Sulfonation of 1,4-diaminoanthraquinone leuco by chlorosulfonic acid:Kinetics and process intensification

The work herein employed a rotating packed bed(RPB)to intensify the sulfonation process of 1,4-diaminoanthraquinone leuco(DL)in an attempt to improve the yield of the product 1,4-diaminoanthra quinone-2-sulfonic acid(DSA).First,the effects of operating conditions in a stirred tank reactor(STR),including stirring speed,chlorosulfonic acid/DL molar ratio(η),solvent/DL mass ratio(ζ),reaction temperature and dropping speed of chlorosulfonic acid,on the yield of DSA were investigated.The yield of DSA can reach 87.34%under the optimal operating conditions:stirring speed of 500 r·min^(-1),ηof 4.5,ζof 7,reaction temperature of 150℃,dropping speed of 0.61 ml·min^(-1).In addition,the kinetics of the sulfonation process via the shrinking core model revealed that the reaction is controlled by diffusion via a product layer under the reaction temperature of 140℃.Furthermore,the RPB was employed to intensify the mass transfer between liquid and solid phases during the sulfonation reaction process.The results showed that the DSA yield of 92.69%obtained by RPB was 5.35%higher than that by STR,indicating that RPB can significantly intensify the mass transfer in the liquid-solid phase sulfonation reaction process.

Efficacy of Topical versus Oral 5-Aminosalicylate for Treatment of 2,4,6-Trinitrobenzene Sulfonic Acid-induced Ulcerative Colitis in Rats

5-aminosalicylic acid（5-ASA） is drug of choice for the treatment of ulcerative colitis（UC）. In this study, the efficacy of topical versus oral 5-ASA for the treatment of UC was examined as well as the action mechanism of this medication. A flexible tube was inserted into the rat cecum to establish a topical administration model of 2,4,6-trinitrobenzene sulfonic acid（TNBS）-induced UC. A total of 60 rats were divided into sham operation group（receiving an enema of 0.9% saline solution instead of the TNBS solution via the tube）, model group, topical 5-ASA group, oral Etiasa group（a release agent of mesalazine used as positive control） and oral 5-ASA group（n=12 each）. Different treatments were administered 1 day after UC induction. The normal saline（2 mL） was instilled twice a day through the tube in the sham operation group and model group. 5-ASA was given via the tube in the topical 5-ASA group（7.5 g/L, twice per day, 100 mg/kg）, and rats in the oral Etiasa group and oral 5-ASA group intragastrically received Etiasa（7.5 g/L, twice per day, 100 mg/kg） and 5-ASA（7.5 g/L, twice per day, 100 mg/kg）, respectively. The body weight was recorded every day. After 7 days of treatment, blood samples were drawn from the heart to harvest the sera. Colonic tissues were separated and prepared for pathological and related molecular biological examinations. The concentrations of 5-ASA were detected at different time points in the colonic tissues, feces and sera in different groups by using the high pressure liquid chromatography（HPLC）. The results showed that the symptoms of acute UC, including bloody diarrhea and weight loss, were significantly improved in topical 5-ASA-treated rats. The colonic mucosal damage, both macroscopical and histological, was significantly relieved and the myeloperoxidase activity was markedly decreased in rats topically treated with 5-ASA compared with those treated with oral 5-ASA or Etiasa. The mRNA and protein expression of IL-1β, IL-6, and TNF-α was down-regulated in the colonic tissue of rats topically treated with 5-ASA, significantly lower than those from rats treated with oral 5-ASA or Etiasa. The concentrations of 5-ASA in the colonic tissue were significantly higher in the topical 5-ASA group than in the oral 5-ASA and oral Etiasa groups. It was concluded that the topical administration of 5-ASA can effectively increase the concentration of 5-ASA in the colonic tissue, decrease the expression of proinflammatory cytokines, alleviate the colonic pathological damage and improve the symptoms of TNBS-induced acute UC in rats.

