom Phever and you know you do, copy and paste this into your profile.
If you freak out when you get a 91, not because of how you thought that you would do previously, but because in Danny Phantom: Teacher of the Year Danny got a 91 on his English exam, copy and paste this into your profile.
If every time the first answer to a test is "D," you laugh silently (or out loud) because of Danny Phantom: The Ultimate Enemy, copy and paste this into your profile.
93 percent of American teens would have a severe emotional breakdown if someone called them a freak. If you're a part of the 7 percent who would ask the person, "What was your first clue?", copy this into your profile.
98 percent of teenagers do or has tried smoking pot. If you're one of the 2 percent who hasn't, copy & paste this in your profile.
If you hate those obnoxious snobby people, PLEASE copy this into your profile.
Some people think I'm insane. If you've ever been called insane before, copy this and put it in your profile.
If you've ever copied and pasted something onto your profile, copy and paste this onto your profile
When you dial a mental hospital:
Welcome to Psychiatric World. If you are obsessive-complusive, please press one repeatedly.
If you are codependent, please ask someone to press 2.
If you have multiple personalities, please press 3, 4, 5, and 6.
If you are paranoid-delusional, we know who you are and what you want. Just stay on the phone so we can trace the call.
If you are schizophrenic, listen carefully and the little voice will tell you which number to press.
If you are manic depressive, it doesn't matter which number you press. No one will answer.
If you are delusional and hallucinate, please be aware that the thing you are holding on the side of your head is alive and about to bite off your ear.
If you ever pushed on a door that said "Pull" copy this into your profile.
If you've ever been so obsessed with something that now everyone is scared of you because of its effects, copy this into your profile.
If there are times when you wanna annoy people just for the heck of it, copy this into your profile.
If you think that those stupid kids should just give that God- forsaken Trix rabbit some Trix, copy this into your profile.
Ninety-five percent of kids out there are concerned with being popular and fitting in. If you're part of the five percent who aren't, copy this, put it in your profile, and add your name to the list. AnimeKittyCafe, Hyperactivley bored, Gem W, Bara- Minamino, Yavie Aelinel, Carzy Billie Joe loving freak, shadow929, The Astrology Nerd, brown-eyed angelofmusic, piratesswriter/ fairy to be, The Gypsy- Pirate Queen, MCR Rocks, Andrew Laplante, 2wingo, Dannyphantomfreeek, xXPeaceBabesXx.
If you think that Writer's Block blows (sucks), copy and paste this into your profile.
If you have ever forgotten what you were going to say, right before you say it, copy this into your profile
Awesome Adam Lambert quotes
"anyone who feels wierd or different, screw it."
"im like your boy next door who decided that he wanted to be a rebel one day. so.. im a nice rebel."
"i wasnt popular in high school. i was the wierd kid. so to all you wierd kids out there-you can do it!"
"i can sang!"
Hey it's Brandi, i might have not updated in a while well, because i share another account with my cousin.
So and i am updating my story as fast as i can.
I love fanfiction, and only because I have many reviews for my one story Start All Over.
|Awesome ghost/Danny Phantom Stories
|Cartoons Danny Phantom

subset: commoncrawl


text:
- Price: $125,000 ($7/sq. ft.)
- 1810 Mercantile Drive
- City: Clarksville
- Subdivision:
- County: Montgomery County
- Beds:
- Baths:
- Type: Commercial
- Elementary School:
- Middle School:
- High School:
MLS #1064829 Official listing information! neighborhood - 9 Eagles Point located in Clarksville TN 37040, priced at $119,900, with bedrooms.9 Eagles Point Clarksville TN - MLS #1064829 Close
Commercial for sale in Clarksville, TN at 9 Eagles Point. This commercial is priced at $7/sqft.
Vacant C-2 Lot w/Utilities Available. Smallest Lot in Eagles Point. Has 114 +/- Ft of Road Frontage. There is an Association. Underground Utilities & Green Areas in Development.
Listing information last updated on May 25th, 2017 at 10:20am CDT.
Have any comments or questions about 9 Eagles Point, Clarksville, TN? Ask your question and/or share your thoughts about this property.


