Structural optimization and performance trade-off strategies for semi-crystalline sulfonated poly(arylene ether ketone) membranes in high-concentration direct methanol fuel cells

Direct methanol fuel cells(DMFCs) have attracted extensive attention as promising next-generation energy conversion devices. However, commercialized proton exchange membranes(PEMs) hardly fulfill the demand of methanol tolerance for DMFCs employing high-concentration methanol solutions.Herein, we report a series of semi-crystalline poly(arylene ether ketone) PEMs with ultra-densely sulfonic-acid-functionalized pendants linked by flexible alkyl chains, namely, SL-SPEK-x(where x represents the molar ratio of the novel monomer containing multiple phenyl side chain to the bisfluoride monomers). The delicate structural design rendered SL-SPEK-x membranes with high crystallinity and well-defined nanoscale phase separation between hydrophilic and hydrophobic phases. The reinforcement from poly(ether ketone) crystals enabled membranes with inhibited dimensional variation and methanol penetration. Furthermore, microphase separation significantly enhanced proton conductivity. The SL-SPEK-12.5 membrane achieved the optimum trade-off between proton conductivity(0.182 S cm^(-1), 80 ℃), water swelling(13.6%, 80 ℃), and methanol permeability(1.6 × 10^(-7)cm~2 s^(-1)). The DMFC assembled by the SL-SPEK-12.5 membrane operated smoothly with a 10 M methanol solution, outputting a maximum power density of 158.3 mW cm^(-2), nearly twice that of Nafion 117(94.2 mW cm^(-2)). Overall, the novel structural optimization strategy provides the possibility of PEMs surviving in high-concentration methanol solutions, thus facilitating the miniaturization and portability of DMFC devices.

Rheological and physicomechanical properties of rod milling sand-based cemented paste backfill modified by sulfonated naphthalene formaldehyde condensate

Rod milling sand(RMS)—a coarse sand aggregate—was recycled for cemented paste backfill(CPB)for the underground mined area at the Jinchuan nickel deposit,named rod milling sand-based cemented paste backfill(RCPB).The adverse effects of coarse particles on the transportation of CPB slurry through pipelines to underground stopes resulting in weakening of the stability of the backfill system are well known.Therefore,sulfonated naphthalene formaldehyde(SNF)condensate was used for the performance improvement of RCPB.The synergistic effect of solid content(SC),lime-to-sand ratio,and SNF dosage on the rheological and physicomechanical properties,including slump,yield stress,bleeding rate,uniaxial compressive strength(UCS),as well as mechanism analysis of RCPB,have been explored.The results indicate that the effect of SNF on RCPB performance is related to the SNF dosage,lime-to-sand ratio,and SC.The slump of fresh RCPB with 0.1wt%-0.5wt%SNF increased by 2.6%-26.2%,whereas the yield stress reduced by 4.1%-50.3%,indicating better workability and improved cohesiveness of the mix.The bleeding rate of fresh RCPB decreased first and then rose with the increase of SNF dosage,and the peak decrease was 67.67%.UCS of RCPB first increased and then decreased with the increase of SNF dosage.At the optimal SNF addition ratio of 0.3wt%,the UCS of RCPB curing for 7,14 and,28 d ages increased by 31.5%,28.4%,and 29.5%,respectively.The beneficial effects of SNF in enhancing the early UCS of RCPB have been corroborated.However,the later UCS increases at a slower rate.The research findings may guide the design and preparation of RCPB with adequate performance for practical applications.

Comprehensive analysis of sodium polystyrene sulfonate-induced colitis:A systematic review