Effect of AMPS(2-acrylamido-2-methylpropane sulfonic acid) content on the properties of polymer gels

The BST oilfield in the northwestern Taklamakan Desert is a fractured carbonate reservoir,but issues of water breakthrough are becoming increasingly severe with the development of water flooding.Unfortunately,the high-temperature and high-salt conditions(130°C,71695 mg/L)of the BST oilfield pose challenges for the development of plugging agents.In this study,the effects of 2-acrylamido-2-methylpropane sulfonic acid(AMPS)content on AM/AMPS copolymers and gels were studied through viscosity measurements,nuclear magnetic resonance(NMR),and cryo-scanning electron microscope(Cryo-SEM).Moreover,the AMPS stabilization mechanism of the polymers and gels was explained.Heatresistant and salt-tolerant gel systems were developed,and their gelation properties,thermal stability,injection capacity,and plugging ability were evaluated.Experimental results showed inconsistencies between the effects of AMPS content on the polymers and gels.For the polymers,the thermal stability increased with increased AMPS content in the polymer.However,excessive AMPS content resulted in poor gelation and low strength.The developed gel systems with S30 polymer(AMPS content is approximately 26%)exhibited excellent thermal stability,controllable gelation time,good injection capacity,and plugging ability.The field application results indicated that most production wells had a positive response,with reduced water-cut and increased daily oil production.

THERMODYNAMIC STUDY ON ADSORPTION OF AROMATIC SULFONIC ACIDS ONTO MACROPOROUS WEAK BASE ANION EXCHANGER FROM AQUEOUS SOLUTIONS

The adsorption equilibrium isotherms of three aromatic sulfonic acid compounds, 2-naphthalenesulfonic acid, p-toluenesulfonic acid and p-chlorobenzenesulfonic acid, from aqueous solutions by macroporous weak base anion exchanger within the temperature range of 293 K-313 K were obtained. Several isotherm equations were correlated with the equilibrium data, and the experimental data was found to fit the three-parameter Redlich-Peterson equation best within the entire range of concentrations. The study showed that the hydrophobicity of solute has distinct influence on adsorption capacity of the anion exchanger for the aromatic sulfonic acid. Moreover, estimations of the isosteric enthalpy, free energy, and entropy change of adsorption were also reported. The positive isosteric enthalpy and entropy change for adsorption indicate an endothermic and entropy driven process in the present study.

Chemical functionalization of chitosan biopolymer and chitosan-magnetite nanocomposite with sulfonic acid for acid-catalyzed reactions

Chemical functionalization of chitosan biopolymer and chitosan-magnetite nanocomposite was performed with sulfonic acid functional groups to achieve new solid acid materials.The sulfonic acid functional groups were created through the ring opening nucleophilic reaction of amine groups of chitosan with 1,4-butane sultone.Fourier transform infrared spectroscopy(FT-IR)and X-ray photoelectron spectroscopies(XPS)verified the successful sulfonic acid functionalization of chitosan.The obtained sulfonic acid functionalized chitosan-magnetite nanocomposite showed superparamagnetic properties according to the vibrating sample magnetometry analysis and exhibited magnetic separation feature from dispersed mixtures.Nitrogen adsorption-desorption analysis indicated the increase in surface area after formation of chitosan-magnetite nanocomposite and functionalization with sulfonic acid.Both of the prepared solid acids exhibited high catalytic activities in the acid-catalyzed acetic acid esterification with n-butanol and benzaldehyde acetalization with ethylene glycol as model reactions.Furthermore,they can be reused several times without considerable loss of their activities.

Key factors in developing the trinitrobenzene sulfonic acid-induced post-inflammatory irritable bowel syndrome model in rats