text:
FLIP REPORT: John flipped the remaining cards for the final contestant at two down because time was running short. The panel had come fairly close with this contestant, guessing both that she "demonstrated something" and was "involved with entertainment." It seemed very likely that they might have figured out the exact line of "demonstrates reducing exercises on TV" if they had more than just a couple minutes to play. John had even eliminated the panel walk-by to make more time for this game, but alas, there was not quite enough time for the panel to discern the guest's exact line. - agent_0042 (2008)
(1) "WML?" SPONSOR AND PANEL WATCH: For the second straight week, Stopette is the main sponsor. This was the first time on which Arlene sat on the far end of the panel, but as history would show, certainly not the last. However, Miss Francis is introduced this evening as "One of television's brightest stars"; it would be a short while before her more famous introduction, "The delightful star of stage and television," is formulated. And this is the first of two guest panelist appearances by Mary Healy.
(2) This was the second straight week in which Bennett introduced John Daly as "the world's leading news analyst and most misleading panel moderator" and the third straight week that the publisher/panelist incorrectly inserted "Francis" into John's name, calling him "John Charles Francis Daly." John's full name, of course, was John Charles Patrick Croghan Daly, which Bennett did get right on a few occasions over the years between 1953 and 1967.
(3) "WML?" OVERLAY FONT WATCH: The customary "last-minute" typesetting was used for the "Builds Jail Cells" overlay of the second contestant.
(4) MYSTERY GUEST NAMEPLATE WATCH: For mystery guest duo Marge and Gower Champion's appearance tonight, the production staff used a different size nameplate with a larger height than the standard nameplate customarily seen. Their names were set on two lines ("MARGE AND GOWER," "CHAMPION") in the then-prevalent overlay font of Kabel Heavy. Of course, when the Champions next appeared as a mystery guest duo on EPISODE #451 of February 8, 1959, the "WML?" production crew had long since switched to having the mystery guests' names briefly displayed in white on the lower third of an overlay screen. In addition, the future show was produced with a new studio set design which would be in use until 1964.
(5) "WML?" CREDITS CRUNCH WATCH: This was another rare occasion where the full production crew credits were shown after the American Airlines plug. Just like clockwork, however, GSN, on its July 25, 2008 airing of this episode, continued to indulge in its "crunching" of the screen, to the viewing audience's eternal dissatisfaction and dismay.
(6) Following the July 25, 2008 airing of tonight's show by GSN, the cable and satellite channel repeated the October 29, 1952 edition of "The Name's the Same," hosted by Robert Q. Lewis, with the panel consisting of Abe Burrows, Joan Alexander and Meredith Willson, and David Niven as the celebrity guest. - W-B (2008)
MYSTERY GUESTS Gower and Marge Champion, husband and wife duo, promoted their 1955 Broadway play "3 for Tonight: A Diversion in Song and Dance" which also stars Harry Belafonte. The original musical revue ran for 85 total performances at the Plymouth Theatre. - Suzanne (2005)
REVIEW: The panel did fairly well this episode. In the first game, Bennett correctly guessed that the charming man from Japan made ladies' stockings. During the game, John made the audience laugh when he told the panel that the product was "connected" to the girdle family. The panel had no idea that John meant literally! This was, of course, before the days of mass-market pantyhose, and stockings needed a girdle or garter belt to hold them up. After the round, John brought up the fact that Mr. Kobayashi was in town for the Rotary Club's annual convention and that he was a high official in the organization. The panel had a little trouble with the second contestant. In fact, they were down to their final "no" when Arlene correctly guessed that he made jail cells for the last-minute save. In the mystery guest round, guest panelist Mary Healy, aka "Miss New Orleans 1918," as her husband Peter Lind Hayes called her, correctly guessed that the mystery guests were Marge and Gower Champion. After the game, Mary paid them a wonderful compliment when she said that the Champions as well as Hume Cronyn and Jessica Tandy were two of the finest couples on Broadway. Unfortunately, the panel ran out of time in the final game and the exercise instructor won the full prize by default. - Sargebri (2005)
PANEL ORDER: It was interesting to see Arlene in the "lead off" position tonight. Early next year, in 1956, she and Dorothy will begin to alternate the position. After Dorothy's 1965 death, the first chair will become predominately Arlene's spot. However, Arlene will also alternate the position with Phyllis Newman and other guest panelists on occasion. - Sargebri (2005)
EARS TO YOU: In the first game, when the questioning was getting "risque" when Arlene brought up the subject of girdles, Bennett made a comment about a "secret" What's My Line? practice. The hidden practice was for John to tug on his ear as a signal to the panel to tone things down. John was sharp, and was never actually caught on film tugging his ear. However, tonight Bennett states, "John's going to start pulling his ear in a minute." In addition to Bennett's revealing comment, the "ear tugging" practice was also written about in magazine articles of the day, such as an article written about Hal Block which appeared in "TV Dial" on December 6, 1952. "TV Dial" was a midwestern forerunner to TV Guide magazine. A complete transcription of this 1952 article can be located on the guide to EPISODE #131. - Suzanne (2005)
EAR TUG: John's "ear tug" is the answer to a trivia question in the TV Guide 40th Anniversary book. The question is: "On What's My Line?, what did it mean when John Daly tugged his ear?" The answer is: "Daly tugged on his ear to indicate that the subject matter was becoming a bit too racy for live television and to change the subject." - Gus S. (2005)
Tidbits: Arlene mentioned that this morning, New York's Herald Tribune newspaper featured a color photograph of the WML panel on the front of their new television supplement. - Suzanne (2005) Mary Healy (4/14/1918 - 2/3/2015) Panel: Arlene Francis, Fred Allen, Mary Healy, Bennett Cerf. Dorothy Kilgallen has the night off. She is vacationing in Paris, France.
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While we're still anticipating the real, sunshine-y arrival of summer, the folks in Sydney are already transitioning into fall. Even though their seasons are inverted, their sense of style sure doesn't feel wonky — in fact, Sydney has some of the most refreshing, inspiring, "effortless" ensembles that we've seen in ages. Check out our street style snaps from Down Under to see how these ladies did summer so sartorially right (consider this a little window into the future, if you'd like!).
When Solange Asks You To Stick To An All-White Dress Code, You Commit


