亲水作用色谱柱与阳离子交换树脂柱结合分离无机离子（英文）

A combination of hydrophilic interaction chromatographic(HILIC) column and a weakly acidic cation-exchange resin(WCX) column was used for simultaneous separation of inorganic anions and cations by ion chromatography(IC).Firstly,the capability of HILIC column for the separation of analyte ions was evaluated under acidic eluent conditions.The columns used were SeQuant ZIC-HILIC(ZIC-HILIC) with a sulfobetaine-zwitterion stationary phase(ZIC-HILIC) and Acclaim HILIC-10 with a diol stationary phase(HILIC-10).When using tartaric acid as the eluent,the HILIC columns indicated strong retentions for anions,based on ion-pair interaction.Especially,HILIC-10 could strongly retain anions compared with ZIC-HILIC.The selectivity for analyte anions of HILIC-10 with 5 mmol/L tartaric acid eluent was in the order of I-> NO-3 > Br-> Cl-> H2PO-4.However,since HILIC-10 could not separate analyte cations,a WCX column(TSKgel Super IC-A/C) was connected after the HILIC column in series.The combination column system of HILIC and WCX columns could successfully separate ten ions(Na+,NH+4,K+,Mg2+,Ca2+,H2PO-4,Cl-,Br-,NO-3 and I-) with elution of 4 mmol/L tartaric acid plus 8 mmol/L 18-crown-6.The relative standard deviations(RSDs) of analyte ions by the system were in the ranges of 0.02%-0.05% in retention times and 0.18%-5.3% in peak areas through three-time successive injections.The limits of detection at signal-to-noise ratio of 3 were 0.24-0.30 μmol/L for the cations and 0.31-1.2 μmol/L for the anions.This system was applied for the simultaneous determination of the cations and the anions in a vegetable juice sample with satisfactory results.     

水为洗脱剂的静电离子色谱-增强电导检测法测定常见的无机阴离子（英文）

To enhance the conductivity detection sensitivity of common anions(Na-anions) in electrostatic ion chromatography(EIC) by elution with water,a conductivity enhancement column packed with strong acid cation exchange resin in the H-form was inserted between an octadecyl silane(ODS)-silica separation column modified with zwitterionic surfactant(CHAPS: 3-{(3-cholamidopropyl)-dimethylammonio}propanesulfonate) and a conductivity detector.Specifically,the Na-anion pairing is converted to H-anion pairing after the EIC separation and then detected sensitively by the conductivity detector.The effects of conductivity enhancement and suppression in the EIC by the enhanced conductivity detection were characterized for the common strong acid anions such as SO2-4,Cl-,NO-3,I-and ClO-4 and weak acid anions such as F-,NO-2,HCOO-,CH3COO-and HCO-3.For the conductivity enhancement effect in the EIC,it is found that the conductivity of measured for all strong acid anions(Na-anions) was enhanced according to the theoretical conductivity predicted for H-anions and that of the measured for weak acid anions was suppressed depending on their pKa of H-anions.For the calibration linearity in the EIC,the strong acid anions were linear(r2=0.99-1.00) because the degree of dissociation is almost 1.0 over all the concentration range and that of the weak acid anions was non-linear because the degree of dissociation decreased by increasing the concentration of the weak acid anions.In conclusion,the EIC by enhanced conductivity detection was recognized to be useful only for the strong acid anions in terms of conductivity detection and calibration linearity.     

