A rate-based method for dynamic analysis and optimal design of reactive extraction: n-Hexyl acetate esterification as an example

The dynamic analysis and optimal design of reactive extraction are challenging due to high nonlinearity of model equations and tough decision of judging criteria. In this work, a dynamic rate-based method is developed on g PROMS platform to get easy access to the solutions of reactive extraction with phase splitting. Based on rigorous criteria, dynamic analysis from initial state to final equilibrium(e.g., evolution of phase composition, mass transfer rate and reaction rate) and optimal design of operating conditions(e.g., extractant dosage and feed molar ratio) are achieved. To illustrate the method, the esterification of n-hexyl acetate is taken as an example. The approach proves to be reliable in the analysis and optimization of the exemplified system, which provides instructive reference for further process design and simulation of reactive extraction.

Reactive dividing-wall column for the co-production of ethyl acetate and n-butyl acetate

Reactive dividing-wall column(RDWC) technology plays a critical role in the energy saving and high efficiency of chemical process.In this article, the process of co-producing ethyl acetate(EA) and n-butyl acetate(BA) with RDWC was studied.BA was not only the product, but also acted as entrainer to remove the water generated by the two esterification reactions.Experiments and simulations of the co-production process were carried out.It was found that the experimental results were in good agreement with the simulation results.Two kinds of RDWC structures(RDWC-FC and RDWC-RS) were proposed, and the co-production process operating parameters of the two types of RDWC were optimized by Aspen Plus respectively.The optimal operating parameters of the RDWC-FC were determined as follows: 0.6 of the reflux ratio of aqueous phase(RR), 0.66 of the vapor split(R_V) and 0.51 of the liquid split(R_L).And the optimal operating parameters of the RDWC-RS were shown as follows: RR was 0.295 and R_V was 0.61.Furthermore, the energy saving analysis of the co-production process was based on the annual output of 10000 tons of EA, compared with the traditional reaction distillation(RD) to prepare EA and BA, the reboiler duty of the RDWC-FC column could save 20.4%, TAC saving 23.6%; RDWC-RS reboiler energy consumption could save 17.0%, TAC 22.2%.

Starch Grafted Water Resistant Polyvinyl Acetate-Based Wood Adhesive: A Review

Global energy issues and the reliance on hydrocarbon resources have resulted in the reduction of petroleum sources, and the focus of the chemical industries has shifted to substitute raw material sources. The major raw materials used in wood adhesives, such as hydrocarbons like polyvinyl acetate, would be gradually replaced by renewable natural polymers. Currently, polyvinyl alcohol has the limitation of petroleum origin, which is non-economical and it will be replaced by biopolymers. Conventionally available wood adhesive emulsions are colloid-like polyvinyl alcohol stabilized. Starch, being a naturally available polymer, has gained interest from researchers for replacing polyvinyl alcohol as a stabilizer. New research on sustainable, economical, biodegradable, renewable, and environmentally friendly starch grafted polyvinyl acetate emulsion that was synthesized by the graft polymerization of vinyl acetate monomer onto starch. However, starch grafted polyvinyl acetate emulsion-based adhesive’s properties, such as poor water resistance, weak adhesion, delayed drying rate and delayed setting speed, have resulted in limitations in its application as a wood adhesive. A detailed review of starch grafting on vinyl acetate and comonomers like acrylamides, and acrylic acid, and the addition of nano-fillers to enhance the water resistance and performance properties of sustainable adhesives has been explained.