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In 2017, the possible end of Obamacare will be a major news story to follow. With attacks on two fronts, the Obama administration could see one of their most notable policies disappear. Or be changed in a way where it is no longer recognizable.
In this audio report, we analyze the problems that may spell doom for Obamacare in the new year. While the system has been beneficial to millions of Americans, its inherent flaws have dogged it since its inception.
Main Photo:


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A good response from vets at the preview of SureFeed confirmed the benefits of a secure feeder for a multi-cat household, according to Judith Bank of SureFlap, the microchip pet product company.
She said: "The London Vet Show was the first opportunity we had to show vets prototypes of our new pet feeders and it was good to gain their input; many said that they had been waiting for such a product."
The SureFeed, unveiled to the profession at LVS 2013, is available in two models: the SureFeed Pet Feeder, designed to keep food fresh and the kitchen free from the smell of wet food, and the SureFeed Microchip Pet Feeder which opens only when it identifies the correct owner of the food bowl from its microchip or RFID collar tag. The product will be available in early 2014.
Judith added: "Many of the vets remarked on the importance of restricting cats on special diets from eating each others food. Additionally, cats are territorial about their feeding areas and vets thought that nervous cats would appreciate the shields incorporated in the feeder that protect them when they eat."
However, it wasn't just cats that vets were interested in feeding… SureFlap ran a "Gourmet Giveaway" competition on its stand, which resulted in several happy winners: Caroline Collins of Pennard Vets won the star prize of a Michelin Star meal for two and Jessica Morgan of Blue Cross, Jessica Hagedorn of Molesey Vets, Susan Pescod of Guide Dogs for the Blind and Robin Holden of VetsNow all won restaurant vouchers.


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Hotel Rio Azul
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Travel Blogs from Quetzaltenango
Yoga, rain and smoking gods in the Mayan highlands
... just in time to witness the heavens open. Exceptionally heavy rain, thunder and lightning were to become the norm over the next couple days. Fortunately, we were staying somewhere perfect for just relaxing and whiling away the time. The first night was open mic night and after a superb dinner, in which we got to know the owners, an Anglo-American couple like us and the former owner, an elderly Brit who sold the hostel years ago but still lives there as a guest, we ...
A day of no pictures! Crazy!
... was mixing words up and it was a slight mess, but we made it through.
After school, I came home to a lunch of potatoes and a chicken patty. It was really pretty delicious. The school didn't have any activities to do after lunch because of the food and dance stuff in the morning, so I decided to walk about the city some.
I had looked up a few places to go to online before I went out. I didn't write down the specific address ...
Back To Winter
... vaccination. So, I had to wait a while. When it was my turn though, I received quality health care, as has been my experience mostly so far in Guatemala. We were in Xela only two days, but we couldn't miss Sabor de la India (an Indian restaurant recommended by Lonely Planet). So, we paid a visit to the establishment. Both of us were satisfied. ...
Lake Lounger
... system for them, so relied on turning up on the day and hoping there would be a vacancy.
Unfortunately I called this one wrong.
I walked on to the next three or four places to be met with either no vacancies or we do have rooms, but they are about two or three times what I was looking to pay.
I kept walking through the village looking to spot a few more hostel signs and noticed a girl walking in the same direction carrying some ...
Back to Guatemala - Land of the tongue twister
... street map a football ground named after Mario Camposecc. Now I'm not going to try and pretend to astonish you with my knowledge of Guatemalan footballers (extensive though it is). But by a coincidence I had come across a little plaque on a house on the hillside that morning dedicated to Mr Camposecc. Apparently he played for the local team that won the regional title ten years in a row from 1940-50, when he was killed in a plane crash. They obviously honoured his memory ...
Other places to stay in Quetzaltenango
Hotel ModeloAvenida 14, Quetzaltenango | Hotelfrom $54
- Clean, friendly and spacio…
Pension Bonifaz Hotel4 St 10-50, Quetzaltenango | 2 star hotelfrom $45


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Hi everyone,
I'm a 30-something wife and mother of two looking to find my inner rockstar!! Well, at least the rockstar body.
I found SimpleFit through the CrossFit forums. It is exactly what I need to prep my body and core strength for the WODs in CrossFit.
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Thanks for creating this site and forum. I look forward to meeting everyone here.


