一种新型比色荧光双通道水相检测氰根离子的化学传感器

合成了一种新型的,能在含水介质中比色荧光双通道单一选择性识别CN^-的传感器分子1-羟基萘甲叉酰肼乙基-3-羟基萘甲叉酰肼甲基苯并咪唑溴鎓盐(J1)。 在J1的DMSO/H₂O (体积比3:2)HEPES 的缓冲体系(pH=7.2)中分别加入F^-、Cl^-、Br^-、I^-、AcO^-、HSO₄^-、ClO₄^-、H₂PO₄^-、SCN^-和CN^-等阴离子后,只有CN^-的加入会使得溶液颜色发生明显的变化,由无色变为深黄色。 相应地在J1的DMSO/H₂O (体积比4:1)HEPES的缓冲体系(pH=7.2)中加入CN^-,溶液发出明亮的黄色荧光。 这一识别过程,不会受到其它阴离子的干扰。 紫外-可见光谱的最低检测限为1.57×10^-7 mol/L,检测线性范围为3.875×10^-4~2.15×10^-2 mol/L。 荧光光谱的最低检测限为4.63×10^-6 mol/L,检测线性范围为0.8×10^-4~1.60×10^-3 mol/L。 此结果表明,J1是一种良好的用于识别 CN^-的化学传感器,在含水介质中对CN^-具有选择性好、灵敏度高以及抗干扰性强的识别性能。 与此同时,基于J1对于CN^-的高选择性识别我们制备了CN^-的检测试纸,该试纸能够方便、快捷、准确地检测水中的CN^-。     

Anion recognition with porphyrin-bottomed tetraurea receptors

Three tetraurea-appended porphyrin-derived anion receptors were synthesized and were found to efficiently encapsulate various anions with high association constants of up to 1.1×10⁸ L/mol.     

两种新型F-荧光化学传感器的合成及其性质研究

本文设计合成了N⁶-对甲苯磺酰胺腺嘌呤(I)和邻苯二对甲苯磺酰胺(Ⅱ)两种主体化合物.通过对其与阴离子物种之间相互作用的研究发现,它们在乙腈溶液中和Cl^-、Br^-、NO₃^-、NO₂^-、HSO₄^-、Ac^-、F^-几种阴离子相互作用时,仅对F^-具有专一的选择性识别作用.F^-离子可使I和Ⅱ主体的荧光吸收猝灭并发生红移.通过试验证明,F^-离子和I、Ⅱ主体的识别作用机理是因形成了激基缔合物.     

A carbazole-hemicyanine dye based ratiometric fluorescent probe for selective detection of bisulfite (HSO3−) in cells and C. elegans

A colorimetric and ratiometric fluorescent probe for selective detection of HSO₃^- based on the 1,4-nucleophilic addition reaction was successfully synthesized and applied to the detection of exogenous HSO₃^- in Hela cells and C. elegans.     

Influence of operating conditions on the retention of phosphate in water by nanofiltration

The objective of this study was to investigate the retention of phosphate anions, H₂PO₄⁻ and HPO₄²⁻, by nanofiltration. The first part of this study deals with the characterisation of the NF200 membrane used in permeation experiments with aqueous solutions of neutral organic and charged inorganic solutes. In the second part the effects of feed pressure, ionic strength, concentration and pH on the retention of phosphate anions were investigated. Results show that the membrane is negatively charged, its pore radius is around 0.5 nm and the retention order for the salts tested was R(Na₂SO₄) > R(NaCl) > R(CaCl₂). The retentions of phosphate anions are in the order of 85% for H₂PO₄⁻ and 96% for HPO₄²⁻. They are relatively high when compared to retentions of other anions with the same charge. The retentions of phosphate anions, particularly the monovalent species, depend on the chemical parameters (feed concentration, ionic strength, and pH) and applied pressure. The experimental data were analysed using the Speigler–Kedem model and the transport parameters, i.e., the reflection coefficient (σ) and solute permeability (P_s) have been determined.     

