线性扫描伏安法测定氟罗沙星

应用线性扫描伏安法和循环伏安法研究氟罗沙星在玻碳电极上的电化学行为。在含有铜离子的pH 6.5的0.10mol.L-1磷酸盐缓冲溶液中,铜离子在玻碳电极上分别于-0.136V和-0.728V处形成两个还原峰,加入氟罗沙星后铜离子的还原峰电位不变但峰电流均降低。在优化的试验条件下,于-0.136V处的峰电流降低值Δip与氟罗沙星浓度在6.40×10-7～1.5×10-4 mol.L-1范围内呈线性关系,检出限为2.10×10-7 mol.L-1。方法用于氟罗沙星片剂中氟罗沙星含量的测定,回收率在96.8%～103.5%之间。     

氟-铁恒电位配位滴定法测定铁离子研究

以氟离子溶液作滴定剂,氟离子选择性电极作指示电极,在pH=1.5的条件下,对恒电位配位滴定法测定铁离子进行了研究。对pH=1.5的条件下使用氟离子选择性电极的可行性,氟-铁的反应速率及电极的响应速率进行了讨论。     

离子选择性电极非线性测定水中氟离子的含量

利用氟离子选择性电极测定系列氟离子标准溶液的电极电位(vs.SCE),用测得的电极电位值与氟离子标准溶液的浓度数据进行非线性工作曲线拟舍,可准确测定1×10~(-6)～1×10~(-5)moL/L氟离子溶液的浓度。该法易于实现氟离子溶液的自动连续监测,适于氟离子溶液浓度的在线测量。     

基于铝氟配位反应的动力学-电位法对铝的测定

以氟离子选择性电极作指示电极,用动力学电位法对铝的测定进行了研究.在低pH条件下,铝氟反应E～t曲线的斜率△E/△t与铝的浓度cAl成正比.实验步骤为:第一步,根据铝的校正溶液与氟反应的△E/△t,作出△E/△t～cAl工作曲线;第二步,根据铝试液与氟反应的△E/△t,求出铝的浓度.合适的实验条件是:pH范围1～2;温度范围288～303 K;铝的浓度范围1×10-3～5×10-2mol/L;加入的氟的浓度范围5×10-4～5×10-2mol/L.此外,对动力学电位法测定铝的计算式进行了理论推导,对该法存在的问题、可以采取的措施及误差的分布进行了讨论.     

硝酸活化高灵敏度离子选择性电极法测定氟

先在0．5 mol·L-1硝酸介质中活化氟离子选择性电极,再在含硝酸的总离子强度调节混合液(TISAM)中测定氟,线性范围为1×10-7～1×10-2mol·L-1,检出限为1．9μg·L-1。该方法应用于绿茶饮料、水、牛奶中痕量氟的测定,结果的RSD小于4．8％,回收率在96．1％至100．2％之间,对氟离子选择性电极在硝酸介质中的活化机理作了阐述。     

氟的离子选择电极瞬时电位法测定

研究了氟离子选择电极瞬时电位分析法，其检出限和Nernst响应下限均低于传统电位分析法，空白液切换到试液时瞬时电位达到稳定的峰电位Vp比传统电位法的响应快得多，可以实现小体积试液的快速准确分析；用该法测定了自来水和矿泉水中氟的含量；利用校正曲线的截距和检出限计算了LaF3的溶度积，在0.1mol/L KNO3介质中Ksp(LaF3)=10^-28.45，在0.001mol/L柠檬酸钠＋HAc-NaAc缓冲液（pH=5.50，离子强度I＝0.10mol/L)介质中溶度积K′sp(LaF3)=10^-26.26；据此，计算得柠檬酸与La^3 络合物的稳定常数K1=10^5.46和K2=10^3.99；用离子水合吉氏自由能ΔGh(F^-,g)解释了不同浓度F^-试液瞬时电位的跃迁时间。     

