Ionic liquid-assisted preparation of hydroxyapatite and its catalytic performance for decarboxylation of itaconic acid

The synthesis of methacrylic acid from biomass-derived itaconic acid is a green route,for it can get rid of the dependence on fossil resource.In order to solve the problems on this route such as use of a preciousmetal catalyst and a corrosive homogeneous alkali,we prepared a series of hydroxyapatite catalysts by an ionic liquid-assisted hydrothermal method and evaluated their catalytic performance.The results showed that the ionic liquid[Bmim]BF_(4) can affect the crystal growth of hydroxyapatite,provide fluoride ion for fluorination of hydroxyapatite,and adjust the surface acidity and basicity,morphology,textural properties,crystallinity,and composition of hydroxyapatite.The[Bmim]BF4 dosage and hydrothermal temperature can affect the fluoride ion concentration in the hydrothermal system,thus changing the degree of fluoridation of hydroxyapatite.High fluoride-ion concentration can lead to the formation of CaF_(2) and thus significantly decrease the catalytic performance of hydroxyapatite.The hydrothermal time mainly affects the growth of hydroxyapatite crystals on the c axis,leading to different catalytic performance.The suitable conditions for the preparation of this fluoridized hydroxyapatite are as follows:a mass ratio of[Bmim]BF4 to calcium salt=0.2:1,a hydrothermal time of 12 h,and a hydrothermal temperature of 130℃.A maximal methacrylic acid yield of 54.7%was obtained using the fluoridized hydroxyapatite under relatively mild reaction conditions(250℃ and 2 MPa of N_(2))in the absence of a precious-metal catalyst and a corrosive homogeneous alkali.

Transforming liquid flow fuel cells to controllable reactors for highlyefficient oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid at low temperature

Highly-efficient oxidation of 5-hydroxymethylfurtural(HMF) to 2,5-furandicarboxylic acid(FDCA) at low temperature with air as the oxidant is still challenging.Herein,inspired by the respirato ry electron transport chain(ETC) of living cells mediated by electron carriers,we constructed artificial ETCs and transformed liquid flow fuel cells(LFFCs) to flexible reactors for efficient oxidation of HMF to produce FDCA under mild conditions.This LFFC reactor employed an electrodeposition modified nickel foam as an anode to promote HMF oxidation and(VO_(2))_(2)SO_(4) as a cathode electron carrier to facilitate the electron transfer to air.The reaction rate could be easily controlled by selecting the anode catalyst,adjusting the external loading and changing the cathodic electron carrier or oxidants.A maximal power density of 44.9 mW cm^(-2) at room temperature was achieved,while for FDCA production,short-circuit condition was preferred to achieve quick transfer of electrons.For a single batch operation with 0.1 M initial HMF,FDCA yield reached 97.1%.By fed-batch operation,FDCA concentration reached 144.5 g L^(-1) with a total yield of 96%.Ni^(2+)/Ni^(3+) redox couple was the active species mediating the electron transfer,while both experimental and DFT calculation results indicated that HMFCA pathway was the preferred reaction mechanism.

Design and manufacture of emulsion liquid membrane based on various amine extractants for separation and extraction of succinic acid from fermentation broth

The aim of this study was to design a new emulsion liquid membrane(ELM)system for the separation of succinic acid from aqueous solutions.The concentration of succinic acid varied from 20 to 60 mmol·L^(-1).The prepared ELM system includes tributylamine(TBA)as a carrier,commercial kerosene as a solvent,Span 80 as a surfactant,and Na2CO3as a stripping agent.In order to control the membrane swelling,different values of cyclohexanone were added to the membrane phase.The effect of various empirical variables on the extraction of the succinic acid such as acid concentration in the feed solution,initial feed concentration,carrier concentration,the stirring speed of the extraction,Na2CO3,surfactant,and cyclohexanone concentrations,and treat ratio in the ELM system.The best result was obtained when TBA was used as the carrier.The final acid extraction efficiency was independent of pH variations of the aqueous feed solution.The extraction of succinic acid solution with a concentration of 40 mmol·L^(-1)was improved by increasing the treat ratio 1:7-1:3,stripping phase concentration 0.5-1.5 mol·L^(-1),stirring speed 300-500 r·min^(-1)and cyclohexanone concentration in the membrane phase 1.2-1.6 mol·L^(-1).No considerable effect on the extraction rate was observed for the carrier concentration in the membrane phase.But,the surfactant concentration in the feed phase showed a dual effect on the extraction efficiency.