Spectral Properties and Solubilization Location of 2′-Ethylhexyl 4-（N,N-Dimethylamino）benzoate in Micelles

Dual fluorescence and UV absorption of 2′-ethylhexyl 4-（N,N-dimethylamino）benzoate （EHDMAB） were investigated in cationic, non-ionic and anionic micelles. When EHDMAB was solubilized in different micelles, the UV absorption of EHDMAB was enhanced. Twisted intramolecular charge transfer （TICT） emission with longer wavelength was observed in ionic micelles, whereas TICT emission with shorter wavelength was obtained in non-ionic micelles. In particular, dual fluorescence of EHDMAB was significantly quenched by the positively charged pyridinium ions arranged in the Stern layer of cationic micelles. UV radiation absorbed mainly decays via TICT emission and radiationless deactivation. The dimethylamino group of EHDMAB experiences different polar environments in ionic and non-ionic micelles according to the polarity dependence of TICT emission of EHDMAB in organic solvents. In terms of the molecular structures and sizes of EHDMAB and surfactants, each individual EHDMAB molecule should be buried in micelles with its dimethylamino group toward the polar head groups of different micelles and with its 2′-ethylhexyl chain toward the hydrophobic micellar core. Dynamic fluorescence quenching measurements of EHDMAB provide further support for the location of EHDMAB in different micelles.

Kinetic Study of Atom Transfer Radical Polymerization of 2-(N,N-Dimethylamino)ethyl Methacrylate

A kinetic model was developed to describe the atom transfer radical polymerization (ATRP) of 2(N,N-dimethylarnino) ethyl methacrylate (DMAEMA). The model was based on a polymerization mechanism, which included the atom transfer equilibrium for primary radical, the propagation of growing polymer radical, and the atom transfer equilibrium for the growing polymer radical. An experiment was carried out to measure the conversion of monomer, the number-average molecular weight of polymer and molecular weight distribution for the ATRP process of DMAEMA. The experimental data were used to correlate the kinetic model and rate constants were obtained. The rate constants of activation and deactivation in the atom transfer equilibrium for primary radical are 1.0 x 10(4) L(.)mol(-1.)s(-1) and 0.04 L(.)mol(-1.)s(-1), respectively. The rate constant of the propagation of growing polymer radical is 8.50 L(.)mol(-1.)s(-1), and the rate constants of activation and deactivation in the atom transfer equilibrium for growing polymer radical are 0.045 L(.)mol(-1.)s(-1) and 1.2 x 10(5) L(.)mol(-1.)s(-1), respectively. The values of the rate constants represent the features of the ATRP process. The kinetic model was used to calculate the ATRP process of DMAEMA. The results show that the calculations agree well with the measurements.

Investigation of the coupled reaction of methyl acetate and n-hexane over HZSM-5

The coupled reaction of methyl acetate and n‐hexane was carried out over a HZSM‐5 catalyst.In addition to a thermal coupling effect,systematic variations in the product distribution were also observed in the coupled system.The bezene‐toluene‐xylene(BTX)selectivity was remarkably improved while the H2,CO,and CO2 selectivity decreased.Rapid deactivation of the catalyst was observed,caused by the extremely high reactivity of methyl acetate,which was alleviated after adding n‐hexane.These results indicated that a coupling effect exists in this system.A detailed pathway for the coupled system is suggested based on the analysis of the surface species,carbonaceous species deposited on the catalyst,as well as the product selectivity changes.The good match between the"hydrogen deficiency"of methyl acetate and the"hydrogen richness"of n‐hexane is consistent with the observed coupling effect.

Synthesis of Poly[(3-octanoylpyrrole-2,5-diyl)-p-(N,N-dimethylamino)benzylidene] and Its Properties by Nitrogen Ion Implantation

A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-(N,N-dimethylamino)benzylidene](POPDMABE), was synthesized firstly by the condensation of 3-octanoylpyrrole with para-dimethylaminobenzaldehyde. The chemical structure of the polymer was characterized by FTIR and 1H NMR spectrometries. The polymer is a potential nonlinear optical(NLO) material. According to the function of optical forbidden band gap(E_g) and photon energy(hν), the optical forbidden band gaps of the polymer before and after ion implantation were calculated. The resonant third-order nonlinear optical properties of POPDMABE before and after ion implantation were also studied by using the degenerate four-wave mixing(DFWM) technique at 532 nm. When the energy is 25 keV and the dose is 2.2×10 17 ions/cm 2, the {polymer′s} optical forbidden band gap is about 1.63 eV which is smaller than that of the non-implanted sample(1.98 eV) and the resonant third-order NLO susceptibility of POPDMABE is about 4.3×10 -7 esu, 1 order of magnitude higher than that of the non-implanted sample(4.1×10 -8 esu). The results show that nitrogen ion implantation is an effective method to improve the resonant third-order NLO property of the polymer.