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U.S. DISTRICT COURTNew Jersey Law Journal
Disability Rights New Jersey Inc. v. Velez
New Jersey's policy governing the involuntary administration of psychotropic drugs in nonemergency circumstances to CEPP patients in the state psychiatric hospitals violates their substantive and procedural due process rights and is discriminatory as to them; it is valid as to the remaining patients.
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The case of a mother who gave her daughter three ecstasy tablets for her 13th birthday present has been cited by the "Robocop" Mayor of Middlesbrough as an example of problem families.
Former police officer Ray Mallon, who gained his nickname for his zero-tolerance approach to policing while serving as a detective superintendent with Cleveland Police, said that there were 360 children in care in the town.
"Many of these children are in care due to neglect because of poor parenting," he said. "There was one where a mother gave a 13-year-old child ecstasy tablets – hard drugs – for her birthday. I just despair."
He added: "One family costs £600,000 a year due to numerous interventions by the council and our partner agencies."
Mr Mallon has been elected Middlesbrough's Mayor as an independent candidate three times since 2002, but announced that he is to stand down in 2015. He said he believed there should be a referendum on whether the position should remain.
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- Children
- Cleveland
- Family And Parenting
- Middlesbrough
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Kattankolathur, Chengalpattu, India- 603203.
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October 3, 2011
Christian Brothers movie tells about Palomattathu Varghese Mappila (Saikumar) and family. He is a retired captain of Indian Army and wealthy. He has two sons Christy (Mohanlal) and Joby (Dileep). Christy who is an informer who is working in Mumbai and getting high amount as remuneration. His brother Joby goes abroad to study theology.


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5.0 stars 1 review
Avvo Rating: 7.5
Review: "I hired miss Moise based on a referral from some very good friends. I couldn't be happier with the representation I recieved from her. I have had a few different attorneys and none have been as thorough and relentles...
Practice areas & skills: Civil Rights, Criminal Defense, Family
5.0 stars 2 reviews
Avvo Rating: 7.2
Co-Counsel on the largest police misconduct verdict in Michigan history and the largest verdict in Michigan this year! On November 3, 2016, a jury in the United States District Court in the Eastern District of Michigan returned a $36,600,000 agai...
Practice areas & skills: Civil Rights, Commercial, Business, Employment & Labor, Criminal Defense
5.0 stars 1 review
Avvo Rating: 6.4
Review: "I was "laid off" from a position I held for 36 years after a new chairperson had been appointed. I believe the cultural differences were a major factor in my dismissal as well as financial considerations to rep...
Practice areas & skills: Civil Rights, Labor & Employment Law, Family
A civil rights attorney helps protect the personal rights granted to you by the government. When someone violates those rights, a civil rights attorney can help you make them stop these violations, or repay you for any damage they have done to you. Your civil rights are spelled out in federal and state constitutions and in discrimination laws. In fact, civil rights attorneys are sometimes called discrimination attorneys because they frequently handle cases involving a person being treated differently based on gender, age, ethnicity, or sexual orientation.


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I just finished Gregory Berns's book Satisfaction: The Science of Finding True Fulfillment. He argues that novelty and challenge are key components of satisfaction. Other studies confirm that people who do new things—travel to new place, learn a new game—have a greater sense of well-being than people who stick to the familiar. Gretchen Rubin
Since I have not read the book she sites here I am taking what she has said here as my guide. I must say that I have been fighting against something that I know to be true - for years. Routine will make a happier home. At first that may seem to contradict what Gretchen has stated above, but in order to do something out of the ordinary first you must have an ordinary.
I have never done well keeping a schedule, or a routine. This weekend I have some time with which I can do whatever I want, I don't have to work around anyone's schedule or worry about what anyone would "like me to be doing". I'm going to spend the weekend looking through old systems that I have tried in the past and work up a simple routine that I can build on. My intention is to get a start, take baby steps, and think about what parts of those systems will make it easier for me to achieve my number one goal before school starts.
Goal #1: Make this house a welcoming home.
In the past that would have meant just cleaning. But I really would like to feel relief when I walk in the door of my home not more chaos. I want to walk in and know that I am in a comfortable place. I am tired of walking in my home and being struck with all that needs to be done. I want to walk into my home and FEEL cushioned from the rest of the world.
Once I get a routine down, then "new" and "challenging" and "novelty" won't be the norm but truly welcome differences.


