Crystallography and Structure–Property Relationships in 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐Dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐ Quaterphenyl (DODECA)

X‐ray crystallographic study of 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐quaterphenyl (DODECA) has been carried out. Nonbonding interatomic distances of oxygen atoms inside of all the nitro groups are shorter than those corresponding to the intermolecular contact radii for oxygen. By means of the DFT B3LYP/6‐31(d, p) method a difference of 136 kJ mol⁻¹ between the X‐ray and DFT structures of DODECA was found. The bearer of the highest initiation reactivity in its molecule in solid phase should be the nitro group at 4′′′‐position, in contrast to those at 2′‐ or 2″‐positions in its isolated molecule. The most reactive nitro group in the DODECA molecule can be well specified by the relationship between net charges on nitro groups and charges on their nitrogen atoms, both of them for the X‐ray structure. The ¹⁵N chemical shift, corresponding to this nitro group for the initiation by impact and shock, correlates very well with these shifts of the reaction centers of the other six “genuine” polynitro arenes.     

Crystallography and Structure–Property Relationships of 2,2″,4,4′,4″,6,6′,6″‐Octanitro‐1,1′ : 3′,1″‐Terphenyl (ONT)

An X‐ray crystallographic study of 2,2″,4,4′,4″,6,6′,6″‐octanitro‐1,1′ : 3′,1″‐terphenyl (ONT) has been carried out. The dihedral angles between benzene rings vary from 84.9° to 89.4°. Nonbinding interatomic distances of oxygen atoms inside all the nitro groups are shorter than the intermolecular contact radii for oxygen. On the basis of the DFT B3LYP/6‐31(d, p) method it was found that the difference between the X‐ray structure in the solid phase and DFT result for the gas phase is 98 kJ mol⁻¹, and the bearer of the highest initiation reactivity of the ONT molecule in the solid phase should be the nitro group at 4″‐position, in contrast to those at 4′‐ or 6′‐position that play this role in the isolated molecule. It has been stated that the nitro groups at the reaction centers of the ONT molecule are relatively well specified by their ¹⁵N NMR chemical shifts.     

Atom‐transfer radical polymerization of methyl methacrylate with α,α′‐dichloroxylene/CuCl/N,N,N′,N″,N″‐pentamethyldiethylenetriamine initiation system under microwave irradiation

The atom‐transfer radical polymerization (ATRP) of methyl methacrylate (MMA), using α,α′‐dichloroxylene as initiator and CuCl/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as catalyst was successfully carried out under microwave irradiation (MI). The polymerization of MMA under MI showed linear first‐order rate plots, a linear increase of the number‐average molecular weight with conversion, and low polydispersities, which indicated that the ATRP of MMA was controlled. Using the same experimental conditions, the apparent rate constant (k) under MI (k = 7.6 × 10^?4 s^?1) was higher than that under conventional heating (k = 5.3 × 10^?5 s^?1). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2189–2195, 2004     

Direct (hetero)arylation polymerization for the synthesis of donor–acceptor conjugated polymers based on N‐benzoyldithieno [3,2‐b:2′,3′‐d]pyrrole and diketopyrrolopyrrole toward organic photovoltaic cell application

In this research, new donor–acceptor (D‐A) photovoltaic polymers were synthesized from dithieno[3,2‐b:2′,3′‐d]pyrrole electron donor derivatives, including N‐benzoyldithieno[3,2‐b:2′,3′‐d]pyrrole and N‐(4‐hexylbenzoyl)dithieno[3,2‐b:2′,3′‐d]pyrrole, in combination with the electron deficient unit 2,5‐bis(2‐ethylhexyl)‐3,6‐di(thiophen‐2‐yl)‐2,5‐dihydropyrrolo[3,4‐c]pyrrole‐1,4‐dione via direct (hetero)arylation polymerization. The D‐A conjugated polymers obtained were characterized via ¹H NMR, gel permeation chromatography, Fourier transform infrared spectroscopy, DSC, XRD, photoluminescence and UV–visible methods. In addition, these D‐A polymers were used as activated layers in bilayer and bulk heterojunction structures for the fabrication of organic photovoltaic cells. © 2019 Society of Chemical Industry     

Preparation and properties of novel fluorinated polyimides based on 2,2′,6,6′-tetrafluorobenzidine

