Crystal Structure and Properties of a Copper(Ⅱ) Complex Containing p-Toluenesulfonate and Imidazole Ligands

A novel supramolecular mixed ligand complex of formula [Cu（PTS）2（Him）2（H2O）2] （C20H26CuN4O8S2,PTS=p-toluenesulfonate,Him=imidazole） has been synthesized in aqueous solution and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The compound crystallizes in the monoclinic system,space group P21/n,Z=2,a=5.650（2）,b=14.671（3）,c=14.638（3）,β=100.10（3）°,V=1194.60（4）3,Dc=1.607 g/cm3,μ（MoKα）=1.143 mm-1,F（000）=598,R=0.0615 and wR=0.1503 for 1752 observed reflections with I 〉 2σ（I）.The copper（II） ion in the complex adopts a slightly distorted octahedral coordination geometry and is six-coordinated with N2O4 donor set consisting of two nitrogen atoms and four oxygen atoms provided by the ligands of two imidazole molecules,two water molecules and two p-toluenesulfonate ions.The sulfonate group of the PTS ligand remains weak-coordinated and forms a number of hydrogen bonds with water molecules and imidazole ligands.X-ray structural analysis reveals that the coordination molecules are connected to form a 3-D supramolecular framework by electrostatic interaction,weak van der Waals forces,hydrogen bonding and π-π interaction.The thermal behaviour of the title complex was investigated by using DSC and TG-DTG techniques.

隔壁塔萃取精馏及共沸精馏分离异丙醇-水体系的模拟与优化

分别采用隔壁塔萃取精馏(EDWC)与隔壁塔共沸精馏(ADWC)工艺制取无水异丙醇(IPA),借助Aspen Plus模拟软件建立二塔等价模型,利用灵敏度分析对主塔进料位置、夹带剂用量、侧线采出位置、侧线采出量及回流比等参数进行优化,结合塔的设计规范,以此确定最佳工艺参数。模拟结果显示,与常规双塔工艺流程相比,在完成相同的分离要求下,EDWC工艺的冷凝器和再沸器热负荷分别降低32.38%,12.39%,设备费用和总年度费用分别节约29.34%,4.87%;ADWC工艺的冷凝器和再沸器热负荷分别降低29.57%,23.41%,设备费用和总年度费用分别节约16.87%,22.41%。ADWC用于制取无水IPA在节能降耗及节约设备成本方面表现出明显的优势。

高原鼠兔血清中N-isopropyl oxamate的RP-HPLC检测方法的建立

目的：探索N-isopropyl oxamate和血清蛋白结合水平,建立高原鼠兔血液中精子型乳酸脱氢酶（LDH-C4）特异性抑制剂N-isopropyl oxamate的高效液相色谱（HPLC）检测方法。方法：取体重150-200 g高原鼠兔20只,随机分为对照组和抑制剂组（n=10）。通过外源性加入不同浓度的N-isopropyl oxamate,检测其与血清蛋白的结合水平。采用将血清先用胰蛋白酶酶解,再加入三氯乙酸的前处理法进行HPLC检测。结果：当空白高原鼠兔血清加入抑制剂标准品达到血清中浓度为0.05 mmol/L、0.1 mmol/L、1 mmol/L、10 mmol/L、16.7 mmol/L、33.3 mmol/L、100 mmol/L时,抑制剂与血清蛋白的结合率分别为100%、100%、100%、86.84%、54.11%、40.10%、20.18%。在本文建立的方法下,回收率、精密度、稳定性均良好。N-isopropyl oxamate在0.0125-0.25 mmol/L内浓度与峰面积线性关系好。空白血清加入标准品达到终浓度为0.15 mmol/L、0.3 mmol/L和1 mmol/L时,平均回收率分别为98.05%、98.98%、98.12%;精密度相对标准偏差（RSD）分别为1.17%、0.92%、0.83%;稳定性RSD分别为1.38%、1.40%、0.88%。方法的重复性RSD为1.76%,最低定量限为0.0125 mmol/L。结论：N-isopropyl oxamate与高原鼠兔血清具有很强的亲和力,直接用三氯乙酸沉淀蛋白的前处理方法无法准确检测其浓度,而先用胰蛋白酶消化血清,再用三氯乙酸沉淀蛋白的方法可实现血液中HPLC的精确检测。

