Upper-rim-modified thioether thiacalix[4]arene used for liquid-liquid extraction of Au(Ⅲ)and Pd(Ⅱ)in hydrochloric acid medium

Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene(TCAET)was synthesized specifically for the capture of Au(Ⅲ)and Pd(Ⅱ)from HCl medium by liquid-liquid extraction.In a 0.1 mol·L^(-1)HCl medium,the transfer of Au(Ⅲ)and Pd(Ⅱ)from the aqueous phase to the organic phase was highly efficient,with a transfer ratio of 100%for Au(Ⅲ)and 98%for Pd(Ⅱ).Furthermore,the extraction equilibrium time for Au(Ⅲ)was just 5 min.Job's method data demonstrated that TCAET formed complexes with Au(Ⅲ)and Pd(Ⅱ)in a ratio of 2:3 and 1:1,respectively,during the extraction process.TCAET showed high selectivity toward Pd(Ⅱ)and Au(Ⅲ)over other competing metal ions.Moreover,both Au(Ⅲ)and Pd(Ⅱ)could be successfully stripped from the loaded organic phases with a 1.0 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl and 0.5 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl,respectively.Results obtained from five consecutive extraction-stripping cycles showed good reusability of TCAET toward Au(Ⅲ)and Pd(Ⅱ)recovery.The conclusion can provide a certain reference for thiacalixarene in the recovery of precious metal species.

The extraction of aromatics using N-methylpyrrolidone: Liquid-liquidequilibrium determination and mechanism exploration

LLE data of cyclooctane/3-methylpentane + benzene/toluene + N-methylpyrrolidone (NMP) at 298.15 Kand 313.15 K under a pressure of 101.3 kPa were measured in this work. The Othmer-Tobias and Handequations were adopted to validate the reliability of LLE data, where the correlation coefficients (R2) wereclose to unity, indicating the high reliability of the experimental data. The experimental data were analyzed using the distribution coefficient (D) and separation factor (S), and the effect of NMP extracting benzene and toluene from aromatics was explored. Meanwhile, the reason for the different extractionefficiencies of benzene and toluene using NMP was analyzed by quantum chemical calculations. TheNRTL and UNIQUAC thermodynamic models were used to correlate the liquid–liquid equilibrium data,and the relevant binary interaction parameters were obtained. The calculated root mean square deviation(RMSD) were all less than 0.0063, indicating that the obtained binary interaction parameters can be usedto simulate and calculate the extraction of aromatics using NMP.

Improved determination of salicylaldoxime in water samples by liquid-liquid extraction followed by high performance liquid chromatographic analysis

For the determination of salicylaldoxime in environmental water samples,a stable and rapid method with low detection was proposed and established,based on the liquid-liquid extraction-high performance liquid chromatography with ultraviolet detector.Parameters including extraction solvent,ionic strength,solution pH,and extraction pattern were discussed for the optimal quantification of salicylaldoxime-spiked water.When the described method was applied to four spiked water samples,the obtained average extraction recovery rate was found between 87%–107%and relative standard deviation was below 6%.At the same time,good linear relationships were observed for spiked water samples from 0.01 to 10μg/mL(R2=0.9993).In addition,the detection limit of salicylaldoxime was revealed between 0.003–0.008μg/mL,which is two orders of magnitude lower than previously reported results.Thus,the presented method may be advantageous for the high-efficiency determination of salicylaldoxime in water samples.