Fluorinated polyimides were prepared from 2,2′,6,6′-tetrafluorobenzidine and four conventional dianhydride monomers by a solution polycondensation reaction followed by a chemical imidization. Polyimide based on 2,2′,6,6′-tetrafluorobenzidine and hexafluoroisopropylidene bis(3,4-phthalic anhydride) (6FDA) is soluble in organic solvents such as NMP, DMA, DMF, THF, chloroform, and acetone while those based on 2,2′,6,6′-tetrafluorobenzidine and pyromellitic dianhydride (PMDA), benzophenone-3,3′,4,4′-tetracarboxylic acid dianhydride (BTDA), diphenylether-3,3′,4,4′-tetracarboxylic acid dianhydride (ETDA) are not. Polyimide from 2,2′,6,6′-tetrafluorobenzidine and 6FDA possesses high optical transparency at 350–700 nm and has a in-plane refractive index of 1.558 at 632.8 nm. All polyimides exhibit glass transition temperatures above 350°C. They also possess very high thermal stability. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1605–1609, 1998     

Treatment of the refinery wastewater in a gas–liquid–solid three‐phase flow airlift loop bioreactor

Aerobic treatment of refinery wastewater was carried out in a 200 dm³ gas–liquid–solid three‐phase flow airlift loop bioreactor, in which a biological membrane replaced the activated sludge. The influences of temperature, pH, gas–liquid ratio and hydraulic residence time on the reductions in chemical oxygen demand (COD) and NH₄‐N were investigated and discussed. The optimum operation conditions were obtained as temperature of 25–35 °C, pH value of 7.0–8.0, gas–liquid ratio of 50 and hydraulic residence time of 4 h. The radial and axial positions had little influence on the local profiles of COD and NH₄‐N. Under the optimum operating conditions, the effluent COD and NH₄‐N were less than 100 mg dm^?3 and 15 mg dm^?3 respectively for more than 40 days, satisfying the national primary discharge standard of China (GB 8978‐1996). Copyright © 2005 Society of Chemical Industry     

Alterations in fatty acid composition and fluidity of cell membranes affect the accumulation of PCB congener 2,2′,5,5′‐tetrachlorobiphenyl by Ralstonia eutropha H850

The effect of alterations in fatty acid composition and fluidity of cell membranes on the accumulation of PCB congener 2,2′,5,5′‐tetrachlorobiphenyl (TeCB) by Ralstonia eutropha (formerly Alcaligenes eutrophus) H850 was studied. Cells of R eutropha H850 grown on either biphenyl or fructose were used. Significant increases in saturated fatty acid composition and decreases in membrane fluidity of bacteria grown on biphenyl at 28 °C were observed compared with those grown on fructose at 17 or 28 °C. The ratio of saturated fatty acids to unsaturated fatty acids and membrane fluidity of R eutropha H850 grown on biphenyl at 28 °C resembled those of cells grown on fructose at 37 °C. No inhibition effect of the uncoupler 2,4‐dinitrophenol (2,4‐DNP) on TeCB accumulation was observed, suggesting an energy‐independent mechanism for TeCB accumulation in cells of R eutropha H850. The amount of TeCB accumulated was considerably higher in R eutropha H850 grown on fructose at 17 and 28 °C than when grown on biphenyl at 28 °C. Similar amounts of TeCB accumulated in bacteria grown on biphenyl at 28 °C as compared with those grown on fructose at 37 °C. These results suggest the alterations in fatty acid composition and membrane fluidity of R eutropha H850 may affect the accumulation of TeCB. © 2002 Society of Chemical Industry     

Ditopic, flexible hydrazone-based building blocks with pendant 2,2′:6′,2′′-terpyridine metal-binding domains

The synthesis and characterization of three new bis(2,2′:6′,2′-terpyridine) (tpy) ligands containing different hydrazone spacers between the metal-binding domains are described. Treatment of 1,4-benzenedicarbaldehyde bis(2,2′:6′,2′′-terpyridin-4′-ylhydrazone) (1) with [(tpy)RuCl₃] in the presence of N-ethylmorpholine results in the formation of [(tpy)Ru(μ-1)Ru(tpy)]⁴⁺. Single crystal X-ray diffraction data for [(tpy)Ru(μ-1)Ru(tpy)][PF₆]₄·8MeCN confirm the ability of the hydrazone-based ligand to bridge two ruthenium(II) centres, providing proof-of-principle for the application of this class of flexible ligand in the design of coordination polymers.     