水工混凝土浸渍型防护涂料抗冰拔性能试验研究

高寒地区的水利大坝等水工混凝土建筑物在结冰期间易出现建筑外层与覆冰层发生抗冰拔破坏的现象,降低了建筑物的耐久性和服役寿命。通过防护涂料中端羟基硅油(PDMS)掺杂不同含量正硅酸乙酯(TEOS)后对水泥基抗冰拔防护性能影响的试验,以及不同浓度梯度的异丙醇(IPA)掺量对涂料渗透性和耐腐蚀性影响的试验,研发出一种以TEOS、PDMS、IPA和乙醇(EtOH)为主要成分,用于高寒地区水利大坝迎水面的浸渍型防护涂料,并与其他品种涂料进行抗冰拔能力对比试验。结果表明:涂料的抗冰拔性能随TEOS用量的增加先增高后降低,TEOS在涂料中质量分数为21%时效果最好;添加18%(质量分数)的IPA可有效减少涂料在使用过程中被污染而导致使用寿命缩短的现象;所研发的防护涂料在与同类型涂料进行抗冰拔与水接触角对比试验中取得了较为良好的效果,接触角为121.5°;提出的检测水泥基与冰层之间冰拔力的试验方法,可以作为检验水泥基涂料抗冰拔能力的一种途径。

生物体中氨基酸单体碳稳定同位素测试方法研究

氨基酸作为蛋白质的基本组成单位,是重要的生命物质,其单体碳同位素研究在生物地球化学、生态学、生物体代谢和环境科学等领域具有重要意义。该文优化了海参和海藻氨基酸提取和纯化流程,通过N新戊酰基-O-异丙酯(NPP)方法衍生化后,分别用气相色谱-质谱(GC-MS)和气相色谱-燃烧-同位素比值质谱(GC-C-IRMS)测试其浓度和碳同位素组成。结果显示,15种氨基酸单体的分离效果较好,回收率为46.4%~96.3%,各氨基酸在1.0~16.0µmol/L范围内线性关系良好(r^(2)为0.987~0.999)。15种氨基酸单体衍生物δ^(13)C值的标准偏差均小于0.30‰(n=10),在0.6~2.0 mmol/L浓度范围内δ^(13)C的平均误差为±0.24‰,方法检出限为0.6 nmol。海参和海藻样品各氨基酸单体δ^(13)C值的范围分别为-31.10‰~-8.58‰和-30.53‰~-13.76‰,标准偏差均在0.33‰以内,可满足生物体氨基酸单体碳同位素的测试精度需求。

硝酸异丙酯/甲醇/空气混合物层流燃烧速度的数值模拟

为了探究硝酸异丙酯(isopropyl nitrate,IPN)对甲醇/空气混合物层流预混火焰反应活性的影响,利用Cantera开源动力学软件对IPN/甲醇/空气混合物的层流燃烧速度展开模拟计算,并对主要中间产物的浓度分布和敏感反应进行分析。结果表明:IPN的添加有助于甲醇/空气混合物燃烧时贫燃区活性自由基(H、O、OH等)的增多、HO_(2)惰性组分的减少、火焰温度的升高及层流燃烧速度的加快。当IPN掺混比例超过10%后,对甲醇层流燃烧速度的促进作用逐渐减弱,富燃区出现抑制影响。纯甲醇/空气混合物中,HCO基的第三体单分子裂解反应(R103:HCO+M=CO+H+M)对层流燃烧速度的敏感性最强。随着IPN添加,在贫燃区中CO+OH=CO_(2)+H变得更重要,H自由基(R9:H+HO_(2)=H_(2)+O_(2))和O自由基(R10:HO_(2)+O=O_(2)+OH)的消耗反应对反应活性的抑制作用减弱。CH3O基是连接甲醇和IPN消耗反应路径中的关键中间组分。

孟鲁司特钠联合异丙托溴铵对老年COPD合并肺感染患者的影响分析

分析孟鲁司特钠联合异丙托溴铵对老年慢性阻塞性肺疾病(COPD)合并肺感染患者肺功能、血肌酐及炎性因子的影响。选取2021年7月—2022年7月期间北京市西城区平安医院收治的COPD合并肺感染老年患者112例,按照治疗方式不同将患者分为观察组(孟鲁司特联合异丙托溴铵治疗)与对照组(异丙托溴铵治疗),每组各56例,比较两组患者治疗前后治疗有效率、肺功能、血肌酐及炎性因子指标,以及不良反应发生情况。结果显示,观察组治疗总有效率显著高于对照组(P<0.05);治疗后,观察组一秒率(FEV_(1)/FVC)、第一秒呼气量占预计值百分比(FEV_(1)%pred)和每分钟最大通气量(MVV)均高于对照组,血肌酐水平低于对照组(P<0.05)。研究发现,孟鲁司特钠联合异丙托溴铵对老年COPD合并肺感染患者的疗效更佳,能快速缓解患者体征与临床症状,不良反应发生率低,可以显著改善患者机体的炎性因子水平、肺功能、血肌酐水平,值得临床应用。