Chuan-Cai Fan;Li-Jin Xu;Han-Yuan Gong;%T Neutral C–H bond vs. electron pair of N（sp~2）： A binding site effect study of macrocycle anion receptor

To evaluate the effect of neutral C–H bond or electron pair of nitrogen atom with sp2hybridization（N（sp2）） involving into the same chemical environment for anion binding, two analogous tetracationic imidazolium macrocycles, namely cyclo[2]（2,6-bis-（1H-imidazol-1-yl）pyridine） [2]（1,3-dimethylenebenzene）（14＋）, and cyclo[2]（2,6-bis-（1H-imidazol-1-yl）pyridine）[2]（2,6-di methylenepyridine）（24＋）were studied in detail as small inorganic anion receptors. The guest anions with different shapes are Cl,N3, NO3, and H2PO4. The host–guest interactions were characterized via1 H NMR spectroscopy,electrospray ionization mass spectrometry（ESI-MS） and single crystal X-ray crystallography. The results implied that macrocyclic hosts with similar backbone but two distinct binding sites（14＋with neutral C–H vs. 24＋with N（sp2）） vary markedly in their response to anions, including the binding modes and association constants. The finding will serve to the construction of new anion receptors, even improve insights into the anion binding process in biology.     

功能化离子液体修饰多壁碳纳米管固定化Candida antarctic lipase B

将带不同阴离子（Br^-、BF₄^-、PF₆^-、H₂PO₄^-）的咪唑离子液体修饰改性的多壁碳纳米管（MWNTs）作为一种全新的载体通过物理吸附法固定化褶皱假丝酵母脂肪酶B（CALB）,对其酶学性能进行测试。并通过透射电镜、拉曼光谱、热重分析、X射线光电子能谱对修饰前后的MWNTs进行表征,研究材料表面修饰对酶学性能的影响。研究结果表明,经过离子液体表面修饰后的MWNTs固定化CALB具有更高的比活力,耐受性（高温、高pH值）、热稳定性和重复使用性也得到进一步增强;离子液体中不同的阴离子对修饰MWNTs固定化酶的酶学性能有显著影响,其中以PF₆^-为阴离子的固定化酶比活力最高,比未修饰的MWNTs提高了5倍。固定化酶的动力学参数分析表明离子液体的引入增强了酶与底物之间的亲和力,从而增强了酶的活性。     

Comparison of Photochemical Reactions of m-Cresol in Aqueous Solution and in Ice

We compared the photochemical reaction of m-cresol containing OH precursors such as H₂O₂, NO₂^- and NO₃^- in aqueous solution with those in ice. The results show that the conversion rate of m-cresol in aqueous solution was higher than that in ice. H₂O₂, NO₂^- and NO₃^- all accelerated the photoconversion of m-cresol in both aqueous solution and ice. The photochemical reactions of m-cresol obeys the first order kinetics equation. According to the photoproducts identified by GC-MS, we proposed that hydroxylation and nitration reactions occurred in both aqueous solution and ice. Coupling reaction was common in ice, however, in aqueous solution it was found only in UV system. Our results suggest that the photochemical reactions of m-cresol were different in aqueous solution and in ice.     

亚胺型比色探针的制备及阴离子识别性能研究

合成了两种亚胺型阴离子识别受体:2-[(2-羟基-5-硝基亚苄基)氨基]4-硝基苯酚(R1)和2-[(蒽-9-亚甲基)氨基]-4-硝基苯酚(R2),其结构经核磁氢谱和红外表征.在紫外光谱实验中,受体R1和R2分别在乙腈和DMSO溶液中可以高选择性识别F-,AcC-和H2PO4-,同时观察到明显的颜色改变.实验结果表明,...     