Preparation and characterization of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride-pyromellitic diahydride alternating polyimides

Four kinds of 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA)-pyromelliitic dianhydride (PMDA) alternating polyimide (BTDA-PMDA API) were obtained by reacting 1 mol BTDA with 2 mol diamines to form BTDA chain-extended diamines (BTDA CED), followed by the addition of 1 mol PMDA to yield the BTDA-PMDA alternating polyamic acids (BTDA-PMDA APA), and finally by imidizing them thermally. BTDA CED were characterized by elemental analysis, infrared (IR), and ¹H-NMR spectroscopy. The structures of BTDA-PMDA APA and BTDA-PMDA API were investigated by IR and ¹H-NMR spectroscopy, and their thermal properties and interfacial tension were also studied. Furthermore, the characteristic properties of BTDA-PMDA API were compared with their corresponding homopolyimides from BTDA (BTDA HPI) and from PMDA (PMDA HPI). It was found that the alternating condensation polymerization is an effective method to modify polyimides interfacial tension with a small influence on the thermal stability. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1585–1593, 1997     

Synthesis of pyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles and pyrazolo[4′,3′:5,6]pyrazino[2,3-d]pyrimidines and their application to polyester fibres

4-Nitroso-1-phenyl-3-methyl-5-aminopyrazole ( 1 ) was condensed with ethylcyanoacetate ( 2 ), malononitrile ( 4a ) and 2-cyanomethylbenzimidazole ( 4b ) to yield 6-hydroxy-5-cyano, 6-amino-5-cyano and 6-amino-5-(benzimidazol-2-yl)-3-methylpyrazolo [3,4-b]pyrazines 3, 5a and 5b , respectively. 5-Cyano-6-chloro derivative 6 obtained from 3 was converted to 3-aminopyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles 8a and 8b by the treatment with hydrazin hydrate ( 7a ) and phenylhydrazine ( 7b ), respectively. Compound 5a was treated with formamide ( 9a ), urea ( 9b ) and thiourea ( 9c ) to give 4-aminopyrazolo[4′,3′:5,6]pyrazino[2′3′-d]pyrimidines 10a–10c. With refluxing acetic anhydride compounds 8a, 8b and 10a gave corresponding acetamido derivatives 8c, 8d and 10d. Compound 5a was treated with ethylorthoformate ( 11 ), acetic anhydride ( 12 ) or benzoylchloride ( 13 ) to give fused benzimidazopyrazolo[4′,3′:5,6]pyrazino[2′,3′-d]pyrimidines, viz., benzimidazol[1,2-c]pyrazolo[4,3-g]pteridines ( 14a–14c ). Some of the compounds 8, 10 and 14 were applied to polyester as disperse dyes and their fastness properties were studied.     

Synthesis of Substituted 2,2′‐Bipyridines and 2,2′:6′,2′′‐Terpyridines by Cobalt‐Catalyzed Cycloaddition Reactions of Nitriles and α,ω‐Diynes with Exclusive Regioselectivity

A variety of substituted 2,2′‐bipyridines were synthesized by a 1,2‐bis(diphenylphosphino)ethane (dppe)/cobalt chloride hexahydrate (CoCl₂⋅6 H₂O)/zinc‐catalyzed [2+2+2] cycloaddition reaction of diynes and nitriles, with all reactions exhibiting exclusive regioselectivity. Thus, symmetrical and unsymmetrical 1,6‐diynes and 2‐cyanopyridine reacted in the presence of 5 mol % of dppe, 5 mol % of CoCl₂⋅6 H₂O and 10 mol % of zinc powder to provide the corresponding 2,2′‐bipyridines. Under identical reaction conditions, 1‐(2‐pyridyl)‐1,6‐diynes and nitriles reacted smoothly with exclusive regioselectivity to produce 2,2′‐bipyridines in good yield. 2,2′‐Bipyridines were also obtained by the double [2+2+2] cycloaddition reaction of 1,6,8,13‐tetraynes with nitriles. Similarly, 2,2′:6′,2′′‐terpyridines were synthesized from 1‐(2‐pyridyl)‐1,6‐diyne and 2‐cyanopyridine. The regiochemistry observed can be explained by considering the electronic nature of cobaltacyclopentadiene intermediates and nitriles. A survey of the exclusive regiochemical trend gives reasonable credence to the synthetic potential of the present method.     