Encapsulation of ionic liquid, phosphotungstic acid inside the nanocages of MIL-101(Cr): Effective and reusable catalyst for efficient solvent-free oxidative desulfurization from fuel oil

Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performance.Successful encapsulation of phosphotungstic acid(HPW)and ionic liquid(BMImBr)inside the mesoporous cages of MIL-101(Cr)was accomplished through a combination of“bottle around ship”and“ship in bottle”methods.The obtained BMImPW@MIL-101(Cr)composite was characterized by XRD,FTIR,BET,SEM,XPS and ICP methods.Results indicated that the BMImPW@MIL-101(Cr)composites with PW^(3−) loading of 23.1–50.7 wt%were obtained,demonstrating that the“bottle around ship”method is beneficial to make full use of nanocages of MIL-101(Cr)to obtain expected high loading of active PW^(3−) .The BMImPW@MIL-101(Cr)exhibits excellent reusability with no evidence of leaching of active PW^(3−) and BMIm^(+),and well-preserved structure after successive cycles of regeneration and reuse.The significantly improved stability of BMImPW@MIL-101(Cr)as compared to HPW@MIL-101(Cr)is possibly because the leaching of the active PW^(3−) −sites can be greatly suppressed by forming large size of BMImPW owing to introduction of BMIm^(+)cation.The BMImPW@MIL-101(Cr)exhibited excellent catalytic activity for solvent free oxidative desulfurization of refractory sulfides.The enhanced oxidative desulfurization activity as compared to HPW@MIL-101(Cr)can be explained by the intimate contact of sulfides with active PW^(3−) sites owing the strong attraction of BMIm^(+)cation with the sulfides.

Determination of Salvianolic Acid B in Yiqi Huayu Prescription by HPLC

[Objectives]To determine the content of salvianolic acid B in Yiqi Huayu Prescription by HPLC.[Methods]The chromatographic column was ZORBAX Eclipse Plus C 18(4.6 nm×250 nm,5μm);the mobile phase was acetonitrile-0.1%phosphoric acid(21:79),the detection wavelength was 286 nm,the column temperature was 30℃,and the flow rate was 1.0 mL/min.A method for determination of salvianolic acid B in Yiqi Huayu Prescription was established.[Results]The linear relationship of salvianolic acid B was good in the range of 0.0214-0.4064 mg/mL.The regression equation was Y=5995.98984 X-0.07332,r=0.9999.The average recovery rate was 98.88%(RSD=1.6%).[Conclusions]The method is reliable,accurate and specific,and can be used for the determination of salvianolic acid B in Yiqi Huayu Prescription.

Preliminary Studies on High-performance Liquid Chro-matography Chemiluminescence Determination of theSaturated Fatty Acids(C_(16) C_(18))in Human Serum

The peroxyoxalate chemiluminescence(CL)detection of fatty acids in human se- rum combined with high-performance liquid chromatography (HPLC)is described.Some fatty acids in serum were extracted with a 1 :1(v/v)mixture of chloroform-n-heptane.2-(4-Hydrazinocarbonyl- phenyl)-4,5-diphenylimidazole (HCPI) was used as a fluorescent labelling reagent of the fatty acids. The labelling reaction was carried out at 30℃ for 1 h at pH 6.5 and the resulting reaction mixture was sudjected to HPLC. The labelled fatty acid C_(17)(P-C_(17))was used as the internal standard. The la- belled fatty acids C_(16) and C_(18) were separated within 18 min on an ODS-8OTM column (150 mm× 6 mm ID,5μm,Tosoh Japan).The calibrlation curves of fatty acids from the spiked control serum were Y_1=-0.003 7 + 0.0028X_1,r=0.994 for FA C_( 16) and Y_2=0.00 1 2 + 0.00098X_2,r=0.999 for FA C_( 18),respectively.The average recoveries of facids from the spiked contrl serum were 107.2%(n=8,RSD=4.3%)for FA C_(16) and 97.35%(n=8, RSD=4.0%)for FA C_(18),respectively.The lower detection limits of fatty acids after reaction were 12μmol per 20μl injection for FA C_(16) and 18 μmol per 20μl injection for FA C_(18),respectively(signal to noise ratio, S/N=2).The HPLC/CL method was applied to the determination of FA C_(16) and FA C_(18) in normal human serum and the results showed that the concentrations of fatty acids in normal human serum were 0.134 ± 0.009 μ mol/ml serum(n=5) for FA C_(16) and 0.052±0.028 μmol/ml serum(n=5)for FA C_(18),respectively.

