Chemsitry

The present work aims to investigate and develop a one-bath dyeing process for most common blend fibres to replace the conventional two-step process usually applied to dye each fibre constituent separately. The main objectives of the proposed process is the conservation of energy, raw materials, dyes, auxiliaries and labour.

With nucleophilic aromatic substitution and ester condensation reactions, several new first-generation dendrimers and star-shaped molecules containing cationic cyclopentadienyl iron moieties were prepared. Although the solubility of the organoiron star-shaped molecules with ether bridges in polar solvents was found to decrease with an increase in the size of the molecule, the addition of ester linkages resulted in a sharp decrease in the solubility, regardless of the size. The thermal behavior of these molecules was examined with differential scanning calorimetry and thermogravimetric analysis. The glass-transition temperatures (T g 's) of these star-shaped molecules ranged from 123 to 170°C. However, the addition of the ester functionality allowed for an increase in the T g 's to 151-194°C. The star-shaped molecules were thermally stable up to 200°C, above which a loss of the cationic cyclopentadienyl iron moieties occurred. Degradation of the ester chains started at 321°C, and degradation of the ether chains started at 408°C. Electrochemical studies of the ether star-shaped molecules showed a reduction of the 18-electron iron centers to 19-electron centers. This redox system was reversible at low temperatures, whereas it was irreversible at room temperature. Moreover, an increase in the number of metal moieties caused an overlap and broadening of the redox wave. Viscosity studies showed a polyelectrolyte effect for the organoiron star-shaped molecules.

A new class of thermochromic polynorbornene with pendent spiropyran moieties has been synthesized. Functionalization of norbornene monomers with spirobenzopyran moieties has been achieved using Steglich esterification. These new monomeric materials were polymerized via Ring Opening Metathesis Polymerization (ROMP). In spite of their poor solubility, polynorbornenes with spirobenzopyran exhibited thermochromic behavior due to the conversion of their closed spiropyran moieties to the open merocyanine form. Moreover, these polymers displayed bathochromic shifts in their optical response, which was attributed to the J-aggregation of the attached merocyanine moieties that were associated with their high concentration in the polymeric chain. The surface of the obtained polymers was exposed to atmospheric pressure air Dielectric Barrier Discharge (DBD) plasma system, which resulted in the reduction of the surface porosity and converted some surface area into completely non-porous regions. Moreover, the plasma system created some areas with highly ordered J-aggregates of the merocyanine form in thread-like structures. This modification of the polymers' morphology may alter their applications and allow for these materials to be potential candidates for new applications, such as non-porous membranes for reverse osmosis, nanofiltration, or molecular separation in the gas phase.

A new class of thermochromic polynorbornene with pendent spiropyran moieties has been synthesized. Functionalization of norbornene monomers with spirobenzopyran moieties has been achieved using Steglich esterification. These new monomeric materials were polymerized via Ring Opening Metathesis Polymerization (ROMP). In spite of their poor solubility, polynorbornenes with spirobenzopyran exhibited thermochromic behavior due to the conversion of their closed spiropyran moieties to the open merocyanine form. Moreover, these polymers displayed bathochromic shifts in their optical response, which was attributed to the J-aggregation of the attached merocyanine moieties that were associated with their high concentration in the polymeric chain. The surface of the obtained polymers was exposed to atmospheric pressure air Dielectric Barrier Discharge (DBD) plasma system, which resulted in the reduction of the surface porosity and converted some surface area into completely non-porous regions. Moreover, the plasma system created some areas with highly ordered J-aggregates of the merocyanine form in thread-like structures. This modification of the polymers' morphology may alter their applications and allow for these materials to be potential candidates for new applications, such as non-porous membranes for reverse osmosis, nanofiltration, or molecular separation in the gas phase.

All manipulations were performed using glove box and Schlenk/vacuum line techniques. Methanol and methylene chloride were dried over CaH 2 and distilled prior to use. Toluene and benzene were dried over Na and distilled prior to use. NMR spectra were acquired on a Bruker AMX 300 NMR spectrometer (300 MHz 1 H; 75.5 MHz 13 C; 121.5 MHz 31 P). 1 H and 13 C spectra were referenced to solvent signals. 31 P spectra were reference to an external H 3 PO 4 standard (δ = 0). UV-vis spectra were obtained on a Ocean Oprtics, Chem 2000-UV-VIS instrument. Photoluminescence spectra were obtained on a HoribaJobin Yvon FluoroMax-3 instrument. Micropowder analysis was preformed on a modified 1 Bruker SMART APEX system in Debye-Scherrer mode with exposures of 1200 x 2 seconds. Data was Collected using SMART 2 and interpreted and integrated using GADDS. 3 Synthesis of (Ph 3 P) 2 CuIn(S t Bu) 4. Single source precursors were prepared according to a previously described procedure. 4 Na[InS t Bu] 4 was prepared by adding 0.48 ml (4.26 mmol) 2,2-dimethylpropanethiol to a methanol solution of NaOCH 3 formed by adding sodium (0.102 g, 4.45 mmol) to 15 mL methanol. After 30 min a methanol solution of InCl 3 (0.2308 g, 1.04 mmol) was added via cannula and the reaction mixture stirred for an