Simulation of Solvent Extraction for Naphthenic Lubricating Base Oils

Solvent extraction is the process of separating aromatics from vacuum distillates for the production oflubricating base oils. In this study, the authors use dimethyl sulfoxide (DMSO) instead of furfural as solvent, in light of itshigher selectivity, to obtain extracts with a high aromatic content for naphthenic lubricating base oils. We systematicallyinvestigated effects of the solvent-to-oil (S/O) ratio and extraction temperature on the yield of the extract, efficiency ofaromatic removal, and composition of the extracts and raffinates. The results showed that the aromatic content of extractsfor naphthenic oils could reach a high value of about 80%. The solvent maintained a high selectivity for aromatics fornaphthenic oils even under a high S/O ratio and a high extraction temperature. Moreover, the efficiency of aromatic removalfor naphthenic lubricating base oils could be enhanced by increasing either the S/O ratio or the extraction temperature,although these measures had limited effects in practice. Following this, we used the non-random two-liquid (NRTL) modelbased on the pseudo-component approach to simulate the liquid-liquid equilibrium of the system of DMSO + naphtheniclubricating base oils, and determined the parameters of binary interaction through regression based on the data on phaseequilibrium. The modeling results showed that the predicted yield, content of the solvent, and composition of the raffinatesand extracts were in good agreement with those obtained in the experiments. This validates the reliability of the model usedto represent the DMSO + naphthenic lubricating base oil system. Both the experimental data and the method of simulationreported here can help optimize the extraction of naphthenic lubricating base oils, and provide a better understanding of thecorresponding process.

Colorimetric determination of nanomolar concentrations of silicate in natural waters after liquid-liquid extraction using methyl isobutyl ketone

A sensitive solvent extraction method for the determination of nonamolar concentrations of silicate in natural waters is developed. According to the traditional aqueous silicate method, silicomolybdenum blue formed by the reaction between silicate and ammoni- um molydate and reduced by metol-sulfite reagent is extracted by methyl isobutyl ketone. The absorbance can be enhanced substantially up to 10-folds. The detection limit of silicate is 8 nmol/dm^3 , which is one tenth smaller than the traditional method, with the precision of 4.0% at a silicate level of 50 nmol/dm^3 and 3.2% at a silicate level of 6 μmol/dm^3. Comparing the calibration curves in the distilled water and seawater, it can be seen that the salt effect also exists in the extraction method. However, the salt effect is a linear function of the salinity and can be corrected by simple calibration. The proposed method is successfully applied to the determination of silicate in natural waters. Natural concentrations of arsenate, arsenite and phosphate cause negligible interference.

Mass transfer coefficient in the eductor liquid-liquid extraction column

In this research gasoil desalting was investigated from mass transfer point of view in an eductor liquid–liquid extraction column(eductor-LLE device).Mass transfer characteristics of the eductor-LLE device were evaluated and an empirical correlation was obtained by dimensional analysis of the dispersed phase Sherwood number.The Results showed that the overall mass transfer coefficient of the dispersed phase and extraction efficiency have been increased by increasing Sauter mean diameter(SMD)and decreasing the nozzle diameter from 2 to 1 mm,respectively.The effects of Reynolds number(R_(e)),projection ratio(ratio of the distance between venturi throat and nozzle tip to venturi throat diameter,Rpr),venturi throat area to nozzle area ratio(R_(th-n))and two phases flow rates ratio(R_(Q))on the mass transfer coefficient(K)were determined.According to the results,K increase with increasing Re and RQ and also with decreasing Rpr and R_(th-n).Semi-empirical models of drop formation,rising and coalescence were compared with our proposed empirical model.It was revealed that the present model provided a relatively good fitting for the mass transfer model of drop coalescence.Moreover,experimental data were in better agreement with calculated data with AARE value of 0.085.

Comparison of liquid-liquid extraction-thin layer chromatography with solid-phase extraction-high-performance thin layer chromatography in detection of urinary morphine

Liquid-liquid extraction-thin layer chromatography （LLE-TLC） has been a common and routine combined method for detection of drugs in biological materials. Solid-phase extraction （SPE） is gradually replacing the tra- ditional LLE method. High performance thin layer chromatography （HPTLC） has several advantages over TLC. The present work studied the higher efficiency of a new SPE-HPTLC method over that of a routine LLE-TLC method, in extraction and detection of urinary morphine. Fifty-eight urine samples, primarily identified as mor- phine-positive samples by a strip test, ＇were re-screened by LLE-TLC and SPE-HPTLC. The results of LLE-TLC and SPE-HPTLC were then compared with each other. The results showed that the SPE-HPTLC detected 74% of total samples as morphine-positive samples whereas the LLE-TLC detected 48% of the same samples. We further discussed the effect of codeine abuse on TLC analysis of urinary morphine. Regarding the importance of morphine detection in urine, the present combined SPE-HPTLC method is suggested as a replacement method for detection of urinary morphine by many reference laboratories.