A new way to synthesize benzoin isopropyl ether on Cu-Fe-hydrotalcite

An efficient synthesis of benzoin isopropyl ether with benzaldehyde and propanol in the presence of heterogeneous recyclable Cu-Fe-hydrotalcite catalyst has been explored. Cu-Fe-hydrotalcite was firstly successfully synthesized over Jahn-Teller effect of Cu^2＋. The catalytic test result showed that Cu-Fe-hydrotalcite could be used as a good catalyst in the synthesis of benzoin isopropyl ether. The highest conversion of ben- zaldehyde was 59.7% and the selectivity of benzoin isopropyl ether was nearly 100%. By this new method, not only was the cyanide poisoning avoided, but also the synthesis of benzoin isopropyl ether could be completed in one step instead of traditional two steps with both condensation and etherification.

ISOBARIC VAPOR-LIQUID EQUILIBRIUMS OF OCTANE-ETHYL ACETATE AND OCTANE-ISOPROPYL ACETATE SYSTEMS

The isobaric vapor-liquid equilibrium data of systems of ethyl acetate（1）-n-octane（2） andisopropyl acetate（1）-n-octane（2） were determined at 0.0709 MPa and 0.1013 MPa by using a modifiedRose-Williams still.The experimental data were tested for thermodynamical consistency and correlatedsatisfactorily with p-T equation of state and Wilson equation.

Synthesis of 2-Isopropyl Naphthalene Catalyzed by Et_3NHCl-AlCl_3 Ionic Liquids

In this paper, 2-isopropyl naphthalene has been synthesized by the reaction of naphthalene and isopropyl bromide, using triethylamine hydrochloride-aluminum chloride ionic liquid as the catalyst. The effect of the catalyst composition, the reaction time, the reaction temperature, the ionic liquid dosage, as well as the molar ratio of the reagents on the 2-isopropyl naphthalene yield was systematically investigated. The optimal reaction conditions cover: an AlCl3 to Et3NHCl ratio of 2.0, a reaction time of 3 h, a reaction temperature of 15.0 ℃, a volume fraction of ionic liquid to the mixture(isopropyl bromide, n-dodecane and n-hexane) of 9%, and a naphthalene/isopropyl bromide molar ratio of 4.0. Under the optimal reaction conditions, the conversion of isopropyl bromide reached 98% and the selectivity of 2-isopropyl naphthalene was equal to 80%. The test results verified good catalytic activity upon using Et3NHCl-AlCl3 ionic liquid as the catalyst for alkylation of naphthalene with isopropyl bromide. The activity of the ionic liquid remains unchanged after it has been recycled for 4 times.

Study on Synthesis and Polymerization of Mono (isopropylmaleate oyloxyl) Diisopropoxyl Dysprosium

Mono(isopropyl maleate-oyloxyl) diisopropoxyl dysprosium(DM) was synthesized by the reaction of dysprosium isopropoxide with maleic anhydride. Dy-containing polymer(PDM) was obtained by the solution polymerization of DM using 2, 2'-azobisisobutyronitrile (AIBN) as an initiator. The kinetic study on the polymerization shows that the polymerization of DM exhibits high apparent activation energy(96.3 kJ.mol(-1)), indicating that the activity of DM is low for polymerization. The kinetic equation of polymerization can be expressed as R-P = k(P)C(DM)(1.23)c(AIBN)(0.82). The polymeric solid material shows excellent heat-stability and strong characteristic fluorescence of Dy3+, (4)Fg(9/2) --> H-6(15/2) and F-4(9/2) --> H-6(13/2).

Catalytic Synthesis of Isopropyl Benzene over SO_4 ^(2-)/ZrO_ 2-MCM-41

Super acid catalyst SO4^2-/ZrO2 was introduced into pure silicone MCM-41 via the impregnation method and the catalyst samples obtained at different temperatures were characterized by means of XRD, IR, and Py-IR techniques. The selectively catalytic gas-phase flow reactions of benzene with propene over the catalyst samples were carried out in a made-to-measure high-pressure flow reactor equipped with a thermostat and a condenser. Effect of the preparative condition on the catalytic synthesis of isopropyl benzene over the catalyst samples was tested. The results show that SO4^2-/ZrO2-MCM-41 （ SZM-41 ） can be used as a catalyst for the title reaction, in which there are a higher conversion （97%） for the propene and a higher selectivity（93% ） for the isopropyl benzene.