AIM:To investigate the key factors in developing the trinitrobenzene sulfonic acid(TNBS)-induced postinflammatory irritable bowel syndrome(PI-IBS)model in rats. METHODS:TNBS was administered to rats at the following conditions:(1)with different doses(20,10,5 mg/0.8 mL per rat);(2)with same dose in different concentrations(20 mg/rat,25,50 mg/mL);(3)in different ethanol percentage(25%,50%);and(4)at depth either 4 cm or 8 cm from anus.At 5 d and 4 wk after TNBS administration,inflammation severity and inflammation resolution were evaluated.At 4 and 8 wk after TNBS application,visceral hyperalgesia and enterochromaffin(EC)cell hyperplasia were assayed by abdominal withdrawal reflex test,silver staining and capillary electrophoresis. RESULTS:Our results showed that:(1)TNBS induced dose-dependent acute inflammation and inflammation resolution.At 5 d post TNBS,the pathological score and myeloperoxidase(MPO)activity in all TNBS treated rats were significantly elevated compared to that of the control(9.48±1.86,8.18±0.67,5.78± 0.77 vs 0,and 3.55±1.11,1.80±0.82,0.97±0.08 unit/mg vs 0.14±0.01 unit/mg,P<0.05).At 4 wk post TNBS,the pathological score in high and median dose TNBS-treated rats were still significantly higher than that of the control(1.52±0.38 and 0.80±0.35 vs 0,P<0.05);(2)Intracolonic TNBS administration position affected the persistence of visceral hyperalgesia.At 4 wk post TNBS,abdominal withdrawal reflex (AWR)threshold pressure in all TNBS-treated groups were decreased compared to that of the control(21.52 ±1.73 and 27.10±1.94 mmHg vs 34.44±1.89 mmHg,P<0.05).At 8 wk post TNBS,AWR threshold pressure in 8 cm administration group was still significantly decreased(23.33±1.33 mmHg vs 36.79±2.29 mmHg,P<0.05);(3)Ethanol percentage affected the TNBS-induced inflammation severity and visceral hyperalgesia.In TNBS-25%ethanol-treated group,the pathological score and MPO activity were significantly lowered compared to that of the TNBS-50%ethanoltreated group,while AWR threshold pressure were significantly elevated(36.33±0.61 mmHg vs 23.33±1.33 mmHg,P<0.05);and(4)TNBS(5 mg/0.8 mL per rat, in 50%ethanol,8 cm from anus)-treated rats recovered completely from the inflammation with acquired visceral hyperalgesia and EC cell hyperplasia at 4 wk after TNBS administration.CONCLUSION:TNBS dosage,concentration,intraco-lonic administration position,and ethanol percentage play important roles in developing visceral hyperalgesia and EC cell hyperplasia of TNBS-induced PI-IBS rats.

Effects of Changtai granules, a traditional compound Chinese medicine, on chronic trinitrobenzene sulfonic acid-induced colitis in rats

AIM: To study the effects of Changtai granules (CTG), a traditional compound Chinese medicine, on chronic trinitrobenzene sulfonic acid-induced colitis in rats. METHODS: Healthy adult Sprague-Dawley (SD) rats of both sexes, weighing 250-300 g, were employed in the present study. The rat colitis models were induced by 2, 4,6-trinitrobenzene sulfonic acid (TNBS) enemas at a concentration of 100 mg/kg in 50% ethanol. The experimental animals were randomly divided into dexamethasone (DX) treatment, CTG treatment, and model control groups, which were intracolicly treated daily with DX (0.2 mg/kg), CTG at doses of 2.9, 5.7 and 11.4 g crude drug/kg, and the equal amount of saline respectively from 6 h following induction of the colitis in rats inflicted with TNBS to the end of study. A normal control group of rats treated without TNBS but saline enema was also included in the study. After 3 wk of treatment, the animals were assessed for colonal inflammatory and ulcerative responses with respect to mortality, frequency of diarrhea, histology and myeloperoxidase activity (MPO).RESULTS: The therapeutic effect of CTG on ulcerative colitis (UC) was better than DX. CTG effectively inhibited the activity of granulocytes, macrophages and monocytes in a dosedependent manner. Also it reduced MPO and formation of inflammation in colonic mucosal tissue. Furthermore, administration of CTG significantly prevented body mass loss and death, and decreased frequency of diarrhea in UC rats, when compared with the model control group rats.CONCLUSION: CTG would prove to be an ideal drug for chronic UC, and is warranted to be studied further.