Effects of sodium chloride on the production of bioactive exopolysaccharides in submerged cultures of Phellinus linteus

BACKGROUND: Polysaccharides isolated from medicinal mushrooms have been shown to exhibit antitumour bioactivity, but the quality and quantity of these polysaccharides are affected by variations in medium composition and operational conditions in the submerged culture. This study was conducted to elucidate quantitatively the effects of sodium chloride (NaCl) supplementation on the production and quality of exopolysaccharides from the medicinal mushroom Phellinus linteus. RESULTS: Supplementation of NaCl to submerged cultures of P. linteus significantly affected the morphology, the exopolysaccharide (PLPS) production, its average molecular weight and its biological activity. Phellinus linteus grew in a filamentous form in NaCl‐free medium, but a pellet form became predominant as NaCl supplemention increased. The specific growth rate decreased monotonically from 0.18 to 0.01 day^?1 as the NaCl concentration increased from 0.0 to 2.0 g dm^?3 (34.22 mmol dm^?3); however, the specific product yield increased monotonically from 3.9 to 98.4 mg g^?1 (25.2‐fold enhancement). Both 14.3‐fold enhancement (from 23 to 329 mg dm^?3) in the production of PLPS and 1.5‐fold enhancement (from 670 to 995 pg TNF‐α (tumour necrosis factor α) cm^?3) in its biological activity were achieved as the NaCl concentration increased from 0.0 to 1.0 g dm^?3 (17.11 mmol dm^?3). The biological activity of PLPS was highly correlated with its average molecular weight (coefficient R² = 0.90). CONCLUSION: The average molecular weight of PLPS was key to its biological activity. Both the quantity and bioactivity of PLPS could be significantly enhanced by appropriate NaCl supplementation to the submerged culture of the medicinal mushroom. Copyright © 2008 Society of Chemical Industry     

An alternative for pre‐treatment of high‐strength raw whey wastewaters: submerged membrane bioreactors

The direct treatment of whey wastewater at various sludge ages (10–75 days) and high biomass concentration (above 50 g mixed liquor suspended solid (MLSS) dm^?3) in a submerged membrane bioreactor (sMBR) is described. The chemical oxygen demand (COD) of raw whey varied in the range of 60 and 90 g dm^?3. After feeding the sMBR with raw whey, effluent COD reduced to about 20 g dm^?3. The effluent was free of suspended solids and total coliform bacteria. Total phosphorus (TP) and orthophosphate (Ortho‐P) in the influent varied between 204 and 880 mg dm^?3 and between 180 and 620 mg dm^?3, and effluent TP and Ortho‐P reduced to 113 and 109 mg dm^?3, respectively. The ammonium and nitrate concentrations in the influent were in the ranges of 3.4 and 120 mg dm^?3 and 10 and 503 mg dm^?3, respectively. The effluent ammonium concentration varied between 17.6 and 198 mg dm^?3 and nitrate concentrations varied between 0.9 and 69 mg dm^?3. Effluent turbidity varied between 23 and 111 FAU (Formazin Attenuation Unit). The results show that sMBR is an effective pre‐treatment system for high‐strength agro‐wastewaters because of its ability to reduce the pollution load. Copyright © 2004 Society of Chemical Industry     

Synthesis and hydrolysis study of polyacrylates containing 2′,5-dichloro-4′-nitrosalicylanilide

Monomers (meth)acryloyloxy-2′,5-dichloro-4′-nitrosalicylanilide have been synthesized by treating 2′,5-dichloro-4′-nitrosalicylanilide (niclosamide) with acryloyl or methacryloyl chloride, and polymerized by free radical polymerization to give a polymer containing chemically bonded niclosamide. The structure of monomer and polymer were confirmed by IR, UV, and elemental analysis. Hydrolysis data of polymer in different media indicated that the hydrolysis rates of polymer were strongly dependent on the nature of the polymer structure and the hydrolyzing medium. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 29–33, 1997     

A study toward the physicochemical properties of graft copolymer (partially carboxymethylated guar gum‐g‐N,N′‐dimethylacrylamide): Synthesis and characterization

Unreported graft copolymer of N,N′‐dimethylacrylamide (DMA) with partially carboxymethylated guar gum (CmgOH) has been synthesized and the reaction conditions have been optimized for affording maximum grafting using a potassium peroxymonosulphate (PMS)/thiourea (TU) redox initiators under nitrogen atmosphere. The study of graft copolymerization has been performed to observe maximum value of grafting parameters except percentage of homopolymer by varying the concentrations of DMA, PMS, and TU. The grafting parameters increase continuously on increasing the concentration of DMA from 8 × 10^?2 to 24 × 10^?2 mol dm^?3, PMS from 5 × 10^?3 to 21 × 10^?3 mol dm^?3, and TU from 1.6 × 10^?3 to 4.8 × 10^?3 mol dm^?3. The optimum temperature and time for grafting of DMA onto CmgOH were found to be 35°C and 120 min, respectively. The water‐swelling capacity of graft copolymer is investigated. Flocculation property for both coking and noncoking coals is studied for the treatment of coal mine waste water. The graft copolymer is characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The effect of lauric acid shock loads on the biological and physical performance of granular sludge in UASB reactors digesting acetate