Extraction Separation of Scandium，Iron and Lutetium with Isopropyl Phosphonic Acid Mono（1－hexyl－4－ethyl）OctylEster

The extraction and stripping of scandium from its sulfate solutions by isopropyl phosphonic acid mono (1-hexyl-4-ethyl) octyl ester (PT-2, HL) diluted with n-hexane are reported. A high efficiency of separation between scandium, iron and lutetium can be achieved by controlling aqueous acidity. Different mechanisms of Sc3+ with PT-2 in various acid range have been proposed.At lower aqueous acidity, it is a cation exchange reaction, while at higher acidity. a solvation reaction was ascertained. Its IR and NMR spectra have been discussed. The effect of temperature on extraction of Sc3+ was observed and thermodynamic functions were calculated.

A Temperature-sensitive Hydrogel Refolding System: Preparation of Poly(N-isopropyl acrylamide) and Its Application in Lysozyme Refolding

Temperature-sensitive hydrogel—poly(N-isopropyl acrylamide) (PNIPA) was prepared and applied to protein refolding. PNIPA gel disks and gel particles were synthesized by the solution polymerization and inverse suspension polymerization respectively. The swelling kinetics of the gels was also studied. With these prepared PNIPA gels, the model protein lysozyme was renatured. Within 24h, PNIPA gel disks improved the yield of lysozyme activity by 49.3% from 3375.2U·mg^-1 to 5038.8U·mg^-1. With the addition of faster response PNIPA gel beads, the total lysozyme activity recovery was about 68.98% in 3h, as compared with 42.03% by simple batch dilution. The novel refolding system with PNIPA enables efficient refolding especially at high protein concentrations. Discussion about the mechanism revealed that when PNIPA gels were added into the refolding buffer, the hydrophobic interactions between denatured proteins and polymer gels could prevent the aggregation of refolding intermediates, thus enhanced the protein renaturation.

Synthesis of Methyl Isopropyl Ketone and Diethyl Ketone over Ni-Na/ZrO_2-MnO_2-ZnO Catalyst

ZrO2-MnO2-ZnO supports were prepared by the co-precipitation method,and then Ni-Na/ZrO2-MnO2-ZnO catalysts were prepared by the impregnation method.In this paper,the reactions to synthesize methyl isopropyl ketone and diethyl ketone by the one-step synthesis method over this catalyst were studied,and meanwhile,the impact of the catalyst preparation conditions and the reaction conditions on catalyst performance was also investigated.It was observed that under the conditions when Ni loading was 25%,calcination temperature was 400℃ and reduction temperature was 410℃,this catalyst had good catalytic performance on the reaction.The suitable reaction conditions were achieved:reaction temperature was 400℃;reaction at atmospheric pressure;liquid hourly space velocity of raw material of 0.5 h 1 ;and the molar ratio of(methanol)/(methyl ethyl ketone)/(water) was equal to 1/1/1.Under such conditions,the conversion of methyl ethyl ketone could achieve 41.7%,and the overall selectivity of methyl isopropyl ketone and diethyl ketone could achieve 83.3%,which was comparable to the conversion of 38.1% and the selectivity of 82.2% achieved by using palladium as the active material.The good stability made this catalyst have good prospects for industrial application.

Indirect Determination of Ascorbic Acid with Ammonium Sulfate and Isopropyl Alcohol by Extraction-flotation of Copper

A new method of indirect determination of ascorbic acid(Vc) with ammonium sulfate and isopropyl alcohol by extraction-flotation of copper is studied in this paper. It shows that a small amount of Cu(Ⅱ) can be reduced to Cu( Ⅰ ) by Vc, then Cu(Ⅰ) reacted with the SCN-, which precipitated on the interface of isopropyl alcohol and H2O. A good linear relationship is observed between the flotation yield(E) of Cu( Ⅱ) and the amount of Vc. The detection limit for Vc is 1.76μg/mL. The method is simple, rapid (5 min), but suffers from little interference of common anions and cations. It has been successfully applied for the determination of Vc in fruits.