Influence of Shenqing Recipe on Morphology and Quantity of Colonic Interstitial Cells of Cajal in Trinitrobenzene Sulfonic Acid Induced Rat Colitis

Objective To observe the influence of Shenqing Recipe (SQR),a kind of Traditional Chinese Medicine,on the morphology and quantity of colonic interstitial cells of Cajal (ICC) in trinitrobenzene sulfonic acid (TNBS)-induced rat colitis,and to investigate the possible mechanism of SQR in regulating intestinal dynamics.Methods Sixty rats were randomly divided into normal control,model Ⅰ,model Ⅱ,mesalazine,and high-dose,and low-dose SQR groups with 10 rats in each group.TNBS (10 mg) dissolved in 50% ethanol was instilled into the lumen of the rat colon of the latter five groups to induce colitis.On the 4th day after administration of TNBS,each treatment group was administered one of the following formulations by enteroclysis gavage once a day for 7 days:600 mg·kg-1·d-1 mesalazine,2.4 g·kg-1·d-1 SQR,and 1.2 g·kg-1·d-1 SQR.Model Ⅱ rats received normal saline solution.After 7 days colonic samples were collected.While the colonic samples of model Ⅰ group were collected on the 3rd day after TNBS administered.Ultrastructure of ICC in the damaged colonic tissues was observed with transmission electron microscope.Expression of c-kit protein in colonic tissue was determined by immunohistochemical staining and Western blot.Results The ultrastructure of colonic ICC in the rat model of TNBS-induced colitis showed a severe injury,and administration of SQR or mesalazine reduced the severity of injury.Similarly,the expression of c-kit protein of TNBS-induced colitis rat model was significantly decreased compared with the normal control group (P<0.05).Treatment with SQR or mesalazine significantly increased the expression of c-kit protein compared with the administration of control formulations (P<0.05),especially the high-dose SQR group.Conclusion SQR could alleviate and repair the injured ICC,and improve its quantity,which might be involved in regulating intestinal motility.

Removal of 5-Amino-2-chlorotoluene-4-sulfonic and Chlorhydric Acids from Wastewater by Weakly Basic Resin

This research deals with an investigation of the adsorption of two acids, namely, 5-amino- 2-chlorotoluene-4-sulfonic and chlorhydric acids from their solution onto weakly basic resin. The screening of res-ins, kinetics, and isotherm were studied. The results indicate that the D301R is more appropriate for the removal of acids from solution. The adsorption of acids obeys Langmuir isotherm and the first-order kinetics model. Sorptive affinity of the two acids on D301R was found to be in the order of 5-amino-2-chlorotoluene-4-sulfonic acid> chlorhydric acid. Thermodynamic parameters for the adsorption of acids were calculated and discussed. The maxi-mum removal of acids was observed around 97% and 76% at 25℃ for 5-amino-2-chlorotoluene-4-sulfonic acid and chlorhydric acid , respectively.

Extraction Behavior and Wastewater Treatment of Amino Sulfonic Acid with Alamine 336

p-Amino benzene sulfonic acid (PABSA) is selected as the solute with amphoteric functional group, Lewis acid and Lewis base, to be separated from its dilute solutions. An aliphatic, straight chain amine, Alamine 336, is used as the extractant, and kerosene, 1-octanol, chloroform, butyl acetate and benzene as the diluent. The effects of pH value of solution, extractant concentration, salt and types of diluent on the distribution coefficient, D, are studied. There is a peak of D value with pH value of solution, the polar diluents are favorable for extracting PABSA, and the salt in aqueous phase reduces values of D apparently. The extraction equilibrium is described using the mass action law, and the calculated data according to the proposed model agree with the experimental data well. Further, the extraction behavior for other amino benzene sulfonic acids, 1-amino-8-naphtol-3,6-disulfonic acid (H acid) and 4,4′-diaminostilbene-2,2′-disulfonic acid (DSD acid), is investigated in a wide pH value region. Finally. H acid and DSD acid are successfully removed from wastewater by the extraction with Alamine 336.

Effect of magnetic field on property and structure of polyaniline doped with multiple sulfonic acids

Polyaniline(PAn)doped with multiple sulfonic acid system of dodecylbenzenesulfonic acid(DBSA)and sulfosalicylic acid(SSA)was synthesized by emulsion polymerization using ammonium persulfate(APS)as an oxidizing agent in the presence and the absence of a constant magnetic field(MF)of 0.8 T.The structure and properties of the PAn were characterized by X-ray diffractometer(XRD),thermogravimetric apparatus(TGA),FT-IR spectroscope(FT-IR)and four probe digital multimeter.The results indicate that,when the molar ratio of DBSA to SSA is 1/3,that of dopant to An is 3/2,that of APS to An is 4/5 in the synthesizing media,and the doping time is 3 h,the conductivity of the PAn synthesized in the presence of the MF of 0.8 T reaches 5.88 S/cm,which is higher than that of the PAn synthesized in the absence of the MF.The thermal stability,the crystallinity and the doping degree of the PAn synthesized in the presence of the MF are also improved.MF not only enhances the conductivity,but also reduces the doping time,the dosage of the dopant and the oxidizing agent when the conductivity reaches the maximum.