6-(N,N-Dimethylamino)-2-naphthoylacryl Acid:a Highly Selective and Sensitive Fluorescent Sensor of Copper(Ⅱ)

A novel fluorescent probe,6-（N,N-dimethylamino）-2-naphthoylacryl acid（ACADAN） was designed and synthesized as a fluorescent sensor for Cu^2＋ in aqueous media.Significant amplification of fluorescence signals without causing any discernible change of maximum fluorescence emission wavelength（λ max） was observed upon the addition of Cu^2＋.Importantly,ACADAN is capable of recognizing Cu^2＋ selectively in aqueous media in the presence of various biologically relevant metal ions and the prevalent toxic metal ions in the environment with high sensitivity（detection limit was 0.1 μmol/L）.

Synthesis of Poly (3-acetylpyrrolyl methine) with Azobenzene Side Groups and Study on Its Third-order Nonlinear Optical Property

A novel soluble π-conjugated polymer, poly [（3-acetylpyrrole-2, 5-diyl） p-（N, N-dimethylamino） azobenzylidene] （PAPDMAABE）, was synthesized by condensation of 3-acetylpyrrole with 4-aldehyde-4＇-dimethylaminoazobenzene （ADMAA）. The chemical structure of PAPDMAABE was characterized by Fourier transform infrared spectroscopy （FTIR）, ^1H-NMR, and UV-Vis-NIR spectra. Transmission electron microscope （TEM） analysis for PAPDMAABE indicates that part of PAPDMAABE is in crystal state, due to the short-range order of the polymer. Thermogravimetric analysis （TGA） curve shows that the polymer has good thermal stability and its decomposition temperature is 248℃. The optical band gap of PAPDMAABE obtained from the optical absorption spectrum is about 1.73 eV. The resonant third-order nonlinear optical property of PAPDMAABE at 532 nm was studied using degenerate four-wave mixing （DFWM） technique. The resonant third-order nonlinear optical susceptibility of the polymer is about 7.48×10^-8 esu.

基于薯蓣皂苷元催化合成N-甲基吲哚孕烯醇酮化合物及其抗肿瘤活性

利用N-甲基吲哚对类固醇药物的前驱体16-脱氢孕烯醇酮乙酸酯(16-DPA)的D环C16位进行修饰,采用ZrCl_4-乙酸乙酯廉价催化体系,合成了16个3β-乙酰氧基-16α-3'-吲哚孕烯醇酮化合物和6个3β-羟基-16α-3'-吲哚孕烯醇酮衍生物.该方法具有收率高、立体选择性好和底物适应性强等优点.通过噻唑蓝(MTT)比色法测试了22个化合物对三阴性乳腺癌细胞(MDA-MB-231)的抗肿瘤活性.初步测试结果表明, 3β-乙酰氧基-16α-3'-吲哚孕烯醇酮化合物6h和6i对MDA-MB-231癌细胞有较好的抑制活性,其半数抑制浓度(IC_(50))分别为18.07和23.22μmol/L;而化合物7a~7f均对MDA-MB-231癌细胞有较好的抑制活性,其中化合物7e的抗肿瘤活性最好,其IC_(50)为12.50μmol/L.目标化合物为药物筛选提供了一定的参考.