Quantitative analysis of trace levels of β-ionone in water by liquid-liquidphase extraction-gas chromatography-mass spectrometry(LLE-GC-MS)

A simple and rapid technique based on liquid-liquid extraction coupled to gas chromatography-mass spectrometric detection(LLE-GC-MS) was developed for analysis of taste and odour compound β-ionone in water. Instrument parameters including programmed oven temperature, injection temperature and ion source temperature were evaluated and optimized. Effects of extraction time, ionic strength and p H on the detection efficiency were investigated and optimum conditions were 8 min of extraction time, without Na Cl addition at p H=9. Good linearity(R2=0.9997) was obtained when the linear range was 10-500 μg/L. The recoveries of β-ionone in ultrapure water and tap water samples were 88%-95% and 110%-114%, respectively. The relative standard deviations(RSD) were less than 10%. The method detection limit(MDL) and rejection quality level(RQL) were achieved at1.98 μg/L and 6.53 μg/L, respectively. LLE-GC-MS was demonstrated to be a rapid and convenient method for the determination ofβ-ionone in water samples.

Salting-Out Assisted Liquid-Liquid Extraction Combined with HPLC for Quantitative Extraction of Trace Multiclass Pesticide Residues from Environmental Waters

In this study, salting-out assisted liquid-liquid extraction combined with high performance liquid chromatography diode array detector (SALLE-HPLC-DAD) method was developed and validated for simultaneous analysis of carbaryl, atrazine, propazine, chlorothalonil, dimethametryn and terbutryn in environmental water samples. Parameters affecting the extraction efficiency such as type and volume of extraction solvent, sample volume, salt type and amount, centrifugation speed and time, and sample pH were optimized. Under the optimum extraction conditions the method was linear over the range of 10 - 100 μg/L (carbaryl), 8 - 100 μg/L (atarzine), 7 - 100 μg/L (propazine) and 9 - 100 μg/L (chlorothalonil, terbutryn and dimethametryn) with correlation coefficients (R2) between 0.99 and 0.999. Limits of detection and quantification ranged from 2.0 to 2.8 μg/L and 6.7 to 9.5 μg/L, respectively. The extraction recoveries obtained for ground, lake and river waters were in a range of 75.5% to 106.6%, with the intra-day and inter-day relative standard deviation lower than 3.4% for all the target analytes. All of the target analytes were not detected in these samples. Therefore, the proposed SALLE-HPLC-DAD method is simple, rapid, cheap and environmentally friendly for the determination of the aforementioned herbicides, insecticide and fungicide residues in environmental water samples.

光子晶体Micro LED微显示阵列加工及光学特性分析

Micro LED器件具有高亮度、低功耗和高可靠性等优点,但Micro LED显示像素巨量转移和光提取效率低的问题为其应用带来挑战。开发了具有高转移效率和出光效率的单片64×64 Micro LED微显示阵列,提出了倒装型GaN基单片Micro LED微显示阵列芯片和Si基驱动电路的设计方法及集成工艺。通过时域有限差分(FDTD)方法对Micro LED微显示阵列光学特性进行了建模分析,设计了一种提高Micro LED微显示阵列出光效率的光提取结构。结合仿真结果,开发了一种在Micro LED蓝宝石衬底表面制备光子晶体结构的聚焦离子束(FIB)微纳加工工艺,并进行了器件加工。测试结果表明,蓝宝石衬底上加工的光子晶体结构可以提高Micro LED器件的表面出光效率,光功率平均值提升了16.36%,对Micro LED微显示阵列加工及微显示像素光提取问题具有借鉴意义。