UV- VIS SPECTRA OF POLYANILINE DOPED WITH CAMPHOR SULFONIC ACID IN DIFFERENT ORGANIC SOLVENTS

The doping reaction of polyaniline with camphor sulfonic acid (CSAH) in different organic solvents was studied by UV Vis spectroscopy. The experimental results show that the polaron band of the species was shifted to shorter wavelength when polyaniline was doped with CSAH in N methyl 2 pyrrolidione (NMP) solvent, while the red shift of polaron band was observed when it was in N, N dimethylformamide (DMF). It indicates that the influence of different processing solvents on the doping property of polyaniline is greatly different. N methyl 2 pyrrolidione is a good solvent for polyaniline, polyaniline chain is unfolded in it. The interaction of NMP with CSAH is so strong that the resulting product is apt to dedoping, while the solubility of polyaniline in DMF is relatively low and polyaniline chain is in partly folded state. Thus the doping reaction is kinetically disadvantageous but thermodynamically advantageous.

Sterically Stabilized Poly(3, 4-ethylenedioxythiophene) Colloidal Dispersions Doped with Different Sulfonic Acids

The preparation of sterically stabilized poly（3, 4-ethylenedioxythiophene）（PEDOT） colloidal dispersions doped with different sulfonic acids is described. Three different sulfonic acids, i.e., p-toluenesulfonic acid, β-naphthalenesulfonic acid and D-camphor-10-sulfonic acid are used, facilitating the preparation of sterically stable PEDOT colloidal particles. The influences of the dopants and concentration of polymeric stabilizer on the yields, morphologies and electrical properties of the resultant colloidal particles were investigated. The colloidal particles with the size ranging from 172 to 334 nm have been obtained in good yields. The compressed pellet conductivity was as high as 4.5 Scm^-1

A STUDY ON THE DEGRADATION MECHANISM OF PHOTOCROSSLINKING PRODUCTS FORMED BY CYCLIZED POLYISOPRENE-DIAZIDE SYSTEM UNDER THE INFLUENCE OF ALKYL BENZENE SULFONIC ACIDS

The degradation mechanism of photocrosslinking products formed by cyclized polyisoprene-diazide system under the influence of the different alkyl benzene sulfonic acids was studied. The effects of alkyl chain length and the concentration of alkyl benzene sulfonic acids on the rate of degradation reaction were discussed. It was found that in the initial stage of degradation, the cyclicity ratio and the average fused ring number did not change considerably, but the percentage of uncyclized parts content varied significantly. The suitable mechanism was supposed.

SYNTHESIS, STRUCTURE AND PROPERTIES OF INTERPENETRATING SULFONIC ACID RESINS WITH HIGH CAPACITY

Two series of interpenetrating sulfonic acid resins (ISAR), 10×n and n×10, were prepared by means of the wet method, and the physicochemical, thermodynamic and kinetic properties of the ISAR were measured. The results show: 10×n resins exhibit better properties than n×10 ones, mainly in higher apparent degree of crosslinking and larger conformational entropy effect, among which, 10×1 resin exhibits the best thermodynamic and kinetic properties. In the DTA graphs of n×10 resins, there are two T_g and two T_(ox), but in those of 10×n, only one T_g and one T_(ox). This result well supports the conclusion that 10×n resins have much better interpenetrating structural aspects.

Synthesis and Characterization of the Terpolymer of Itaconic Acid with Acrylamide and 2-Acrylamido-2-methylpropanesulfonic Acid

The terpolymer of itaconic acid, acrylamide and 2-acrylamido-2-methyl-1-propane sulfonic acid was synthesized through the free-radical polymerization. The IR spectra confirmed that there was no olefinic band, while the TGA results revealed that the terpolymer was of high thermal stability.