The Microwave-assisted Preparation and X-Ray Structure of 3-Bromocarbazole-N-Acetic Acid

The rapid synthesis of 3-bromocarbarole-N-acetic acid was performed using microwave irradiation. Under the optimal conditions the yield was 85.6% . The crystal structure showed that the carboxylic groups form bifurcated hydrogen bonds and the hydroxyl oxygen atoms serve as proton donors and also acceptor. Each carboxylic group was involved in four hydrogen bonds. The package of crystal was dominated by links of these hydrogen bonds.

Synthesis,Structure and DFT Calculations of a Novel Copper(Ⅱ)Complex Based on Tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate

A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.

ResearchonS202一／Zr02solidsuperacidinsynthesisofn—amylacetateundermicrowaveradiation

采用沉淀一浸渍法制得S2O62 8-／ZrO2固体超强酸，在微波辐射下催化合成乙酸正戊酯。通过单因素实验和正交实验优化了合成的反应条件；采用Hammett指示剂法、BET法、红外光谱、电子透镜技术和x_射线衍射对其进行了表征。实验结果表明，采用最佳制备条件下得到的催化剂在微波辐射下催化合成乙酸正戊酯的最优合成条件为：醇酸摩尔比1．9：1，反应温度135℃，反应时间25min，催化剂用量1．2g，功率500W，收率为97．8％。该工艺具有绿色、安全、操作简单和收率高等优点。

Regioselective Deprotection of 1,3-Dibenzyl-5-(N,N-dimethylamino)-6-phenylethyluracil

The deprotection of 1,3-dibenzyl-5-（N,N-dimethylamino）-6-phenyl-ethyluracil I was investigated. A practical, regioselective N3 deprotection of compound I was performed with excellent yield using cyclohexene as a hydrogen donor.

α-Oxoketene Cyclic S, S-cetals Chemistry-Substitution Reaction of α,α'-Dicinnamoyl Ketene Cyclic S, S-Acetals with Ethylenediamine

α,α'-Dicinnamoyl ketene cyclic S, S-acetals 4 were reacted with ethylenediamine to afford α,α'-dicinnamoyl ketene cyclic N,N-acetals 5. This process provides a new method for thesynthesis of 5 in high yield under mild conditions.

Preparation, Characterization and Catalytic Performance of La-SO_4^(2-)/SBA-15 in Esterification of Acetic Acid with n-Butanol

La-SO42-/SBA-15 was synthesized with various amounts of lanthanum via incipient-wetness impregnation. Characterization was done by X-ray diffraction（XRD）, transmission electron micrographs（TEM）, nitrogen adsorption, FTIR spectroscopic analysis, thermogravimetric analysis, and the total amount of acidity of catalyst was estimated by TPD of NH3. The results indicate that lanthanum has been incorporated into SBA-15 molecular sieve. The prepared materials（La-SO42-/SBA-15） keep the highly ordered mesoporous two-dimensional hexagonal structure and do not change the mesoporous channel structure of the support SBA-15. The catalyst showed best catalytic activity in the synthesis of n-butyl acetate. The optimum conditions of the esterification by orthogonal experiments were studied： the molar ratio of n-butanol to acetic acid 1：1.2, the amount of catalyst 7.5%, reaction time 80 min. The yield of n-butyl acetate could reach 93.2% under the optimum conditions. The catalyst was recyclable, cost effective and environmental friendly.

In vitro cytotoxicity of Indonesian stingless bee products against human cancer cell lines