Determination of organochlorine pesticides from juice samples using magnetic biochar-based dispersive micro-solid phase extraction in combination with dispersive liquid-liquid microextraction

Analysis of pesticide residue levels in juice beverages is important to ensure safe consumption and avoid global trade concerns associated to pesticide contaminations.A simple,inexpensive and effective method was developed for the determination of organochlorine pesticides(OCPs)in bottled juice drinks using GC-MS.Sample pretreatment was performed using dispersive solid-phase microextraction(D-μ-SPE)for matrix desorption and dispersive liquid-liquid microextraction(DLLME)for analyte enrichment.In this study,an affordable and effective sorbent for the adsorption of OCPs from juice samples was synthesized from avocado seeds mixed with magnetic precursors for D-μSPE.The ground avocado seeds combined with a magnetic precursor nanocomposite were characterized using various instruments including scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and Brunauer-Emmett-Teller(BET)analysis.The solution obtained from D-μ-SPE desorption was used as a dispersant for the subsequent DLLME,which made the combination of D-μ-SPE with DLLME much easier.The effectiveness of the method was enhanced by optimizing the influential parameters in both D-μ-SPE and DLLME.Then after,the optimal values were determined for the real sample analysis.Accordingly,there was good linear dynamic range with a coefficient of determination(r2)≥0.9989.The limit of detection and quantification were 0.02–0.69 and 0.06–2.10 ng/L respectively.The method showed high enrichment factors ranging from 96 to 313 with recoveries of 87–100%.Intraday and interday precisions were≤4%.Compared with other reported methods,this method is a one-step,simple,cheap,fast,and environmentally friendly alternative and straightforward method for adsorbing organochlorine pesticides from sample solutions.These results demonstrates the high potential of the proposed method for the extraction and cleanup of contaminants in selected juices and other related samples.

Outcome of repeated micro-surgical testicular sperm extraction in patients with non-obstructive azoospermia

Aim： To evaluate the outcome of repetitive micro-surgical testicular sperm extraction （mTESE） attempts in non-obstructive azoospermia （NOA） cases, in relation to patients＇ initial testicular histology results. Methods： A total of 68 patients with NOA in whom mTESE had been performed in previous intracytoplasmic sperm injection （ICSI） attempts were reviewed. Results： Among the 68 patients with NOA, the first mTESE yielded mature sperm for ICSI in 44 （64%） （Sp^＋）, and failed in the remaining 24 （36%） （Sp^-）. Following their first trial, 24 patients decided to undergo a second mTESE. Of these 24 patients, no spermatozoa were obtained in 5 patients, and Sp^＋ but no fertilization/pregnancy were achieved in 19. In these 24 cases, mTESE was successively repeated for two （n = 24）, three （n = 4） and four （n = 1） times. The second attempt yielded mature sperm in 3/5 patients from the Sp group and 16/19 patients from the Sp^＋ group. At the third and fourth trials, 4/4 and 1/1 of the original Sp^＋ patients were Sp^＋ again, respectively. Distribution of main testicular histology included Sertoli cell-only syndrome （16%）, maturation arrest （22%）, hypospermatogenesis （21%） and focal spermatogenesis （41%）. Overall, in repetitive mTESE, 24/29 （82%） of the attempts were finally Sp^＋. Conclusion： Repeated mTESE in patients with NOA is a feasible option, yielding considerably high sperm recovery rate. In patients with NOA, mTESE may safely be repeated one or more times to increase sperm retrieval rate, as well as to increase the chance of retrieving fresh spermatozoa to enable ICSI.