Liquid biopsy in patients with pancreatic cancer: Circulating tumor cells and cell-free nucleic acids

Despite recent advances in surgical techniques and perioperative management, the prognosis of pancreatic cancer(PCa) remains extremely poor. To provide optimal treatment for each patient with Pca, superior biomarkers are urgently needed in all phases of management from early detection to staging, treatment monitoring, and prognosis. In the blood of patients with cancer, circulating tumor cells(CTCs) and cell-free nucleic acids(cf NAs), such as DNA, m RNA, and noncoding RNA have been recognized. In the recent years, their presence in the blood has encouraged researchers to investigate their potential use as novel blood biomarkers, and numerous studies have demonstrated their potential clinical utility as a biomarker for certain types of cancer. This concept, called "liquid biopsy" has been focused on as a less invasive, alternative approach to cancer tissue biopsy for obtaining genetic and epigenetic aberrations that contribute to oncogenesis and cancer progression. In this article, we review the available literature on CTCs and cfN As in patients with cancer, particularly focusing on PCa, and discuss future perspectives in this field.

Synthesis and Characterization of Dual Acidic Ionic Liquids

Novel ionic liquids with dual acidity, of which the cation contains Brφnsted acidity and anions contain Lewis acidity were synthesized. These ionic liquids obtained were identified by NMR, FF-IR, SDT and FAB-MS. Their acidities were determined by pyridine probe on IR spectrography.

Efficient Esterification of Ferrocenecarboxylic Acid in Ionic Liquids

An efficient esterification of ferrocenecarboxylic acid with substituted phenols has been achieved using DCC / DMAP protocol in ionic liquids. The corresponding esters are produced in high yields.

Liquid biopsy in patients with hepatocellular carcinoma: Circulating tumor cells and cell-free nucleic acids

Hepatocellular carcinoma(HCC), with its high incidence and mortality rate, is one of the most common malignant tumors. Despite recent development of a diagnostic and treatment method, the prognosis of HCC remains poor. Therefore, to provide optimal treatment for each patient with HCC, more precise and effective biomarkers are urgently needed which could facilitate a more detailed individualized decision-making during HCC treatment, including the following; risk assessment, early cancer detection, prediction of treatment or prognostic outcome. In the blood of cancer patients, accumulating evidence about circulating tumor cells and cell-free nucleic acids has suggested their potent clinical utilities as novel biomarker. This concept, so-called "liquid biopsy" is widely known as an alternative approach to cancer tissue biopsy. This method might facilitate a more sensitive diagnosis and better decision-making by obtaining genetic and epigenetic aberrations that are closely associated with cancer initiation and progression. In this article, we review recent developments based on the available literature on both circulating tumor cells and cell-free nucleic acids in cancer patients, especially focusing on Hepatocellular carcinoma.

Synthesis of Tetrahydrofuran and Tetrahydropyran Derivatives Catalyzed by Tungstophosphoric Acid in Ionic Liquid

Synthesis of tetrahydrofuran and tetrahydropyran derivatives catalyzed by tungstophosphoric acid （H3PW12040） were conveniently performed with high yield from the corresponding unsaturated alcohols in ionic liquid. Sufuric acid （H2SO4）, trifluoromathanesulfonic acid （TfOH） and p-toluenesulfonic acid （TsOH） were also explored for preparing these products in ionic liquid. The catalysts and ionic liquid can be easily recovered and reused.