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。     

十四烷基二甲基苄基氯化铵萃取Au(CN)2-的微观机理

通过萃取平衡、傅里叶变换红外光谱及分峰技术研究了季铵盐十四烷基二甲基苄基氯化铵(TDM-BAC)-磷酸三丁酯(TBP)-正庚烷体系萃取Au(CN)₂^-的机理及过程.提出了萃合物的结构模型是基于氢键的超分子体系,组成为[R₄N⁺]·[Au(CN)₂^-]·4H₂O·4TBP.当有机相金浓度大于3g·L^-1时,有机相中存在聚集现象.通过激光光散射技术测定了有机相中反向胶团的大小,表明萃取过程是分散在水相中的胶团在协萃剂(或助表面活性剂)作用下溶入有机相,转型为反向胶团或微乳液(W/O型)聚集状态.     

Temperature dependence of adlayers on Pt(1 1 1) and Au(1 1 1) in a sulfuric acid solution studied by in situ IRAS

Temperature dependence studies of adsorption of sulfuric acid species on Pt(1 1 1) and Au(1 1 1) electrodes were carried out using in situ infrared reflection absorption spectroscopy. A temperature-dependent shift of the interconversion potential between HSO₄⁻/H₃O⁺ and H₂SO₄ on a Pt(111) electrode was observed. A temperature-dependent frequency shift of the absorption bands of HSO₄⁻ was also observed on both Pt(1 1 1) and Au(1 1 1) electrodes in the potential region where a √3×√7 structure evolved. Modelling experiments in ultrahigh vacuum revealed that ordering of the overlayer water molecules played an important role in the frequency of the absorption bands of HSO₄⁻.     

Pd2X2(dpm)2(X＝NCO-,CH3CO2-,SCN-,NO3-;dpm＝Ph2PCH2PPh2配合物与H2S反应的NMR研究

采用NMR方法考察了室温和低温(-78～60℃)下Pd₂X₂(dpm)₂(X=NCO^-,CH₃CO₂^-,SCN^-和NO₃^-,dpm=Ph₂PCH₂PPh₂)与H₂S在CD₂Cl₂或CDCl₃中的反应。结果表明,在X=NCO^-和CH₃CO₂^-的情况下,H₂S优先与这些Pd配合物的阴离子作用生成相应的共轭酸HX和Pd₂(SH)₂(dpm)₂,后者在H₂S存在下又进一步转化为Pd₂(SH)₂(dpm)₂(μ-S);当X=SCN^-和NO₃^-时,反应则生成结构可能为[Pd₂(H)(SH)(μ-SH)(dpm)₂]⁺的双核Pd配合物。     

无机盐活化剂-氨基酸盐基溶液捕集温室气体CO2

将无机盐K₃PO₄、K₂HPO₄和KH₂PO₄作为活化剂,分别添加于氨基乙酸盐溶液中,形成CO₂活化吸收剂,采用膜接触器 再生循环装置,评价和比较了氨基乙酸盐和活化吸收剂捕集CO₂的性能,研究了活化剂的浓度、气液流速等因素对总体积传质系数、传质通量和捕集率的影响。结果表明,磷酸盐活化剂在氨基乙酸盐吸收剂中,对CO₂的捕集均产生影响,活化效应存在PO₄^3－＞HPO₄^2－＞H₂PO₄^－的规律;添加少量活化剂的作用比添加较多量的活化作用大;活化吸收剂的捕集率明显大于非活化吸收剂;膜吸收流体力学状态的改变,能够改善膜接触器传质性能,增大传质通量,但增大的程度有限。     

The electrolyte NRTL model and speciation approach as applied to multicomponent aqueous solutions of H2SO4, Fe2(SO4)3, MgSO4 and Al2(SO4)3 at 230–270 °C