A number of red to violet thienyl-2-azo and thienyl-5-azo disperse dyes were prepared using Gewald's methodology. Structural characterization of these novel dyes was carried out using IR, NMR and mass spectroscopy. UVevisible studies of these azo dyes in a number of polar solvents showed a considerable difference in the l max. The introduction of various substituents to these azo dyes as well as the polarity of solvents resulted in absorption in the visible region ranging from 461 to 555 nm.

The synthesis of the title complexes was achieved via the reaction of g 6-p-dichlorobenzene-g 5cyclopentadienyliron cations with 4,4¢-bis(4-hydroxyphenyl)valeric acid to produce the diiron complexes which were then reacted with a number of arylazo dyes to give cationic bis(cyclopentadienyliron)arene complexes containing the arylazo dyes. These iron-containing monomers were subsequently polymerized via nucleophilic aromatic substitution using 1,8octanedithiol, 4,4¢-thiobisbenzenethiol, or bisphenol A to produce the desired coloured cationic organoiron polymers. The weight-average molecular weights were estimated to range from 11,800 to 31,600. UV-vis studies conducted in dimethylformamide (DMF) showed that the metallated polymers exhibited k max of 412-491 nm. Addition of HCl to the polymer solution caused a bathochromic shift into the range of 515-530 nm. Thermogravimetric analysis (TGA) revealed that the iron moieties were cleaved between 205 and 248°C while the polyether/thioether backbone degraded between 380 and 613°C. Differential scanning calorimetry (DSC) showed that the polymers exhibited glass transition temperatures (Tg) ranging from 106 to 184°C.

A series of star-shaped macromolecules bearing distinct symmetrical branches with alternating organoiron complexes and azobenzene moieties were synthesized using both convergent and divergent approaches. The various azo dye and organoiron-containing branches were reacted with multifunctional cores via metal-mediated nucleophilic aromatic substitution and ester condensation reactions to afford multi-substituted three-and four-arm star-shaped oligomers. UV-vis spectral studies of complexes 15 and 22 (k max = 435 and 427 nm, respectively) show bathochromic shifts (k max = 576 and 558, respectively) at various HCl concentrations indicating their use as potential acid sensors. Cyclic voltammetric studies of the octa-iron oligomer 22 were reversibly reduced at E 1/2 =-1.53 V. Keywords Star-shaped Á Organoiron Á Azo dye Á Ferrocene cyclopentadienyliron Á Arene complexes Á Substitution reaction This paper is dedicated to Professor Charles U. Pittman, Jr. in recognition of his outstanding contribution to the field of inorganic and organometallic polymers.

A series of novel 4H-benzo[h]chromenes 4, 6-11, 13, 14; 7H-benzo[h]chromeno[2,3-d] pyrimidines 15-18, 20, and 14H-benzo[h]chromeno[3,2-e][1,2,4]triazolo[1,5-c]pyrimidine derivatives 19a-e, 24 was prepared. The structures of the synthesized compounds were characterized on the basis of their spectral data. Some of the target compounds were examined for their antiproliferative activity against three cell lines; breast carcinoma (MCF-7), human colon carcinoma (HCT-116) and hepatocellular carcinoma (HepG-2). The cytotoxic behavior has been tested using MTT assay and the inhibitory activity was referenced to three standard anticancer drugs: vinblastine, colchicine and doxorubicin. The bioassays demonstrated that some of the new compounds exerted remarkable inhibitory effects as compared to the standard drugs on the growth of the three tested human tumor cell lines. The structure-activity relationships (SAR) study highlights that the antitumor activity of the target compounds was significantly affected by the lipophilicity of the substituent at 2-or 3-and fused rings at the 2,3-positions.

In our effort to develop novel and powerful agents with anti-proliferative activity, two new series of 1H-benzo[f]chromene derivatives, 4a-h and 6a-h, were synthesised using heterocyclocondensation methodologies under microwave irradiation condition. The structures of the target compounds were established on the basis of their spectral data, IR, H NMR,  C NMR,  C NMR-DEPT/APT, and MS data. The new compounds have been examined for their anti-proliferative activity against three cancer cell lines, MCF-7, HCT-116, and HepG-2. Vinblastine and Doxorubicin have been used as positive controls in the viability assay. The obtained results confirmed that most of the tested molecules revealed strong and selective cytotoxic activity against the three cancer cell lines. Moreover, these molecules exhibited weak cytotoxicity on the HFL-1 line, which suggested that they might be ideal anticancer candidates. The SAR study of the new benzochromene compounds verified that the substituents on the pheny...