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Be thankful for contributions of military spouses
By Col. Aaron Burgstein, Air Force Public Affairs
Editor's Note: Air Force Col. Aaron "Chewy" Burgstein wrote this unpublished commentary in the fall of 2014 while undergoing medical treatment for a brain tumor. He unfortunately passed away on Jan. 27, 2015. In recognition of Military Spouses Appreciation Day on May 21 and Memorial Day on May 31, Air Force News is publishing Col. Burgstein's commentary in remembrance of his contributions to Air Force Public Affairs and as a reminder of the timeless contributions made by military spouses every day around the world.
In my nearly 20 years of military service, I have moved 12 times. It is more frequent than most service members, but yet not that unusual. Along the way in my career, I picked up a spouse. She has moved a total of nine times in our 13 years of marriage. Our children are just breaking into double digits and they have moved six times.
Read more: Be thankful for contributions of military spouses


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The EY Global Hedge Fund Symposium Series is hosted in 19 financial centers worldwide, and is attended by more than 5000 senior executives from some of the world's largest hedge funds and leading service providers.
Thought leaders from the firm and industry across the globe provide in-depth coverage, commentary and share insights on the multi-faceted issues facing the hedge fund industry.
We will also share with attendees the results of the 2016 Global Hedge Fund Survey.
For more information, or to invite your clients to the New York Hedge Fund Symposium, please contact Andrew Borys (+1 212 773 4313). To request information on other symposium locations, please click on any of the cities below.


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27006 N 164TH Street, Scottsdale, AZ 85262
4 beds, 3 baths, 3,282 sqft
Status: Active
Property Description
Priced below recent appraisal!!Tucked back in off main road for more privacy. Unobstructed view of Four Peaks. Very nice open kitchen with lots of countertops and large eat in area. Living room with dual fireplace, lots of niches (some lighted), beautiful high tongue and groove ceilings gives nice touch to rooms, extra large laundry room and tons of storage. Surround sound in kitchen, living room and patio. Grassy area on side of yard for pets and small garden.4 homes on shared well. Home has central vac installed,but not hooked up, no equipment in garage. Come live where the air is clean, cooler temps, clear skies and occasional wildlife. The Owner added on an additional master bedroom/bath in 2004.Nice big bedrooms, arched doorways,saltillo tile floors give a real southwestern flavor.
Listing Information for 27006 N 164TH Street Scottsdale, AZ 85262
Well Shared
Septic In and Connected
Ceiling Fan(s),Multi-Zones
School Information for 27006 N 164TH Street Scottsdale, AZ 85262
Room Information for 27006 N 164TH Street Scottsdale, AZ 85262
Family Room
Other Bedroom Walkin Closet
Master Bedroom Walkin Closet
Breakfast Bar, Eat-in Kitchen
Pantry, Kitchen Island, Granite Counter-tops
Double Sinks,Tub with Jets,Separate Shwr & Tub,Private Toilet Room,Full Bth Master Bdrm
Dual Sinks, Jetted Tub, Separate Tub & Shower
Interior Features for 27006 N 164TH Street Scottsdale, AZ 85262
Microwave, Wall Oven, Electric Range/Cooktop, Disposal, Dishwasher
Tile, Carpet
Electric Heating
Double Pane
1, Two Way Fireplace, Gas Fireplace, Fireplace Living Rm
Central Vacuum, Skylight(s), No Interior Steps
Exterior / Lot Features for 27006 N 164TH Street Scottsdale, AZ 85262
2 Garage Spaces, 2 Parking Spaces, Attached Garage Cabinets, Side Vehicle Entry, RV Parking, Over Height Garage, Electric Door Opener, Direct Entry from Garage
Stucco, Painted
Balcony, Covered
Built Up, Foam
Swse4NE4SW4EX 505' Sec.34 T5N R4E
Balcony/Deck(s), Private Yard(s)/Courtyard(s), Covered Patio(s), Mountain View(s), Street(s) Not Paved
Community Features for 27006 N 164TH Street Scottsdale, AZ 85262
Driving Directions to 27006 N 164TH Street Scottsdale, AZ 85262
South on 164th Street to easement past Pinnacle Vista. Turn right to last house at end of street.
Financial Considerations for 27006 N 164TH Street Scottsdale, AZ 85262
Listing Price History for MLS#: 5502577
Scottsdale AZ Real Estate and Scottsdale AZ Homes for Sale
Scottsdale is located in the state of Arizona. The zip code of 85262 has a population of 236,839. The median age of people living in Scottsdale, AZ 85262, is 46.1 years.
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Shop Media stands where alter asked the Dark them for certain solution that remove her powers. Iron Revealed That there was accurate.
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Only 821 feet to the shores of Uzungol (Long Lake), Serah Apart Motel offers a restaurant serving local dishes and self-catering apartments with mountain and lake views. All apartments at Serah come with a flat-screen TV and a balcony. The kitchens include an electric kettle, stove and cooking utensils. A bathroom with hairdryer is standard. Daily breakfast is served in buffet style. The hotel's à la carte restaurant serves a variety of grills (fish, meatballs, chicken) and local dishes such as sac kavurma (diced lamb fried on iron plate) and kuymak (a Black Sea dish made with cheese, butter and corn flour). The hotel staff can arrange tours to the landmarks such as Ayder Plateau, Sumela Monastery and Karaca Caves. Airport shuttle service can be provided at a surcharge. Free Wi-Fi is available in all areas. Trabzon Airport is 55.9 miles away. Free private parking is available on site.