This work presents chemical modeling of solubilities of metal sulfates in aqueous solutions of sulfuric acid at high temperatures. Calculations were compared with experimental solubility measurements of hematite (Fe₂O₃) in aqueous ternary and quaternary systems of H₂SO₄, MgSO₄ and Al₂(SO₄)₃ at high temperatures. A hybrid model of ion-association and electrolyte non-random two liquid (ENRTL) theory was employed to fit solubility data in three ternary systems H₂SO₄–MgSO₄–H₂O, H₂SO₄–Al₂(SO₄)₃–H₂O at 235–270 °C and H₂SO₄–Fe₂(SO₄)₃–H₂O at 150–270 °C. Employing the Aspen Plus™ property program, the electrolyte NRTL local composition model was used for calculating activity coefficients of the ions Al³⁺, Mg²⁺ Fe³⁺ and SO₄²⁻, HSO₄⁻, OH⁻, H₃O⁺, respectively, as well as molecular species. The solid phases were hydronium alunite (H₃O)Al₃(SO₄)₂(OH)₆, hematite Fe₂O₃ and magnesium sulfate monohydrate (MgSO₄)·H₂O which were employed as constraint precipitation solids in calculating the metal sulfate solubilities. A correlation for the equilibrium constants of the association reactions of complex species versus temperature was implemented. Based on the maximum-likelihood principle, the binary interaction energy parameters for the ionic species as well as the coefficients for equilibrium constants of the reactions were obtained simultaneously using the solubility data of the ternary systems. Following that, the solubilities of metal sulfates in the quaternary systems H₂SO₄–Fe₂(SO₄)₃–MgSO₄–H₂O, H₂SO₄–Fe₂(SO₄)₃–Al₂(SO₄)₃–H₂O at 250 °C and H₂SO₄–Al₂(SO₄)₃–MgSO₄–H₂O at 230–270 °C were predicted. The calculated results were in excellent agreement with the experimental data.     

离子色谱法同时测定火场爆炸残留物中9种典型阴离子

建立了离子色谱（IC）同时测定火场爆炸残留物中9种典型阴离子（Cl^-、NO₂^-、ClO₃^-、NO₃^-、CO₃^2-、SO₄^2-、S₂O₃^2-、SCN^-、ClO₄^-）的分析方法。使用高容量阴离子交换柱IonPac AS20（250 mm×4 mm）分离,以氢氧化钾（KOH）溶液为流动相,梯度淋洗,进样量为20 μL,柱温为40℃,流速为1.20 mL/min,在25 min内完成了9种典型阴离子的分离分析。9种阴离子在各自的范围内均呈现良好的线性关系,相关系数均大于0.999。9种阴离子的平均加标回收率为92.5%~101.3%,相对标准偏差为1.9%~2.8%（n=6）。该方法简便快捷,选择性好,灵敏度高,可满足火场爆炸残留物中无机离子的分析要求。     

离子液体中18-冠醚-6添加剂对三价铬电沉积的影响

在1-丁基-3-甲基咪唑硫酸氢盐（[BMIM]HSO₄）电镀液中,探究了18-冠醚-6添加剂对电沉积铬的影响. 紫外-可见光谱结果表明,18-冠醚-6与Cr³⁺形成配合物,使最大吸收波长发生红移. 循环伏安研究表明,Cr³⁺的还原经历了两步. 18-冠醚-6的添加使Cr³⁺的峰电位和起始还原电位均正移了220 mV. 能谱仪（EDS）结果显示,在18-冠醚-6的作用下镀层中铬含量有所提高. 铬镀层的扫描电子显微镜（SEM）表征结果表明,加入18-冠醚-6后,所得镀层的颗粒变大. 18-Crown-6/CrCl₃/[BMIM]HSO₄/H₂O电镀液中工艺优化的结果为：在温度为50 ^oC、pH值为3.5、电流密度为1200 A·m^-2、电镀时间为1.5 h的最佳工艺条件下,铬镀层的厚度达到72.5 μm,电流效率为42.3%.     