Novel fused chromenes (4,7–11) and pyrimidines (12–16) were designed, synthesized, and evaluated for their mammary gland breast cancer (MCF-7), human colon cancer (HCT-116), and liver cancer (HepG-2) activities. The structural identity of the synthesized compounds was established according to their spectroscopic analysis, such as FT-IR, NMR, and mass spectroscopy. The preliminary results of the bioassay disclosed that some of the target compounds were proven to have a significant antiproliferative effect against the three cell lines, as compared to Doxorubicin, Vinblastine, and Colchicine, used as reference drugs. Particularly, compounds 7 and 14 exerted promising anticancer activity towards all cell lines and were chosen for further studies, such as cell cycle analysis, cell apoptosis, caspase 3/7 activity, DNA fragmentation, cell invasion, and migration. We found that these potent cytotoxic compounds induced cell cycle arrest at the S and G2/M phases, prompting apoptosis. Furtherm...

Novel flavanones that incorporate chromene motifs are synthesized via a one-step multicomponent reaction. The structures of the new chromenes are elucidated by using IR, 1H-NMR, 13C-NMR, 1H-1H COSY, HSQC, HMBC, and elemental analysis. The new compounds are screened for their in vitro antimicrobial and cytotoxic activities. The antimicrobial properties are investigated and established against seven human pathogens, employing the agar well diffusion method and the minimum inhibitory concentrations. A majority of the assessed derivatives are found to exhibit significant antimicrobial activities against most bacterial strains, in comparison to standard reference drugs. Moreover, their cytotoxicity is appraised against four different human carcinoma cell lines: human colon carcinoma (HCT-116), human hepatocellular carcinoma (HepG-2), human breast adenocarcinoma (MCF-7), and adenocarcinoma human alveolar basal epithelial cell (A-549). All the desired compounds are subjected to in-silico s...

New modified acidic catalysts were prepared from the treatment of silica, titania and silica prepared from hydrolyzed tetraethyl orthosilicate (TEOS) with sulfuric and phosphoric acid. The sulfated and phosphated silica synthesized from TEOS were calcined at 450 and 650 • C. These catalysts were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), and scanning electron microscope (SEM). The surface areas, total pore volume, and mean pore radius of the acidic catalysts were investigated, while the pore size distribution was determined by the Barrett, Joyner and Halenda (BJH) method. The catalytic activity of the sulfated and phosphated silica and/or titania were examined with the Pechmann condensation reaction, in which different phenols reacted with ethyl acetoacetate as a neat reaction to obtain the corresponding coumarin derivatives. The results indicated that the treatment of the catalysts with sulfuric or phosphoric acid led to a decrease in the phases' crystallinity to a certain degree. The morphology and the structure of the acidified catalysts were examined and their particle size was calculated. Furthermore, the amount of the used catalysts played a vital role in controlling the formation of the products as well as their performance was manipulated by the number and nature of the active acidic sites on their surfaces. The obtained results suggested that the highest catalytic conversion of the reaction was attained at 20 wt % of the catalyst and no further increase in the product yield was detected when the amount of catalyst exceeded this value. Meanwhile the phenol molecules were a key feature in obtaining the final product.

The synthesis of an aromatic ether complex of cyclopentadienyliron containing two terminal aldehyde groups was achieved via metal-mediated nucleophilic aromatic substitution reactions. This dialdehyde monomer was subsequently reacted with a variety of aliphatic and aromatic diamines to produce the corresponding soluble cationic organoiron polyether-imines. These cationic organometallic polymers were characterized using IR, 1 H, and 13 C NMR, viscosity and thermogravimetric analysis. Viscosity measurements showed that these polymers exhibited polyelectrolyte effects in DMSO solutions. Thermogravimetric analysis showed that decoordination of the iron moieties occurred at about 300°C for polymers with aliphatic spacers in their backbones, while the cyclopentadienyliron moieties were cleaved from the polymers with aromatic spacers in their backbones at about 200°C. Photolytic demetallation of the organoiron polymers resulted in the removal of the pendent cyclopentadienyliron moieties and allowed for the isolation of their organic analogs. While the organoiron polymers were soluble in polar organic solvents, the corresponding organic polymers exhibited very limited solubilities or were insoluble. The organic polymers had glass transition temperatures between 101 and 120°C