QSAR Study of the Action Strength of DOM of Phenyl-isopropyl-amine Dopes Using MLR and BP-ANN

Based on Hall et al. electrotopological state indices（EK） of atom types, two quantitative structure-activity relationship（QSAR） models were developed to estimate and predict the action strength（W） of D（OM）（dimethoxy-methyl-amphetamine） for 18 phenyl-isopropyl-amine dopes（PPAD） through linear method（multiple linear regression, MLR） and non-linear method（Back propagation artificial neural network, BP-ANN）. On the basis of EK, the optimal three-parameter（E14, E9, E7） QSAR model of W for 18 PPAD was constructed. The traditional correlation coefficient（R^2） and cross-validation correlation coefficient（Rcv^2） are 0.878 and 0.815, respectively. The result demonstrates that the model is highly reliable（from the point of view of statistics） and has good predictive ability by using R^2, Rcv^2, VIF, FIT, AIC and F tests. Form the three parameters of the model, it is known that the dominant influence factors of inhibited activity are the molecular structure fragments： =CH–（secondary carbon）, =C〈（tertiary carbon atom） in aromatic ring and –O–（phenol ether bond）. The results showed that the structure parameters E14, E9 and E7 have good rationality and efficiency for the W of phenyl-isopropyl-amine dope（PPAD） analogues. A BP-ANN with 3-3-1 architecture was generated by using three electrotopological state index descriptors（E14, E9, E7） appearing in the MLR model, the above descriptors were inputs and its output was action strength（W）. The nonlinear BP-ANN model has better predictive ability compared to the linear MLR model with R^2 and Rcv^2 of leave-one-out（LOO） to be 0.995 and 0.994, respectively. The regression method gave support to the neural network with physical explanation, which offers a more accurate model for QSAR. Those models can be used in the rational design of higher stimulating extent PPAD, which provide meaningful reference information to improve the detection methods of PPAD.

Analysis and Characterization of Isopropyl Carbanilate Herbicide and Its Photoproducts

The phototransformation of the herbicide Isopropyl carbanilate (IPC) has been investigated under UV light. Irradiation of the herbicide at room temperature in aqueous and organic solvents such as hexane and methanol afforded new photo-products formed as a consequence of various processes including photo-Fries rearrangement, ring solvolysis, hydrolysis of the amide/carbamoyl and ester bonds, ring coupling and polymerization. The percentage remaining of the herbicide as a function of time was followed periodically starting from zero time up to three hours. Analyses were performed by GC-FID equipped with a semipolar glass column operated at 170?C. The rate of photo disappearance of IPC under controlled lab condition followed 1st order kinetics and found to be solvent dependent in the manner of non polar > polar solvents. The photo-products were successfully separated by GC and preparative TLC (Silica gel F-254) and were identified using either GC-MS and/or MS. Identifications were assigned on the bases of molecular ions, mass fragmentation pattern and whenever possible by comparison with the mass spectra of literature analogues.

Hydrothermally Synthesizing Nanospheres of Pd Loaded TiO_2 for Photocatalytically Reducing CO_2 in Isopropanol to Isopropyl Formate

Photocatalytic reduction of CO2 was carried out on villiform spherical catalysts of Pd-TiO2 in isopropanol solution.The catalysts were synthesized by hydrothermal method,their structures,morphologies and optical absorption properties were characterized by X-ray diffraction（XRD）,energy dispersive X-ray spectroscopy（EDS）,scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,highresolution transmission electron microscopy（HRTEM）and UV-vis absorption spectroscopy（UV-vis）.The photocatalytic activities with different loading amounts and morphologies were evaluated for determining the dominant effect and optimizing the catalyst preparation.Based on a villiform spherical TiO2 with the largest specific surface area in our experiments,we prepared a set of catalysts with various loading amounts of palladium and tested them by bubbling CO2 through the slurry of catalyst and isopropanol.The highest formation rate of isopropyl formate was 276.6μmol/g？cat/h.Eventually we proposed the reaction mechanism.

Thermo- and pH-Responsive Hydrogels Based on N-Isopropylacrylamide and Allylamine Copolymers

The thermo- and pH-responsive hydrogels were synthesized via copolymerization of N-isopropylacrylamide and al-lylamine hydrochloride monomers. The equilibrium swelling of the hydrogels was studied as a function of temperature and pH in aqueous solutions. It was shown that controlled alteration of the hydrogel phase transition temperature can be achieved by changing their composition and pH of the environment. Increase in content of hydrophilic allylamine from 10 to 60 wt% in monomer mixture causes a shift of the phase transition temperature from 35oC to 47oC. Hydrogels with N-isopropylacrylamide/allylamine hydrochloride mass ratio of 3:2 show the highest pH-response. Values of average molecular weight between polymer cross-links, , and Flory parameter, χ, were calculated using temperature dependences of the equilibrium swelling of the synthesized hydrogel.