One Dimensional Iron Molybdophosphate Anionic Chains with Different Structural Arrangements Reflecting a Flexibility Character

Structural comparison of a new compound[(bpp)₃H₆]Fe₂^IIIFe₂^IIMo₂₄^V(H₂PO₄)₈(HPO₄)₄(PO₄)₄O₄₈(OH)₁₂· (H₂O)₄·2H₂O(1)[bpp=1,3-di(4-pyridyl)propane] with our previously reported two compounds[(bpy)₃Fe^II]₃· Fe₂^IIIFe₂^IIMo₂₄^V(H₂PO₄)₈(HPO₄)₄(PO₄)₄O₄₈(OH)₁₂(H₂O)₄·12H₂O(2) and[(bpy)₃Fe^II]₂Fe^IIFe^IIIMo₁₂^V(H₂PO₄)₂(H_2-xPO₄)·(H_1+xPO₄)(HPO₄)₂(PO₄)₂O₂₄(OH)₆(H₂O)₂·9H₂O(x=0―1)(3)(bpy=2,2'-bipyridine), which all exhibit one-dimensional mixed-valence iron molybdophosphate anionic chains constructed by alternating connection of Fe^III ions and magic[Fe^II(Mo₆P₄O₃₁)₂] units, reveals that the non-hydrogen atomic ratios of Mo:Fe:P:O within the polymeric anionic chains are the same for all the three compounds, while the polymeric anionic chains of the different compounds bear different numbers of negative charges. And therefore there exist different numbers of counter cations per {Fe₂^III[Fe₂^II(P₁₆Mo₂₄^VO₁₂₄)]} unit found in the titled compounds. It discloses that not only are the spatial assembling of counter cations and polymeric inorganic chains of three compounds quite different, but also the O―Fe^III―O bond angles and Fe^III―O bond lengths of the three different inorganic chains exhibit small differences. What is more important is that such small changes in bond length and bond angle in the assemblage of Fe^III―O bonds lead to the considerable fluctuations of inorganic chains in their structural conformation within the three compounds, reflecting an interesting phenomenon of “flexibility" in the pure inorganic one dimensional mixed-valence iron molybdophosphate chains.     

酸功能化离子液体催化合成聚缩醛二甲醚

对以酸功能化离子液体[Hnmp]HSO4、[Hnmp]H2PO4、[Hnmp]PTSA和[PyN(CH2)3SO3H]HSO4催化三聚甲醛和甲醇缩合制备聚缩醛二甲醚(PODEn,n1)的反应进行了研究,考察了催化剂用量、物料配比、温度和时间等对反应活性的影响。结果表明,离子液体的催化活性与其酸性相关。[PyN(CH2)3SO3H]HSO4具有较高的催化活性;当[PyN(CH2)3SO3H]HSO4的用量为2.0%、甲醇和三聚甲醛的物质的量比为2.0、反应温度110℃、反应压力2.0 MPa、反应时间6 h时,三聚甲醛的转化率和PODE3~8的选择性分别为97.69%和32.54%。反应结束后,[PyN(CH2)3SO3H]HSO4与产物可自动分成两相。     

高压离子色谱法快速测定饮用水中7种无机阴离子

建立了使用高压离子色谱快速测定饮用水中7种无机阴离子的方法。环境水样经0.22 μm尼龙滤膜过滤后可直接进样分析。采用Dionex Integrion高压离子色谱仪和AS22-Fast-4 μm阴离子交换柱（150 mm×4 mm）,可在5 min内完成对F^-、Cl^-、Br^-、NO₂^-、NO₃^-、SO₄^2-和PO₄^3-这7种阴离子的分析。以4.5 mmol/L碳酸钠和1.4 mmol/L碳酸氢钠为淋洗液,流速为2mL/min。7种阴离子的检出限为0.007~0.07 mg/L（S/N=3）,在较宽范围内有良好的线性关系（相关系数不小于0.999）和重现性（相对标准偏差不大于0.48%,n=8）。实际样品加标回收率为91.4%~109.7%,相对标准偏差为0.30%~0.45%（n=5）。将该方法应用于饮用水厂进出水的分析,结果表明在进出水中检出6种阴离子,以Cl^-、NO₃^-和SO₄^2-为主。该方法简便快速、灵敏准确,尤其适合高通量样品中阴离子的快速分析。