BACKGROUND Sodium polystyrene sulfonate(SPS)is commonly prescribed for the management of hyperkalemia,a critical electrolyte imbalance contributing to over 800000 annual visits to emergency departments.AIM To conduct a systematic review of documented cases of SPS-induced colitis and assess its associated prognosis.METHODS Following the PRISMA-P guidelines,our study employed Medical Subject Headings and Health Sciences Descriptors,skillfully combined using Boolean operators,to conduct comprehensive searches across various electronic databases,including Scopus,Web of Science,MEDLINE(PubMed),BIREME(Biblioteca Regional de Medicina),LILACS(Latin American and Caribbean Health Sciences Literature),SciELO(Scientific Electronic Library Online),Embase,and Opengray.eu.Language criteria were confined to English,Spanish,and Portuguese,with no limitations on the publication date.Additionally,we manually scrutinized the reference lists of retrieved studies.To present our findings,we utilized simple descriptive analysis.RESULTS Our search strategy yielded a total of 442 references.After rigorous evaluation,we included 51 references,encompassing 59 documented cases of colitis.Predominant clinical presentations included abdominal pain,observed in 35(60.3%)cases,and bloating,reported in 18(31%)cases.The most frequently affected sites of inflammation were the cecum,rectum,and small intestine,accounting for 31%,25.8%,and 22.4%of cases,respectively.Colonoscopy findings were described in 28(48.2%)cases,and 29(50%)of patients required surgical intervention.Among the subset of patients for whom outcome data was available,39(67.2%)experienced favorable outcomes,while 12(20.6%)unfortunately succumbed to the condition.The mean time required for resolution was 36.7 d,with a range spanning from 1 to 120 d.CONCLUSION SPS demonstrates the capacity to effectively lower serum potassium levels within 24 h.However,this benefit is not without the risk of bowel injury.Our study highlights the absence of high-quality data pertaining to the incidence of adverse events associated with SPS usage,making it challenging to determine whether the potential risks outweigh the benefits.However,a significant mortality rate related to SPS-induced colitis was noted.Future investigations should prioritize randomized controlled trials with a sufficiently large patient cohort to ascertain the true utility and safety profile of this medication.

Effect of Temperature and Sulfonation Extent on Fluorescence Emission of Sulfonated Polystyrene

研究不同磺化度的磺化聚苯乙烯（ＳＰＳ）的荧光特性，ＳＰＳ的荧光光谱在２８５，３３５和３８０ｎｍ的发射峰分别对应于单体、激基缔合物及类激基缔合物的荧光发射．基态磺化苯乙烯基团形成的二聚体在光激发下产生类激基缔合物，类激基缔合物荧光随着ＳＰＳ磺化度的增加而增强．稀溶液中ＳＰＳ激基缔合物形的活化能和焓随着ＳＰＳ磺化度的增加而增大。

Determination of genotoxic alkyl methane sulfonates and alkyl paratoluene sulfonates in lamivudine using hyphenated techniques

Two highly sensitive methods for the determination of genotoxic alkyl methane sulfonates (AMSs) and alkyl paratoluene sulfonates (APTSs) in lamivudine using hyphenated techniques have been presented. AMSs were determined by GC-MS method using GSBPINOWAX (30 m 0.25 mm 0.25 mm) column. Temperature program was set by maintaining at 100 1C initially for 3 min, then rised to 220 1C at the rate of 15 1C/min and maintained at 220 1C for 16 min. N,N-dimethyl formamide was used as diluent. APTSs were determined by LC-MS using Zorbax, Rx C8, 250 mm 4.6 mm, 5 mm column as stationary phase. 0.01 M ammonium acetate is used as buffer. The mixture of buffer and methanol in 75:25 (v/v) ratio was used as mobile phase A and mixture of buffer and methanol in 5:95 (v/v) ratio was used as mobile phase B. The gradient program (T/%B) was set as 0/28, 16/50, 17/100, 23/100, 27/28 and 40/28. Both the methods were validated as per International Conference on Harmonization guidelines. Limit of quantitation was found 1.5 mg/mL for AMSs and was in the range of 1.0-1.5 mg/mL for APTSs.

Effect of temperature on the sorption and desorption of perfluorooctane sulfonate on humic acid

Sorption and desorption of perfluorooctane sulfonate （PFOS） on humic acid at different temperatures were studied. It was found that the sorption process could be modeled with power kinetic equation very well, suggesting that diflusion predominated the sorption of PFOS on the humic acid. The sorption capacity was doubled when the temperature increased from 5 to 35°C, and thermodynamics parameters △G0 was calculated to be –7.11 to –5.04 kJ/mol, △H0 was 14.2 kJ/mol, and △S 0 was 69.5 J/（mol·K）, indicating that the sorption was a spontaneous, endothermic, and entropy driven process. Desorption hysteresis occurred at all studied temperatures which suggested that humic acid may be an important sink of PFOS in the environment.