MICELLIZATION STUDIES OF DODECYL BENZENESULFONIC ACID AND ITS INTERACTION WITH POLYVINYLPYRROLIDONE

Dodecyl benzenesulfonic acid(DBSA)surfactant was used in the present study to find the effect of concentrationon its electrical conductance in solution from 293-323 K above and below the critical micelle concentration(CMC).Themicellization parameters i.e.degree of counter ion binding(β),aggregation number(n)and number of counter ion micelle(m)were measured.The interaction of DBSA with polyvinylpyrrolidone(PVP)was also studied at 293 K throughconductance and surface tension measure ments.A number of important parameters i.e.critical aggregation concentration(CAC),Gibb's free energy(△G)and binding ratio(R)were determined and the effect of NaCl on the CAC and polymersaturation point(PSP)was also investigated.

Effect of Dodecylbenzene Sulfonic Acid Used as Additive on Residue Hydrotreating

The effect of additive—dodecylbenzene sulfonic acid(DBSA)—on residue hydrotreating was studied in the au toclave. The results showed that the additive improved stabilization of the colloid system of residue, which could delay th aggregation and coke formation from asphaltenes on the catalyst, and make heavy components transformed into light oi The residue conversion in the presence of this additive increased by 1.94%, and the yield of light oil increased by 1.53%when the reaction time was 90 min. The surface properties of the catalyst in the presence of this additive were better tha that of the blank test within a very short time(30 min) and deteriorated rapidly after a longer reaction time due to highe conversion and coke deposition. Compared with the blank test, the case using the said additive had shown that the structur of hydrotreated asphaltene units was smaller and the condensation degrees were higher. The test results indicated that th additive could improve the hydrotreating reactivity of residue via permeation and depolymerization, the heavier componen could be transformed into light oil more easily, and the light oil yield and residue conversion were higher for the case usin the said additive in residue hydrotreating process.

PREPARATION,CHARACTERIZATION AND ELECTROCHEMICAL PROPERTIES OF POLYPYRROLE-POLYSTYRENE SULFONIC ACID COMPOSITE FILM

Polypyrrole-polystyrene sulfonic acid(PPy-PSSA)composite films have been electrosynthesized in an aqueoussolution of PSSA.The electro-active films exhibit cation exchange during the redox process.Infrared,Raman and energy-dispersive spectroscopic results demonstrated that the polyanion of PSS^- is co-deposited into the PPy matrix and couldn't bestripped fiom the film extensively by dedoping.The doping level together with dipolaron content of the PPy-PSSAcomposite film increases during electrochemical polymerization process.SEM images revealed that the composite film hassmooth and compact morphology and AFM pictures suggested that PPy chains are possibly grown perpendicular to theelectrode surface.TGA tests indicated that the composite films has much better thermal stability than that of pure PPy.Furthermore,electrochemical studies showed that the relaxation process at certain holding potential has great effect on theshape of the cyclic voltammetric curves of PPy-PSSA composite film.The composite film exhibits cation and anionexchange during the redox process after undergoing the relaxation step.It is more difficult for divalent anion to enter thepolymer matrix than a univalent ion,and a large cation such as(CH_3CH_2CH_2CH_2)_4N^+ cannot be involved in the ionexchange process.

Preconcentration of Rare Earth Elements with 8-Hydroxyquinoline-5-sulfonic Acid Chelated Cellulose Filter Prior to Determination by Inductively Coupled Plasma Atomic Emission Spectrometry

Hydroxyquinoline 5 sulfonic acid, covalently bound to filter cellulose, was used for preconcentrating trace rare earth element(REE) ions from complex matrices and matrix separation, respectively. Multi REE ions were preconcentrated on the column filled with 8 hydroxyquinoline 5 sulfonic acid cellulose filter and analysed by ICP AES after being eluted with dilute HNO 3. In the given pH range, alkali and alkaline earth metal ions can be separated as matrix elements; a high concentration factor is obtained and the eluates can be measured without interference. The usefulness of the method is shown by the control analyses of standard reference materials. [WT5FZ]