Epoxidation of Unsaturated Fatty Acid Methyl Esters in the Presence of SO_3H-functional Brφnsted Acidic Ionic Liquid as Catalyst

The epoxidation of unsaturated fatty acid methyl esters(FAMEs)by peroxyacetic acid generated in situ from hydrogen peroxide and acetic acid was studied in the presence of SO3H-functional Brnsted acidic ionic liquid (IL)[C3SO3HMIM][HSO4]as catalyst.The effects of hydrogen peroxide/ethylenic unsaturation ratio,acetic acid concentration,IL concentration,recycling of the IL catalyst,and temperature on the conversion to oxirane were studied.The kinetics and thermodynamics of unsaturated FAMEs epoxidation and the kinetics of oxirane cleavage of the epoxidized FAMEs by acetic acid were also studied.The conversion of ethylenic unsaturation group to oxirane, the reaction rate of the conversion to oxirane,and the rate of hydrolysis(oxirane cleavage)were higher by using the IL catalyst.

Plasma free amino acid profiling of esophageal cancer using high-performance liquid chromatography spectroscopy

AIM: To perform plasma free amino acid (PFAA) profiling of esophageal squamous cell carcinoma (ESCC) patients at different pathological stages and healthy subjects.

Synthesis of 4,4＇-MDC in the Presence of Sulfonic Acid-functionalized Ionic Liquids

The synthesis of methylene diphenyl dimethylcarbamate （4,4＇-MDC） from methyl N-phenyl carbonate （MPC） and formaldehyde （HCHO） was conducted in the presence of sulfonic acid-functionalized ionic liquids （ILs） as dual solvent-catalyst. The influences of the kind of anion in the ionic liquids, reaction conditions and the recycle of the ionic liquid on 4,4＇-MDC synthesis reaction were investigated. In addition, the acid strength of ILs was de-termined by the Hammett method with UV-visible spectroscopy, and the acid strength-catalytic activity relationship was correlated. The activity estimation results showed that [HSO3-bmim]CF3SO3 was the optimal dual solvent-catalyst. Under the suitable reaction conditions of 70℃, 40 min, molar ratio of nMPC/nHCHO= 10/1 and mass ratio of WILs/WMPC = 4.5/1, the yield of 4,4＇-MDC based on HCHO was 89.9 % and the selectivity of 4,4＇-MDC with respect to MPC was 74.9%. Besides, [HSO3-bmim]CF3SO3 was reused four times after being purified and no significant loss in the catalytic activity was observed.

The alcoholysis of acetonitrile prompted by Brфnsted acidic ionic liquid [HSO_3-pmim]HSO_4

BrФnsted acidic ionic liquids based on imidazolium cation were employed as a series of environmentally benign catalysts and mediums in the alcoholysis of acetonitrile to synthesize ester. The results showed that BrФnsted acidic ionic liquid [HSO3- pmim]HSO4 was an efficient catalyst and medium for the alcoholysis of acetonitrile which could be recycled easily without obvious decline in catalytic activity, the highest yield could reach 85%.

One-pot Synthesis of Lewis Acidic Ionic Liquids for Friedel-Crafts Alkylation

Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. The ionic liquids were used as catalyst for Friedel-Crafts alkylation of benzene and 1-dodecene. The turnovers of l-dodecene were higher than 99%. Monoalkylbenzene selectivity was 98%, while the 2-substituent product selectivity was 45%.

Liquid biopsy of gastric cancer patients:Circulating tumor cells and cell-free nucleic acids

To improve the clinical outcomes of cancer patients, early detection and accurate monitoring of diseases are necessary. Numerous genetic and epigenetic alterations contribute to oncogenesis and cancer progression, and analyses of these changes have been increasingly utilized for diagnostic, prognostic and therapeutic purposes in malignant diseases including gastric cancer (GC). Surgical and/or biopsy specimens are generally used to understand the tumor-associated alterations; however, those approaches cannot always be performed because of their invasive characteristics and may fail to reflect current tumor dynamics and drug sensitivities, which may change during the therapeutic process. Therefore, the importance of developing a non-invasive biomarker with the ability to monitor real-time tumor dynamics should be emphasized. This concept, so called “liquid biopsy”, would provide an ideal therapeutic strategy for an individual cancer patient and would facilitate the development of “tailor-made” cancer management programs. In the blood of cancer patients, the presence and potent utilities of circulating tumor cells (CTCs) and cell-free nucleic acids (cfNAs) such as DNA, mRNA and microRNA have been recognized, and their clinical relevance is attracting considerable attention. In this review, we discuss recent developments in this research field as well as the relevance and future perspectives of CTCs and cfNAs in cancer patients, especially focusing on GC.