离子排斥色谱结合光度检测的水质监测系统用于测定离子型营养物（英文）

A unified ion-exclusion chromatography(IEC) system for monitoring anionic and cationic nutrients like NH + 4,NO 2,NO 3,phosphate ion,silicate ion and HCO 3 was developed and applied to several environmental waters.The IEC system consisted of four IEC methodologies,including the IEC with ultraviolet(UV) detection at 210 nm for determining NH + 4 on anion-exchange separation column in OH form connected with anion-exchange UV-conversion column in I form in tandem,the IEC with UV-detection at 210 nm for determining simultaneously NO 2 and NO 3 on cation-exchange separation column in H + form,the IEC with UV-detection at 210 nm for determining HCO 3 on cation-exchange separation column in H + form connected with anion-exchange UV-conversion column in I form in tandem,and the IEC with visible-detection based on molybdenum-blue reaction for determining simultaneously silicate and phosphate ions on cation-exchange separation column in H + form.These IEC systems were combined through three manually-driven 6-port column selection valves to select each separation column to determine selectively the ionic nutrients.Using this sequential water quality monitoring system,the analytical performances such as calibration linearity,reproducibility,detection limit and recovery were also tested under the optimized chromatographic conditions.This novel water quality monitoring system has been applied successfully for the determination of the ionic eutrophication components in sub-urban river waters.     

同时测定无机离子的改良离子色谱法在河水和废水质量监控中的应用（英文）

In this study,our recent work on advanced ion chromatographic methods for the simultaneous determination of inorganic ionic species such as common anions(SO2-4,Cl-and NO-3) and cations(Na+,NH+4,K+,Mg2+,and Ca2+),nutrients(phosphate and silicate) and hydrogen ion/alkalinity are summarized first.Then,the applications using these methods for monitoring environmental water quality are also presented.For the determination of common anions and cations with nutrients,the separation was successfully performed by a polymethacrylate-based weakly acidic cation-exchange column of TSKgel Super IC-A/C(Tosoh,150 mm×6.0 mm i.d.) and a mixture solution of 100 mmol/L ascorbic acid and 4 mmol/L 18-crown-6 as acidic eluent with dual detection of conductivity and spectrophotometry.For the determination of hydrogen ion/alkalinity,the separation was conducted by TSKgel ODS-100Z column(Tosoh,150 mm×4.5 mm i.d.) modified with lithium dodecylsulfate and an eluent of 40 mmol/L LiCl/0.1 mmol/L lithium dodecylsulfate/0.05 mmol/L H2SO4 with conductivity detector.The differences of ion concentration between untreated and treated wastewater showed the variation of ionic species during biological treatment process in a sewage treatment plant.Occurrence and distribution of water-quality conditions were related to the bioavailability and human activity in watershed.From these results,our advanced ion chromatographic methods have contributed significantly for water quality monitoring of environmental waters.     

离子色谱法测定啤酒中的F~-、CI~-、SO_4~(2-)、NO_3~-和PO_4~(3-)

建立了以ASII-HC型阴离子交换柱分离、NaOH溶液为淋洗液、甲醇为有机改进剂、化学抑制电导检测测定啤酒中的F~-、cl~-、SO_4~(2-)、NO_3~-和PO_4~(3-)的离子色谱方法。各被测离子的线性关系良好,相关系数为0.9778～0.9991,测定结果的相对标准偏差为0.02％～3.60％,样品回收率为97.88％～103.80％。     

Ca2Y7.9（SiO4）6O2-0.5xFx:Eu0.1（3+,2+）荧光粉的合成和发光特性

采用高温固相反应法在弱还原气氛下制备了Ca2Y7.9(SiO4)6O2-0.5xFx:Eu(2+,3+)0.1(x=0～4)系列荧光粉。晶胞参数a,c和晶胞体积V均随着F-置换量的增加呈线性减小,晶胞参数a和c的变化率相近。荧光体中Eu2+和Eu3+共存,Eu2+3d5/2与Eu3+3d5/2电子结合能分别为1128.4和1136.3 eV,Eu2+的3d5/2与3d3/2的电子结合能差为28.4 eV。Eu2+和Eu3+的3d5/2态XPS峰面积比为6.9∶1。激发光谱由Eu3+的两个电荷迁移(CTS)带和f-f跃迁激发线组成,x=0,1的试样中出现了Eu2+的f-d跃迁强激发谱带。激发到Eu3+的电荷迁移态或激发Eu2+,除了来自Eu3+的5D0能级的发射之外,还观察到了5D1能级的强发射和5D2能级的弱发射,并且激发Eu2+时5D1→7F4发射强度超过5D0→7F2,没有出现Eu2+的明显发射,Eu2+对Eu3+发光起到很好的敏化作用。5DJ(J>0)高能级发射来自4f格位的Eu3+发光中心,Eu2+的敏化起关键作用。Eu3+在4f和6h两种格位的分布比为4∶6。     