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The Paradise – a new eight-part BBC One TV drama will be shot in North East England – after receiving support from Northern Film & Media's Production Service.
Sarah Lancashire (Lark Rise To Candleford, Five Daughters), David Hayman (Trial And Retribution), Elaine Cassidy (Harper's Island, Fingersmith), Matthew McNulty (The Syndicate, Misfits), Joanna Vanderham (The Runaway, Dancing on the Edge) and Emun Elliott (Lip Service, Game Of Thrones), will star in Bill Gallagher's adaptation of Emile Zola's novel.
The Paradise is the story of a love affair set against the backdrop of the opening of the first department store told over eight episodes.
The series was commissioned by Ben Stephenson, Controller Drama Commissioning and will be shot on location in County Durham by BBC Drama Productions from June.
"The Paradise is the biggest BBC drama to be made in the North East," said Pat Connor of BBC North.
"BBC North is proud to support this production which underlines our commitment to making the very best programming here in the North for the entire UK."
"The Paradise is the latest in a string of TV dramas to take advantageof the North East's fantastic locations and crews and supportive local authorities, said Tom Harvey, Northern Film & Media's chief executive.
"Vera, Inspector George Gently and now The Paradise headline an increasingly impressive slate of dramas that will present the North East to millions of viewers worldwide and we are extremely proud to have played a role in bringing the show to the North East."
Northern Film & Media | BALTIC Centre for Contemporary Art | South Shore Road | Gateshead | NE8 3BA | firstname.lastname@example.com | 0191 4404940
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Who Won the Belmont Stakes 2016 ?In a close call between Destin and Creator., an unexpected contestant won the 2016 Belmont stakes. It was a very close call between Destin and Creator, but Creator finally won $1.5million.
|creator wins belmont stakes 2016
Exaggerator jumped to a fiery start but couldn't keep up..!!
More updates and detailed Analysis coming soon.!!Belmont Stakes 2016 Live Stream Now, See Results, Live @ 6:32 pm #BelmontStakes #Belmont2016https://t.co/4V9uesKE0S pic.twitter.com/upNlqj6sZb— Filmetriks (@iamfilmetriks) June 11, 2016


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Come try our jerky! Hand made fresh every week right here, not in some big factory. Cuz local makes a difference!!
Fresh Cut Meats and Deli counter
Need some ground beef for the burger cookout?
Come by and see our selection of locally processed and fresh cut meats. Whether your looking for smoked brisket, fully cooked and smoked hot links and sausages we have them available for you to pickup. We also carry a selection of Boar's Head meat and cheese products.
How about some steaks for that cookout?
If you don't have time to smoke a brisket we have some already smoked and ready for you to pickup.
We have a great selection of Bolner's Fiesta Spices


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What is your favorite shoe brand?
Converse, Uggs and Nikes
In what year did the Skechers shoe brand start?
Skechers USA Inc. was founded in 1992 and is headquartered in Manhattan Beach, Calif. Skechers now sells casual shoes in more than 900 different designs through department stores, online retailers ...
Read More »
In what year did the Sketchers shoe brand start?
Skechers U.S.A. Inc. was founded in 1992 by Robert Greenberg who was one of the founders of L.A. Gear. Other brands owned by Skechers according to its website include "Unltd. by Marc Ecko, Red by M...
Read More »
What brand of shoe does David Letterman wear on his show?
What color bra is the most worn by woman?


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Product Description
This beautifully handcrafted Oak Wood Picture Frame is a wonderful gift for yourself or someone special. The custom frames has either 3x4 or 5x7inch openings to display pictures. The frame comes with glass and a sawtooth hanger. This frame makes a perfect gift for any special occasion. Please feel free to e-mail us with any questions you may have.