Histological changes of the testis and epididymis in adult rats as a result of Leydig cell destruction after ethane dimethane sulfonate treatment： a morphometric study

Aim： To quantitatively study the histological changes of the testis and epididymis as a result of a drastic reduction of testosterone secretion. Methods： Fourteen adult Sprague-Dawley rats were injected intraperitoneally with ethane dimethane sulfonate （EDS, 75 mg/kg） and the same number of animals were injected with normal saline as a control. At days 7 and 12 （after treatment）, respectively, half of the animals from each group were killed. The testes and epididymides were removed and tissue blocks embedded in methacrylate resin. The cell number per testis was estimated using the stereological optical disector and some other parameters were obtained using other morphometric methods. Results： The EDS treatment resulted in an almost complete elimination of Leydig cells but had no effect on the numbers of Sertoli cells per testis. At day 7 after EDS treatment, many elongated spermatids were retained in the seminiferous epithelium and many round spermatids could be seen in the epididymal ducts. At day 12, a looser arrangement of spermatids and spermatocytes became evident, with apparent narrow empty spaces being formed between germ cells in an approximately radial direction towards the tubule lumen; the numbers （per testis） of non-type B spermatogonia and spermatocytes were similar to controls, whereas that of type B spermatogonia increased by 59%, and that of early round, elongating and late elongated spermatids decreased by 37%, 72% and 52%, respectively. Conclusion： The primary spermatogenic lesions following EDS administration were （i） spermiation failure and （ii） detachment of spermatids and spermatocytes associated with impairment in spermiogenesis and meiosis.

Water solubility enhancements of PAHs by sodium castor oil sulfonate microemulsions

Water solubility enhancements of naphthalene(Naph), phenantherene(Phen) and pyrene(Py) in sodium castor oil sulfonate(SCOS) microemulsions were evaluated. The apparent solubilities of PAHs are linearly proportional to the concentrations of SCOS microemulsion, and the enhancement extent by SCOS solutions is greater than that by ordinary surfactants on the basis of weight solubilization ratio(WSR). The log K em values of Naph, Phen, and Py are 3 13, 4 44 and 5 01 respectively, which are about the same as the log K ow values. At 5000 mg/L of SCOS conccentration, the apparent solubilities are 8 80, 121, and 674 times as the intrinsic solubilities for Naph, Phen, and Py. The effects of inorganic ions and temperature on the solubilization of solutes are also investigated. The solubilization is improved with a moderate addition of Ca 2+ , Na +, NH + 4 and the mixture of Na +, K +, Ca 2+ , Mg 2+ and NH + 4. WSR values are enhanced by 22 0% for Naph, 23 4% for Phen, and 24 6% for Py with temperature increasing by 5℃. The results indicated that SCOS microemulsions improve the performance of the surfactant enhanced remediation(SER) of soil, by increasing solubilities of organic pollutants and reducing the level of surfactant pollution and remediation expenses.

Changes of c-fos and c-jun mRNA Expression in Angiotensin Ⅱ-induced Cardiomyocyte Hypertrophy and Effects of Sodium Tanshinone ⅡA Sulfonate

The changes of proto-oncogene c-fos and c-jun mRNA expression in angiotensin Ⅱ （AngⅡ）-induced hypertrophy and effects of sodium tanshinone ⅡA sulfonate （STS） in the primary culture of neonatal rat cardiomyocytes were investigated. Twelve neonatal clean grade Wistar rats were selected. The cardiomyocytes were isolated, cultured and divided according to different treatments in the medium. The cardiomyocyte size was determined by phase contrast microscope, and the rate of protein synthesis was measured by [3H]-Leucine incorporation. The c-fos and c-jun mRNA expression in cardiomyocytes was detected by reverse transcription polymerase chain reaction （RT-PCR）. It was found after cardiomyocytes were treated with AngⅡ for 30 min, the c-fos and c-jun mRNA expression in cardiomyocytes was increased significantly （P〈0.01）. After treatment with AngⅡ for 24 h, the rate of protein synthesis in AngⅡ group was significantly increased as compared with control group （P〈0.01）. After treatment with AngⅡ for 7 days, the size of cardiomyocytes in AngⅡ group was increased obviously as compared with control group （P〈0.05）. After pretreatment with STS or Valsartan before AngⅡ treatment, both of them could inhibit the above effects of AngⅡ （P〈0.05 or P〈0.01）. It was suggested that STS could ameliorate AngⅡ-induced cardiomyocyte hy- pertrophy by inhibiting c-fos and c-jun mRNA expression and reducing protein synthesis rate of cardiomyocytes.