离子色谱法同时测定化妆品中的铵和6种烷基胺

建立同时测定化妆品中铵和6种烷基胺的离子色谱(IC)分析方法。优化了色谱条件和样品前处理方法,样品经100 mmol/L乙酸-20%(v/v)乙腈溶液浸提,固相萃取(SPE)柱去除阴离子、中和氢离子后进样测定。考察了提取溶液的pH、有机溶剂和共存离子对测定结果的影响。分析方法的线性范围为0.3～15 mg/L,检出限为2.1～7.9 mg/kg,定量限为7～26 mg/kg。采用建立的分析方法测定了清洗、柔肤、祛斑、防晒、烫发、染发和育发类化妆品的加标回收率的范围在80.2%～109.2%之间,相对标准偏差(RSD)的范围为0.5%～3.1%。方法选择性好,灵敏度高,抗干扰强,用于实际样品测定结果准确。     

Determination of No2 -/NO3 - Mixtures by Titration with Ascorbic Acid

Abstract

The analysis of nitrite-nitrate mixtures by indirect titration with ascorbic acid performed before and after passage through a reducing Cd column is proposed and discussed with particular reference to experimental conditions, calculation scheme and concentration ranges.     

离子色谱-抑制电导检测法同时测定草甘膦母液中的含磷副产物及无机阴离子

建立了一种抑制电导检测-离子色谱(IC)同时测定草甘膦生产工艺中母液里的草甘膦及其副产物、无机阴离子的方法。样品经过滤后直接进样,色谱条件: IonPac AS11-HC分离柱(250 mm×4 mm)和IonPac AG11-HC保护柱(50 mm×4 mm),在线淋洗液发生器KOH梯度淋洗,流速1.0 mL/min,采用抑制电导检测。草甘膦、甲基草甘膦、六甲基磷酰三胺(HMPA)、增甘膦、亚磷酸、磷酸、Cl~和SO2~4的线性范围分别为0.1～20 mg/L、0.1～20 mg/L、0.1～50 mg/L、0.25～50 mg/L、0.05～20 mg/L、0.2～50 mg/L、0.02～20 mg/L和0.05～50 mg/L,相关系数分别为0.9995、0.9993、0.9999、0.9998、0.9999、0.9985、0.9999和0.9980,加标回收率为93.7%～104.0%,相对标准偏差均小于2.5% (n=7),检出限(以信噪比(S/N)=3计)为0.002～0.025 mg/L。该方法用于草甘膦生产工艺中母液里草甘膦及其含磷副产物和无机阴离子的测定,结果令人满意。     

离子色谱-抑制型电导检测法同时测定食品级润滑油中的3种无机阴离子

建立了离子色谱-抑制型电导检测同时测定食品级润滑油中Cl^-、NO₃^-、SO₄^2- 3种代表性无机阴离子的方法。样品经50%(v/v)甲醇水溶液超声提取,离心后所得下层水相用0.22 μm混合纤维过滤膜净化,以15 mmol/L KOH溶液为淋洗液,采用抑制型电导检测器进行检测,外标法定量。在上述条件下,Cl^-、NO₃^-、SO₄^2- 3种无机阴离子在0.10~20.00 mg/L范围内具有良好的线性关系(R²>0.999);检出限(S/N=3)为0.01~0.03 mg/kg;在1.00、5.00、10.00 mg/kg添加水平下,实际样品中3种阴离子的加标回收率为90.0%~103.6%,相对标准偏差为2.8%~5.7%。结果表明,该方法无需燃烧、灰化油相基质等繁琐耗时的前处理过程,可以快速、准确定量测定食品级润滑油中Cl^-、NO₃^-、SO₄^2- 3种无机阴离子的含量,适用于润滑油等油品中痕量无机阴离子的同时分离与测定。     

抑制型离子色谱法测定蔬菜中的NO2-和NO3-

用抑制型离子色谱法定量测定了NO2-和NO3-.两种阴离子在最佳色谱条件下,8 m in内达到基线分离.对于NO2-,检出限为0.002 mg/L,相对标准偏差为2.58%,线性范围0.2 mg/L~20 mg/L,相关系数0.999 6.对于NO3-,检出限为0.011 mg/L,相对标准偏差为2.01%,线性范围0.3 mg/L~30 mg/L,相关系数0.999 2.该法用于蔬菜中NO2-和NO3-的测定,结果良好.     