Determination of Melamine in Fresh Milk by Electrochemistry with Solid Phase Microextraction at Bismuthyl Chloride Modified Graphite Epoxy Composite Electrode

Melamine as an important chemical raw material and a harmful additive in foods has attracted many people’s attention. In the present paper, The graphite-epoxy composited solid phase electrode was modified with bismuth layer by cyclic voltammetric deposition of bismuth from Bi(NO3)3 aqueous solution including 0.10 M HNO3, and hydrolyzed into micro bismuthyl chloride on-sites. Melamine in fresh milk was extracted with solid phase micro-extraction on the bismuthyl chloride modified graphite-epoxy composited solid electrode. The adsorption of melamine on bismuthyl chloride particle surfaces follows a Freundlich adsorption model, and results in the decrease of the reduction peak current of bismuth in bismuthyl chloride, and determined by differential pulse voltammetry from fresh milk in a larger concentration range of 10–4 ? 10–12 M with detection limit of 2.5 ? 10–12 M and relative standard deviation of 2.7%. The method is sensitive, convenient and was applied in the detection of melamine in fresh milk with relative deviation of 4.2% in content of 0.45 mg/kg melamine in the fresh milk.

Determination of 16 Species of OCPs in Water by Liquid-liquid Extraction-GC

[Objective] The research aimed to study the determination of 16 kinds of OCPs in water by liquid-liquid extraction -GC. [Method] The new method for determining 16 kinds of OCPs in water by liquid-liquid extraction -GC was established, and the influencing factors such as nitrogen pressure and water bath temperature were discussed. [ Result] Detection limit of the method was from 3.2 to 14.1 ng/L, the relative standard deviation was between 4.0% and 9.6%, and the average recovery ranged from 80.8% to 106.0%. By optimizing nitrogen pressure and water bath temperature in the sample pretreatment process, when nitrogen pressure was ＋0.087 kPa, and water bath temperature was ±36 ℃, recovery effect of this method was better. [ Conclusion] The determination method had accurate qualitative and quantitative results, and met detection requirement of 16 kinds of OCPs in water.

Modeling of Liquid-Liquid Extraction Process for Glycerol Purification from Biodiesel Production

This paper shows some generalities about the glycerin byproduct obtained from biodiesel production process, presents an analysis of the ternary equilibrium between methanol, water and glycerol, and shows the influence that temperature has on the balance. This phase diagram illustrates ternary equilibrium at 10, 20 and 50 ℃, keeping the pressure constant at 1 atm （atmosphere） to standardize the analysis. The purpose of it is to establish the best temperature for the purification of glycerol by liquid-liquid extraction method under the ＂extraction in several stages cross flow＂ taking an initial mixture of glycerol with composition 15 wt.% water, 25 wt.% methanol and 60 wt.% glycerol. Water was used as liquid-liquid extraction solvent in order to remove as much methanol as possible from the initial solution due to the existence of a zone of insolubility between the glycerol and water in the ternary equilibrium. By this reason, two solutions are obtained, one consisting of water and methanol containing a trace of glycerin and the other consisting of water, glycerine and traces of methanol, which contain only 4.62% of the total methanol which enter in the process of liquid-liquid extraction, with 60.62% of the total glycerol, which is sent to a fractional distillation process to purify glycerin up to 98% by weight.

Liquid-liquid extraction pretreatment samples method used for pharmacokinetic study of rhubarb in rats after oral administrated

Objective:Pretreatment of biological samples is the most critical step in pharmacokinetic studies,especially pre-treatment of plasma samples.The pretreatment of biological samples in pharmacokinetic study of Traditional Chinese Medicines (TCM) is difficult due to the complexity of the ingredients.An organic solvent system ethyl acetate:acetone (10:1) solution used for liquid-liquid extraction has been developed in this study and compared with the commonly used protein precipitation method.Methods:Rats,Beagle dogs and humans plasma samples were adopted in this study in order to demonstrate the universality of the pretreatment method.Feasibility of this pretreatment method was also verified through its application to the pharmacokinetics of rhubarb in rats.Results:According to the results of extraction recovery matrix effect,it was indicated that the liquid-liquid extraction methods with new organic solvent might be suitable for variety of structures of compounds and various types of plasma samples.The pharmacokinetic study result showed that the developed pretreatment method could successfully be used for simultaneous determination of three active compounds modin,emodin-8-O-β-D-glucopyranoside (EDG) and rhein in rat plasma with high sensitivity,accuracy,and recovery by liquid chromatography tandem mass spectrometry (LC-MS/MS).Conclusion:The pretreatment method of liquid-liquid extraction methods with new organic solvent could be successfully applied for multi-component pharmacokinetics of TCM.