Treatment of drilling wastewater from a sulfonated mud system

Treatment of drilling wastewater from a sulfonated drilling mud system in the Shengli Oilfield, East China, was studied. The wastewater was deeply treated by a chemical coagulationcentrifugal separation-ozone catalytic oxidation combined process. The factors （i.e. pH value, chemical dosage, reaction time, etc.） influencing the treatment effect were investigated, and pH = 7 was determined as optimal for the coagulation; polymeric aluminum chloride （PAC） was selected as the optimal coagulant with a dosage of 18 g/L; cationic polyacrylamide （CPAM） with molecular weight of 8 million was selected as the optimal coagulant aid with an optimum dosage of 8 mg/L; and the optimal condition of catalytic ozonation was found to be a pH of 12 and an oxidation time of 40 min. The results showed that the combined treatment process was effective. The oil content and suspended solids content of the effluent reached the first class discharge standard according to China＇s standard GB 8978-1996 （Integrated Wastewater Discharge Standard） and the chemical oxygen demand （COD） decreased to 195 mg/L from 2.34×10^4 mg/L after coagulation process and ozone oxidation at pH = 12 for 40 min.

Sulfonated carbon catalyzed oxidation of aldehydes to carboxylic acids by hydrogen peroxide

Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H2O2 as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.

Quinone-mediated decolorization of sulfonated azo dyes by cells and cell extracts from Sphingomonas xenophaga

The effects of various quinone compounds on the decolorization rates of sulfonated azo dyes by Sphingomonas xenophaga QYY were investigated. The results showed that anthraquinone-2-sulfonate （AQS） was the most effective redox mediator and AQS reduction was the rate-limited step of AQS-mediated decolorization of sulfonated azo dyes. Based on AQS biological toxicity tests, it was assumed that AQS might enter the cells and kill them. In the cytoplasmic extracts from strain QYY, AQS more effectively increased decolorization rates of sulfonated azo dyes than other quinone compounds. In addition, we found a NADH/FMN-dependent AQS reductase using nondenaturing polyacrylamide gel electrophoresis （Native-PAGE）.

Determination of petroleum sulfonates in crude oil by column-switching anion-exchange chromatography

A column-switching anion-exchange chromatography method was described for the separation and determination of petroleum monosulfonates （PMS） and petroleum disulfonates （PDS） in crude oil that was simply diluted with the dichloromethane/methanol （60/40）. The high performance liquid chromatography （HPLC） system consisted of a clean-up column and an analytical column, which were connected with two six-port switching valves. Detection of petroleum sulfonates was available and repeatable. This method has been successfully applied to determine PMS and PDS in crude oil samples from Shengli oil field.

New Spirostanol Sulfonate from the Rhizomes of Helleborus thibetanus(Ranunculaceae)

A new spirostanol sulfonate, spirost-5,25（27）-dien-1β,3β-diol 1-sulfonate（1）, was isolated from the rhizomes of Helleborus thibetanus（Ranunculaceae）, and the structure was identified on the basis of a detailed spectroscopic analyses, including 2D NMR spectrometry, IR and HRESI-MS.

Synthesis of Poly(phthalazinone ether ketone) Containing Sodium Sulfonate Groups via Direct Polymerization

Dihydro-4-(4-hydroxyphenyl)(2H)phthalazin-1-one(DHPZ) was sulfonated in con- centrated sulfuric acid. Poly(phthalazinone ether ketone) containing pendant sodium sulfonate group was synthesized from sulfonated and pure 1,2-dihydro-4-(4-hydroxyphenyl)(2H)phthalazin- 1-one, and 4,4-difluorodiphenylketone. The sulfonated monomer and sulfonated polymer were characterized with FT-IR and 1H-NMR.

Protective Effect and Mechanism of Sodium Tanshinone ⅡA Sulfonate on Microcirculatory Disturbance of Small Intestine in Rats with Sepsis

To explore the protective effect of sodium tanshinone ⅡA sulfonate（STS） on microcirculatory disturbance of small intestine in rats with sepsis,and the possible mechanism,a rat model of sepsis was induced by cecal ligation and puncture（CLP）.Rats were randomly divided into 3 groups：sham operated group（S）,sepsis group（CLP） and STS treatment group（STS）.STS（1 mg/kg） was slowly injected through the right external jugular vein after CLP.The histopathologic changes in the intestinal tissue and changes of mesenteric microcirculation were observed.The levels of tumor necrosis factor-α（TNF-α） in the intestinal tissue were determined by using enzyme-linked immunoabsorbent assay（ELISA）.The expression of intercellular adhesion molecule-1（ICAM-1） in the intestinal tissue was detected by using immunohistochemisty and Western blot,that of nuclear factor κB（NF-κB） and tissue factor（TF） by using Western blot,and the levels of NF-κB mRNA expression by using RT-PCR respectively.The microcirculatory disturbance of the intestine was aggravated after CLP.The injury of the intestinal tissues was obviously aggravated in CLP group as compared with S group.The expression levels of NF-κB p65,ICAM-1,TF and TNF-α were upregulaed after CLP（P0.01）.STS post-treatment could ameliorate the microcirculatory disturbance,attenuate the injury of the intestinal tissues induced by CLP,and decrease the levels of NF-κB,ICAM-1,TF and TNF-α（P0.01）.It is suggested that STS can ameliorate the microcirculatory disturbance of the small intestine in rats with sepsis,and the mechanism may be associated with the inhibition of inflammatory responses and amelioration of coagulation abnormality.