The specific activity of acetotrophic methanogens and the physical behaviour of granular sludge in laboratory-scale upflow anaerobic sludge bed (UASB) reactors subjected to shock loads of lauric acid in the absence and presence of calcium were studied. In the absence of calcium, lauric acid completely inhibited acetotrophic methanogens above a threshold level of 100 mg C_12:0dm^?3, whereas no inhibition occurred below this threshold concentration. Addition of an equivalent amount of calcium to wastewater containing lauric acid prevented inhibition of acetotrophic methanogens at least up to 1500 mg C_12:0dm^?3. Addition of less than an equivalent amount of calcium apparently removed more than a stoichiometric amount of lauric acid: 50 % inhibition occurred at approximately 700 mg ‘free’ or excess C_12:0dm^?3. The results indicate that complete sludge wash-out from conventional UASB reactors is likely to occur within 2-8 h if the system is overloaded with an influent containing more than 100 mg C_12:0dm^?3. Calcium did not prevent wash-out.     

Determination of potential methane production capacity of a granular sludge from a pilot‐scale upflow anaerobic sludge blanket reactor using a specific methanogenic activity test

A 450 dm³ pilot‐scale upflow anaerobic sludge blanket (UASB) reactor was used for the treatment of a fermentation‐based pharmaceutical wastewater. The UASB reactor performed well up to an organic loading rate (OLR) of 10.7 kg COD m^?3 d^?1 at which point 94% COD removal efficiency was achieved. This high treatment efficiency did not continue, however and the UASB reactor was then operated at lower OLRs for the remainder of the study. Specific methanogenic activity (SMA) tests were, therefore, carried out to determine the potential loading capacity of the UASB reactor. For this purpose, the SMA tests were carried out at four different initial acetate concentrations, namely 500 mg dm^?3, 1000 mg dm^?3, 1500 mg dm^?3 and 2000 mg dm^?3 so that substrate limitation could not occur. The results showed that the sludge sample taken from the UASB reactor (OLR of 6.1 kg COD m^?3 d^?1) had a potential acetoclastic methane production (PMP) rate of 72 cm³ CH₄ g^?1 VSS d^?1. When the PMP rate was compared with the actual methane production rate (AMP) of 67 cm³ CH₄ g^?1 VSS d^?1 obtained from the UASB reactor, the AMP/PMP ratio was found to be 0.94 which ensured that the UASB reactor was operated using its maximum potential acetoclastic methanogenic capacity. In order to achieve higher OLRs with desired COD removal efficiencies it was recommended that the UASB reactor should be loaded with suitable OLRs pre‐determined by SMA tests. © 2001 Society of Chemical Industry     

Bis(4′-phenyl-2,2′:6′,2″-terpyridine)ruthenium(II): Holding the {Ru(tpy)2} embraces at bay

The solid state structure of [Ru(Phtpy)₂][PF₆]₂ · 4MeCN has been determined (Phtpy = 4′-phenyl-2,2′:6′,2″-terpyridine); [Ru(Phtpy)₂]²⁺ cations pack into sheets by virtue of {M(tpy)₂}₂ embraces, and the MeCN solvent molecules are involved in NH–C interactions which prevent the efficient packing of adjacent sheets. Comparisons with related structures lead to some generalizations about packing motifs in salts containing [M(Phtpy)₂]²⁺ or [M(pytpy)₂]²⁺ cations (pytpy = 4′-pyridyl-2,2′:6′,2″-terpyridine).     

Reaction kinetics and thermal properties of epoxidised cresol novolac/4,4′‐diglycidyl (3,3′,5,5′‐tetramethylbiphenyl) epoxy resin composite cured with aromatic diamine

A series of novel composites based on different ratios of epoxidised cresol novolac (ECN) and 4,4′‐diglycidyl(3,3′,5,5′‐tetramethylbiphenyl) epoxy resin (TMBP) have been prepared with the curing agent 4,4′‐methylenediamine (DDM) and 4,4′‐diaminodiphenylsulfone (DDS), respectively. The investigation of cure kinetics was performed by differential scanning calorimetry using an isoconversional method. The high thermal stabilities of the cured samples were also studied by thermogravimetric analysis. In addition, no phase separation was observed for cured ECN/DDM and ECN/DDS blending with different amounts of TMBP by dynamic mechanical analysis and scanning electron microscopy. Moreover, the cured systems also exhibited excellent impact properties and low moisture absorption. All the results indicate that the ECN/TMBP/DDM and ECN/TMBP/DDS systems are promising materials in electronic packaging. Copyright © 2011 Society of Chemical Industry