离子色谱法同时测定土壤中Cl-、SO42-和 NO3-

利用离子色谱法同时测定土壤中的Cl^-、SO4^2-、NO3^-三种无机阴离子。采用30 mmol/L KOH淋洗液在1.2 mL/min流速下对Cl^-、SO4^2-、NO3^-三种无机阴离子进行分离测定,混合标准溶液的相对标准偏差为0.16%~0.84%,三种阴离子的线性范围都在0~150 mg/L,线性相关系数均大于0.999。三种阴离子的检出限分别是0.062、0.096和0.064 mg/L。对四种国家标准物质的测定结果表明(n=9),测定值与标准值一致,相对标准偏差(RSD)<3%,三种阴离子的加标回收率为95.6%~109%。采用离子色谱法测定土壤中的Cl^-、SO4^2-、NO3^-三种无机阴离子,方法简便、快捷、无污染,对人体无任何伤害,真正实现了绿色化学的分析要求。在6 min以内完成分析,适合大批量土壤水溶盐阴离子的测定。     

Synthesis and crystal structure of New Amminecopper(II) Nitrates: [Cu(NH3)2](NO3)2 and [Cu(NH3)](NO3)2

[Cu(NH₃)₂](NO₃)₂ ( I ) and [Cu(NH₃](NO₃)₂ ( II ) were synthesized by interaction of molten NH₄NO₃ with [Cu(NH₃)₄](NO₃)₂ and Cu(NO₃)₂ · 3 H₂O, respectively, at 180 to 195°C for 24 hr. According to X-Ray single crystal analysis, I is orthorhombic (sp. gr. Pbca) with a = 5.678(1), b = 9.765(2), c = 11.596(2) Å, Z = 4, R = 0.060; II is monoclinic (sp. gr. P2₁/c) with a = 6.670(1), b = 8.658(2), c = 9.661(2) Å, β = 101.78(2)°, Z = 4, R = 0.027. In both structures, the nearest coordination environment of Cu is a slightly distorted square formed by N (from NH₃) and O atoms (from NO₃ groups). The structure of I consists of centrosymmetrical [Cu(NH₃)₂](NO₃)₂ molecules linked by hydrogen bonds. The Cu? N and Cu? O distances are 1.98 and 2.01 Å, respectively. In II , the Cu? N distance is 1.95 Å, the Cu? O distances are 1.96, 2.02, and 2.03 Å. The [CuO₃NH₃] squares are connected by NO₃ bridges into zigzag chains, which are linked into layers by longer Cu? O interactions (2.31 Å). Obviously, the layers are additionally strengthened and held together by hydrogen bonds.     

Sensitive determination of aliphatic amines by high-performance liquid chromatography with a new fluorogenic probe 3-(4-fluorinebenzoyl)-2-quinoline carboxaldehyde

A new fluorogenic reagent 3-(4-fluorinebenzoyl)-2-quinoline carboxaldehyde (FBQCA) has been synthesized and used as a derivatizing reagent for the determination of aliphatic amines with HPLC. The reagent is nonfluorescent, but forms highly fluorescent isoindole upon the reaction with primary amines in alkaline medium. Eleven amine derivatives were baseline separated in 8 min using a gradient elution on a C(8) column and detected with fluorescence detection at lambda(ex)/lambda(em) = 480/546 nm. The detection limits were in the range of 0.5-2 nM (S/N = 3). The proposed method has been successfully applied to the analysis of aliphatic amines in food and environmental samples, including white wine, soybean oil, soil, and tap water with satisfactory recoveries in the range of 94-106%.