STUDY ON LIGHTLY SULFONATED SYNDIOTACTIC POLYSTYRENE IONOMERS

Sulfonated syndiotactic polystyrene ionomers (SsPS) with 1.8 mol% degree of sulfonation have been studied. WAXD shows that the crystallinity of SsPS ionomers was decreased with increasing diameter size of the counter ions and sPS > SsPS-H > SsPS-K > SsPS-Zn. Moreover, SsPS ionomers only have alpha crystal form, while original sPS has two crystal forms: alpha and beta crystal form. TGA shows that the thermal stability of SsPS ionomers is higher than that of the original sPS and SsPS-Zn > SsPS-K > SsPS-H. DSC shows that all the glass transition temperatures (T-g) of SsPS ionomers are higher than that of the neat sPS and SsPS-Zn > SsPS-Na > SsPS-K > SsPS-H. However, the melting temperature (T-m) and crystallization peak temperature (T-p) of SsPS ionomers are lower and SsPS-H > SsPS-Zn > SsPS-K > SsPS-Na, while the crystallinity (X-c) of SsPS-Zn is the lowest. Nonisothermal crystallization kinetics shows that the Avrami index of sPS and SsPS-H are both about 4, suggesting the nucleation growth of SsPS-H with lower degree of sulfonation still keeps its three-dimension form. FTIR spectra of SsPS ionomers show a splitting absorption band for asymmetric stretching vibration of sulfonation group. The CH in-plane bending vibration of benzene ring shifted to higher wavenumber and the symmetric stretching vibration of sulfonation group changed slightly with different counter ion neutralized SsPS ionomers.

Kinetic and thermodynamic studies of the esterification of acidified oil catalyzed by sulfonated cation exchange resin

This study describes the kinetics and thermodynamics of the esterification of acidified oil with methanol catalyzed by sulfonated cation exchange resins（SCER）. The effects of the mass ratio of methanol to acidified oil,reaction temperature,and catalyst loading were studied to optimize the conditions for maximum conversion of free fatty acids（FFAs）. The results showed that the optimal conversion rate of FFAs was 91.87% at the mass ratio of methanol to acidified oil of 2.5：1.0,reaction temperature of 65.0 °C,catalyst loading of 5.0 g and reaction time of 8.0 h. The external and internal mass transfer resistances were negligible based on the experimental results and a pseudo-homogeneous kinetic model was proposed for the esterification. The activation energy and thermodynamic parameters including G,S and H were determined. The conversion rates of FFAs obtained from the established model were in good agreement with the experimental data.

Synthesis and Characterization of Ion-exchange Sulfonated Poly (ether sulfone)

N,N＇-Bis（3-hydroxyphenyl）-1,8,4,5-naphthalenetetracarboxylic bisimide was prepared from the reaction of 1,8,4,5-naphthalenetetrcarboxylic acid dianhydride and 2-aminophenol in N, N-dimethylformamide. Polymerization of this bisimide with 4,4＇-difluorodiphenylsulfone and disodium 3,3＇-disulfonate4,4＇-difluorodiphenylsulfone gave ion-exchange sulfonated poly（ether sulfone）. The structure of the title compound was characterized with H-NMR and its polymer was characterized with FT-IR.

SYNTHESIS AND PROPERTIES OF SULFONATED POLY(ARYLENE ETHER) CONTAINING TRIPHENYL METHANE MOIETIES FROM ISOCYNATE MASKED BISPHENOL

A novel sulfonated poly（arylene ether） containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N＇-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton＇s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly （MEA） prepared with the asmade film （706 EW, 100 μm dry thickness） shows better cell performance than Nation 115-MEA in the whole current density range.