Objective:To screen crude extracts of propolis,bee pollen and honey from four stingless bee species[Trigona incisa(T.incisa)],Timia apicalis,Trigona fuso-baltata and Trigona filscibasis)native to East Kalimantan.Indonesia for cytotoxic activity against five human cancer cell lines(HepG2,SW620,ChaGo-1,KATO-Ⅲand BT474).Methods:All samples were extracted with methanol,and then subpartitioned with n-hexane and ethyl acetate.Each crude extract was screened at 20μg/mL for in vitro cytotoxicity against the cell lines using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay.Tn addition,four previously shown bioactive components from propolis(apigenin,cafieic acid phenyl ester,kaempferol and naringenin)and two chemotherapeutic drugs(doxorubicin and 5-fluorouracil)were used to evaluate the sensitivity of the cell lines.Results:Overall,crude extracts from propolis and honey had higher cytotoxic activities than bee pollen,but the activity was dependent upon the extraction solvent,bee species and cell line.Propolis extracts from T.incisa and Tarda apicalis showed the highest and lowest cytotoxic activity,respectively.Only the HepG2 cell line was broadly sensitive to the honey extracts.For pure compounds,doxorubicin was the most cytotoxic,the four propolis compounds the least,but the ChaGo-I cell line was sensitive to kaempferol at 10μg/mL and KATO-Ⅲwas sensitive to kaempferol and apigenin at 10μg/mL,.All pure compounds were effective against the BT474 cell line.Conclusions:Propolis from f,incisa and Trigona fusco-balteata contain an in vitro cytotoxic activity against human cancer cell lines.Further study is required,including the isolation and characterization of the active antiproliferative agent(s).

VINYL MONOMERS BEARING CHROMOPHORE MOIETIES AND THEIR POLYMERS——Ⅹ.INITIATION AND PHOTOCHEMICAL PROPERTIES OF p-(N,N-DIMETHYLAMINO)STYRENE AND ITS POLYMERS

A vinyl monomer having an electron-donating moiety, p-(N,N-dimethylamino)styrenc (DMAS),was synthesized. It was combined with benzoyl peroxide (BPO) to form a redox initiation system to initiatethe polymerization of methyl methacrylate (MMA). UV spectra measurements show that DMAS enters thePMMA chain as well. Both DMAS and its polymer P(DMAS) display strong fluorescence, and thefluorescence can be quenched by electron-deficient compounds such as methacrylonitrile, fumaronitrile andmethyl methacrylate etc. Moreover, DMAS can also form charge transfer complex (CTC) with strongelectron acceptors such as tetracyanoethylene (TCNE). The difference between the photochemical propertiesof DMAS and P(DMAS) were explained in terms of molecular structure change and polymer conformationeffect in solution. In addition, the CTC and exciplex formation of DMAS or P(DMAS) with C_(60) were alsostudied.

基于DMC法的α-氨基酸-N-环内酸酐的绿色合成

针对传统方法合成α-氨基酸-N-环内酸酐(NCAs)毒性大、对环境不友好的问题,以氨基酸为原料,以乙酸锌为催化剂,以碳酸二甲酯(DMC)为环化剂,通过“一锅法”高效环保地合成了L-苯丙氨酸-N-羧基环内酸酐(Phe-NCA)、L-天冬氨酸-4-苄酯-羧基环内酸酐(H-Asp-Obzl-NCA)和Nε-苄氧羰基-L-赖氨酸环内酸酐(Cbz-Lys-NCA)等3种新型NCAs。通过GC-MS、NMR、FT-IR等对其进行定性表征;讨论了反应温度、反应物比例等因素对氨基酸转化率与NCAs产率的影响;并通过对比催化剂乙酸锌在反应前后的XPS和XRD等表征,分析乙酸锌的催化机理。结果表明:反应中氨基酸∶去质子碱∶催化剂的摩尔比为1:1.5:0.2,反应分别在160、120、140℃进行8 h后,去质子氨基酸与DMC在乙酸锌的作用下发生甲氧羰基化反应,进一步关环,Phe-NCA、H-Asp-Obzl-NCA和Cbz-Lys-NCA最佳产率可分别达到55.22%、56.30%和46.46%;乙酸锌的催化机理为Zn^(2+)与DMC中的羰基氧进行配位络合后实现氨基酸靶向甲氧羰基化,促进邻近COO-与羰基碳发生亲核取代,从而实现精准关环,得到NCAs。