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Physiotherapy for Incontinence after prostate surgery
More and more Men over 50 years are experiencing prostate problem. Most of the cases are without symptoms. Only test that can detect the early stage of prostate problem is PSA (Prostate Specific Antigen). This can be done during a regular Master Health Check-up.With an elevated PSA prostate cancer can be detected early with further investigation.
A prostatectomy is the surgical removal of the prostate gland which is located just under the bladder and has the urethra travelling through it.
In the above picture one can see the pelvic floor muscles. The floor of the pelvis is made of layers of muscle and other tissues. These layers stretch like a hammock from the tailbone at the back to the pubic bone in front. A man's pelvic floor supports his bladder and bowel. The urine tube and back passage all pass through the pelvic floor muscles. One's pelvic floor muscles help one to control his bladder and bowel. It also helps in sexual function. It is vital to keep one's pelvic floor muscle strong.
These Pelvic floor muscles could either be too weak, too tight or uncoordinated resulting in pelvic floor dysfunction after the surgery.
Stress Incontinence: Weak pelvic floor muscles cannot squeeze tightly when there is a sudden increase in the abdominal pressure due to sudden sneeze, coughing, laughing or lifting weight resulting in urine leakage.
Constant Dribbling: Some may experience constant dribbling throughout the day with increased leakage during physical activity.
Leakage and Erectile Function: When pelvic floor muscles are too tense or restricted both leaking and erectile dysfunction can occur.
Physiotherapy is a successful treatment option for men experiencing pelvic floor dysfunction following prostectomy. First, Physiotherapists who are trained in pelvic floor muscle examination educate the clients who are going in for surgery about the importance of exercises for the pelvic floor muscles and make them understand the right exercises to work only concentrate on pelvic floor muscles and not on lower abdominals, inner thigh or buttocks muscles. Then after surgery they evaluate the function of pelvic floor muscles and then plan the treatment protocol.
After the evaluation, Physiotherapy for incontinence includes manual therapy, biofeedback therapy, strengthening and coordination training.A tailored home exercise program is taught to help men improve their pelvic floor muscle awarenessduring home/work/sport and empowers men to improve pelvic floor muscles function.With dedicated physiotherapy most men with symptoms of incontinence post-prostectomy can regain full continence in 2-3 months.
Have questions about Physiotherapy in general? Here are few myth-busters you can read about!


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Having problems with your Toshiba Satellite L505-S5966 Notebook ?
The keyboard doesn't work. I have restarted the PC with no possitive results
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Case Conclusion Date: 09.30.1997
Practice Area: Insurance
Outcome: Triple damages and attorneys' fee awarded
Description: The case arose from the bad faith of Utica Mutual Insurance Company, and its failure to settle a claim arising from a car accident. The plaintiff was badly injured in the accident, and was permanently disabled. The underlying case was finally settled just prior to trial, and the case against the insurance company for bad faith insurance practices continued to trial and then to appeal. The trial judge found that the insurance company had violated M.G.L. c. 93A and c. 176D, and awarded triple damages to the plaintiff. The insurance company appealed, and the plaintiff cross-appealed. The matter was transferred to the Massachusetts Supreme Judicial Court. The SJC found in favor of the plaintiff in all respects, except for the calculation of damages. The matter was sent back to the trial judge for re-calculation of the damages. Triple damages against the insurance company for the plaintiff's loss of the use of the money plus attorneys' fees. The damages exceeded $670,000.