Optimization on the Conversion of Bamboo Shoot Shell to Levulinic Acid with Environmentally Benign Acidic Ionic Liquid and Response Surface Analysis

Levulinic acid（LA） has been identified as a promising green,biomass derived platform chemical.Response surface analysis（RSA） with a four-factor-five-level central composite design（CCD） was applied to optimize the hydrolysis conditions for the conversion of bamboo（Phyllostachys Praecox f.preveynalis） shoot shell（BSS） to LA catalyzed with ionic liquid [C4mim]HSO4.The effects of four main reaction parameters including temperature,time,C[C4mim]HSO4（initial [C4mim]HSO4 concentration） and XBSS（initial BSS intake） on the hydrolysis reaction for yield of LA were analyzed.A quadratic equation model for yield of LA was established and fitted to the data with an R2 of 0.9868,and effects of main factors and their corresponding relationships were obtained with RSA.Model validation and results of CCD showed good correspondence between actual and predicted values.The analysis of variance（ANOVA） of the results indicated that the yield of LA in the range studied was significantly（P＆lt;0.05） affected by the four factors.The optimized reaction conditions were as follows：temperature of 145 ℃,time of 103.8 min,C[C4mim]HSO4 of 0.9 mol.L-1 and XBSS of 2.04%（by mass）,respectively.A high yield [（71±0.41）%（by mol）,triplicate experiment] was obtained at the optimum conditions of temperature of 145 ℃,time of 104 min,C[C4mim]HSO4 of 0.9 mol.L-1 and XBSS of 2%（by mass）,which obtained from the real experiments,concurred with the model prediction [73.8%（by mol） based on available C6 sugars in BSS or 17.9%（by mass） based on the mass of BSS],indicating that the model was adequate for the hydrolysis process.

Liquid chromatography–tandem mass spectrometry method for simultaneous determination of valproic acid and its ene-metabolites in epilepsy patient plasma

A simple and high throughput method was developed and validated for simultaneous determination of valproic acid and its two toxicant ene-metabolites, 2-enevalproic acid and 4-enevalproic acid in epilepsy patient plasma using liquid chromatography-tandem mass spectrometry. Probenecid was used as in- ternal standard and solid-phase extraction was selected for sample preparation. A chromatographic separation was performed on an Agilent Poroshell SB-C18 column （50 mm × 4.6 mm i.d., 2.7μm） by an optimized gradient elution at a flow rate of 0.9 mL/min. The total run time was 7 rain. Electrospray ionization was used in negative ion mode by multiple reaction monitoring of the precursor-to-product ion transitions at m/z 143.0→143.0 for valproic acid, m/z 140.9 →140.9 for 2-enevalproic acid and 4-enevalproic acid for their poor fragments, and m/z 283.9→239,9 for probenecid. The results showed good linearity ofvalproic acid, 2-enevalproic acid and 4-enevalproic acid in their respective linear ranges. The correlation coefficients were more than 0.998, The intra- and inter-day precision of the assay was less than 11.0% and the accuracy ranged from 2% to 12%. This analytical method was successfully applied to assay plasma concentrations of valproic acid and its two ene-metabolites in epilepsy patient plasma and used for therapeutic drug monitoring.

Preparation of fructone catalyzed by water-soluble Brφnsted acid ionic liquids

Fructone （2-methyl-2-ethylacetoacetate-1, 3-dioxolane）, a flavouring material, has been synthesized from ethyl acetoacetate and glycol using five water-soluble Brφnsted acid ionic liquids as catalysts for the first time. The used Brφnsted acid ionic liquids include [Hmim]Tfa, [Hmim]Tsa, [Hmim]BF4, [Bmim]HSO4, [Bmim]H2P04, and [Hmim]BF4 showed the highest catalytic activity for the preparation of fructone. After reaction, the product could be isolated from the reaction system automatically, and the ionic liquid could be directly reused without dehydration.