Sinomenine Purification by Continuous Liquid-Liquid Extraction Process with Centrifugal Extractors

Continuous manufacturing is considered as one of the future trends of pharmaceutical engineering. In this work, continuous liquid-liquid extraction for sinomenine purification was realized with the usage of centrifugal extractors. Chloroform was used as the extractant because of the high distribution coefficient (>100). Higher extraction ratio can be obtained when using the centrifugal extractor of Model CWL50-N. The extraction ratio of the second-stage extraction was higher than that of the first-stage extraction. The extraction ratio of the second-stage countercurrent extraction was higher than that of second-stage cross-flow extraction. When chloroform phase was recycled for liquid-liquid extraction, the extraction ratio was also higher than 95%. This work can also be an example of continuous liquid-liquid extraction for the separation of other Chinese medicine components.

Homogeneous Liquid-Liquid Extraction (HoLLE) of Palladium in Real Plating Wastewater for Recovery

On the basis of homogeneous liquid-liquid extraction (HoLLE) with Zonyl FSA to plating water containing 1 mg palladium, 96.6% of the palladium was extracted into the sedimented liquid phase. After phase separation, the volume ratio (Va/Vs) of the aqueous phase (Va) and the sedimented liquid phase (Vs) was 556 (50 mL → 0.09 mL). The assessment of the potential implementation of this procedure to wastewater treatment showed that HoLLE was satisfactorily achieved when the volume was scaled up to 1000 mL. Moreover, HoLLE was conducted to real palladium plating wastewater generated in the plating industry. 94.5% of the palladium was extracted into the sedimented liquid phase. After phase separation, the volume ratio (Va/Vs) of the aqueous phase (Va) and the sedimented liquid phase (Vs) was 500 (50 mL → 0.1 mL). In addition, HoLLE could separate palladium from coexisting metals in real plating wastewater. This knowledge is expected to lead to the development of new separation and concentration technologies of rare metals from real plating wastewater.

STUDY ON TREATING ALKALI EXTRACTION-STAGE EFFLUENT FOR COLOR REMOVAL BY MICRO-ELECTROLYSIS METHOD

The micro-electrolysis technology was applied in the decolorizing treatment of bleaching E-stage effluent and the influencing factors were discussed in this paper. The initial pH and the retention time were main factors influencing the color removal rate, in addition, adding air and enough pH for neutralization were necessary for the treatment. The test showed that the decolorizing result was efficient by micro-electrolysis treatment when adding air, initial pH was 3, 20 minutes of reaction time, the final pH 10 for neutralization. The color removal rate was up to 90%. The chance of ultraviolet absorption spectrum also demonstrated the mechanism of color removal in the wastewater treatment.

High-Precision Wideband Phase-Derived Velocity Measurement for Micro-Motion Extraction

A phase-derived velocity measurement method is proposed in a wideband coherent system,based on a precise echo model considering the inner pulse Doppler effect caused by fast moving targets.The Cramer-Rao low band of velocity measurement precision is deduced,demonstrating the high precision of the proposed method.Simulations and out-field experiments further validate the effectiveness of the proposed method in high-precision measurement and micro-motion extraction for targets with weak reflection intensity.Compared with the long-time integration approaches for velocity measurement,the phase-derived method is easy to implement and meets the requirement for high data rate,which makes it suitable for micro-motion feature extraction in wideband systems.