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Fergie is one of the top female performers as she and The Black Eye Peas have become a household name. Fergie just married her long time fiance Josh Duhammel. Fergie music videos, pictures, and news at Gossip Center with Josh and Fergie's band.
Showing off her fabulous form, Stacy "Fergie" Ferguson was spotted on the beach in Brazil yesterday afternoon (November 3).
The "Big Girls Don't Cry" songstress looked dy-no-mite in a black two-piece swimsuit as she enjoyed time with her husband Josh Duhamel and some friends.
Stepping out for an evening of sport, Jennifer Lopez was spotted at the Miami Dolphins' season opener last night (September 26).
The "Waiting for Tonight" songstress looked to be in a great mood as she mingled with fellow celebs and fans at the Sun Life Stadium.
Now that they boast a full slate of celebrity co-owners, the Miami Dolphins kicked off their season opener to quite the star-studded atmosphere on Sunday night (September 26).
Prior to kickoff, stars such as Kim Kardashian, Fergie and Tara Reid all worked their way down the orange arrivals carpet at Sun Life Stadium while readying to watch the hometown team take on the visiting New York Jets.
Looking to help out a good cause, Stacy "Fergie" Feguson and Josh Duhamel were spotted at the Avon Breast Cancer Walk in Santa Barbara yesterday (September 12).
The "Fergalicious" songstress and her handsome husband both looked to be in good spirits as they helped to raise money for the charity.
Continuing forth with her hectic traveling schedule, Fergie offered up a smile as she landed at LAX Airport in Los Angeles, CA on Tuesday night (August 24).
Fresh off of performing with her band the Black Eyed Peas in Canada, the "I Gotta Feeling" singer also made time for husband Josh Duhamel's family during a stop in Winnipeg.
She's no doubt one of the hottest performers out there, so it comes as no surprise that Fergie was chosen to pay an upcoming tribute to former "Guns N' Roses" guitarist, Slash.
Coming up on Thursday of next week, Slash will join the "Black Eyed Peas" on stage at this year's Sunset Strip Music Festival at the House of Blues.
Stepping out for a special night, Fergie was spotted at the launch of her first fragrance at the Prudential Center in Newark, New Jersey last evening (August 4).
The Black Eyed Peas beauty looked amazing in a black and tan get-up while having a marvelous time as she introduced the new scent, "Outspoken."
Taking their high-energy show to New York City, the Black Eyed Peas performed on "Good Morning America" today (July 30).
Stacy "Fergie" Ferguson, will.i.am, Apl.de.ap, and Taboo took the stage at the Rumsey Playfield before a massive crowd of fans.
She's always up to something, and yesterday (July 27) Stacy "Fergie" Ferguson was spotted out and about in Toronto, Canada.
The "My Humps" songstress made her exit from her hotel and headed off to sound check for her concert with the Black Eyed Peas.
After a rumor began circulating last week, Fergie has confirmed that she will not be leaving the Black Eyed Peas.
Recent reports claimed that the "My Humps" singer was set to quit the group due to tensions with bandmate Will.i.am.
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Case Conclusion Date: 01.01.2003
Practice Area: Employment and labor
Outcome: Case was resolved prior to trial
Description: Together with co-counsel Leon Marks, I obtained preliminary injunctive relief returning health care coverage to Mr. York. He had been diagnosed with non-Hodgkin's lymphoma and because of failure to properly provide him a COBRA notice, his health insurance coverage was terminated while he was hospitalized and unable to return to work. Before the case was filed, Mr. York had been denied a bone marrow transplant which his doctor later testified was critical for him.


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Colombian Peso Posts Biggest Drop in Emerging Markets This WeekAndrea Jaramillo
Colombia's peso plunged the most among major emerging-market currencies this week on speculation inflows into the Andean country will slow.
The peso weakened 2.1 percent this week, including a 0.2 percent slide today to 1,924.21 per dollar at the close in Bogota. The currency is now at its weakest since May.
Policy makers including Finance Minister Mauricio Cardenas and central bank co-director Adolfo Meisel said this week that the foreign-exchange impact of JPMorgan Chase & Co.'s decision to more than double Colombia's weighting in two of its bond indexes is fading. The disclosure last week that the government would delay its planned sale of an estimated $2.6 billion stake in power company Isagen SA led some investors to unwind bets that the transaction would bring dollar inflows, according to Francisco Chaves, head analyst at Corredores Asociados brokerage.
"You won't see those dollars from the sale of Isagen come in, and that's something investors had been expecting," Chaves said in a phone interview from Bogota.
Local banks were also buying dollars in anticipation of increased demand for the greenback at the end of the year as foreign companies repatriate revenue, Chaves said. While the end of the year is several months off, they were loading up in expectation that a further weakening of the peso would make the dollars more expensive.
While the increase in Colombia's weighting in bond indexes is carried out between May and September, most of the demand for local debt likely will happen through the end of this month, Chaves predicts.
Cardenas said Aug. 12 the government would wait as long as a year to auction a 57.6 percent stake in Isagen, for which Colombia wanted to get at least 5 trillion pesos ($2.6 billion) to help fund new roads. Several international companies had expressed interest.
The price on the nation's benchmark peso bonds due 2024 rose 0.38 centavo to 124.12 centavos per peso, according to data from the central bank. The yield fell 5 basis points, or 0.05 percentage point, to 6.61 percent.


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Deals of the day- Mergers and acquisitions
(Adds Braemar Shipping Services, Wesizwe, MOL, Banco Sabadell; Updates AstraZeneca, London Stock Exchange)
May 20 (Reuters) - The following bids, mergers, acquisitions and disposals were reported by 2000 GMT on Tuesday:
** AstraZeneca shareholder Schroders urged the company to restart takeover talks with Pfizer, adding its voice to criticism of the British drugmaker's rejection of the U.S. firm's 70 billion pound ($118 billion) bid.
** Canada's Valeant Pharmaceuticals International Inc said it will not make an all-cash bid for drugmaker Allergan Inc as many had expected last week when the company said it would improve its cash and stock offer for the Botox maker.
** Germany's Commerzbank is finalizing the sale of Spanish property loans to U.S. investors for up to 3.9 billion euros ($5.4 billion), sources said, in what would be one of the biggest deals of its kind since Spain's 2008 real estate crash.