离子选择性电极快速测定植物中氟

氟离子选择电极测定植物中氟有灰化法,氧瓶燃烧法、氢氧化钠熔融法和酸浸提法等。这些方法分析时间长、操作繁琐,且均需加入TISAB(总离子强度缓冲溶液)使pH=5～5.5,以防止低pH值时生成HF缔合物和高pH值时OH的干扰。为了达到快速分析的目的,我们在pH≈1时,不加TISAB,用标准加入法直接测定植物中氟,每次测定只需约30min。方法的精密度与准确度较好,分析结果与盐酸浸提法结果无     

控制电位氟-镓配位滴定法测定镓

以氟离子溶液作滴定剂,氟离子选择性电极作指示电极,利用氟-镓之间的配位反应及控制电位滴定法,对镓的测定进行了研究.控制溶液的pH约为4.2,实验温度为298 K,离子强度调节剂(NaNO3)的浓度为0.1 mol/L.对溶液控制的pH,氟离子的酸效应和镓离子的羟基配位效应对测定结果的影响,共存的Cu2 ,Zn2 ,Ni2 及Co2 等离子的干扰进行了讨论.     

新型1-烷基-2,3-二甲基咪唑六氟磷酸盐离子液体/过氧化氢酶电极电化学性能研究与应用

合成了5种新型1-烷基-2,3-二甲基咪唑六氟磷酸盐类离子液体,并以离子液体为介质制备空白电极及过氧化氢酶电极.采用循环伏安法研究电极电化学行为,结果表明离子液体有优良的电化学性质.离子液体空白电极的基体峰电流都在数nA范围内,电化学窗口大于4 V;不同离子液体酶电极的电化学行为存在明显差异.在5种离子液体中,仅有1-戊基-2,3-二甲基咪唑六氟磷酸盐能很好地保持酶活,呈现灵敏的电化学响应.此外,该酶电极还具有良好的稳定性,4 ℃保存30 天后,电化学性质没有明显变化.在0.1 mol/L的H3PO4缓冲溶液(pH 7.0)中,该酶电极还原峰电流随溶液中H2O2浓度的增加而增大.当H2O2浓度在3.17×10-6～12.4×10-6 mol/L之间,酶电极的还原峰电流符合线性关系,其检出限为1.1×10-6 mol/L.方法已用于环境水中痕量H2O2的测定.     

离子选择电极测定维生素C生产过程中钠含量

采用钠离子选择电极测定维生素C(VC)生产过程中钠的含量。试验表明:该离子选择性电极对钠具有良好的选择性和电位响应特性。在pH≥10介质中,电极电位呈现能斯特响应,线性范围为1.0～10.0mg.L-1,斜率为55.18mV.pc-1。将该电极用于测定维生素C生产过程中的钠含量,测得方法的回收率在85.4%～99.0%之间,相对标准偏差(n=6)在1.3%～1.4%之间。     

Local structural analyses on molten terbium fluoride in lithium fluoride and lithium-calcium fluoride mixtures

X-ray absorption fine structure (XAFS) measurements on terbium fluoride in molten lithium fluoride and in molten lithium-calcium fluoride mixtures, (e.g. 0.20TbF₃-0.80LiF, 0.20TbF₃-0.62LiF-0.18CaF₂, 0.20TbF₃-0.48LiF-0.32CaF₂, 0.50TbF₃-0.50LiF, and 0.50TbF₃-0.38LiF-0.12CaF₂), have been carried out. In the solid state, coordination number of terbium (N_i) and inter ionic distances between terbium and fluorine in the first neighbor (r_i) are nearly constant in all mixtures. In 0.20TbF₃-0.80LiF, 0.20TbF₃-0.62LiF-0.18CaF₂ and 0.50TbF₃-0.50LiF mixtures, N_i's decrease from ca. 8 to 6 and r_i's also decrease from ca. 2.29 to 2.26 Å on melting. On the other hands, in molten 0.20TbF₃-0.48LiF-0.32CaF₂ and 0.50TbF₃-0.38LiF-0.12CaF₂ mixtures, N_i's are slightly larger than 6 and r_i's do not change. These facts correspond to the amount of F⁻ supplied by solvent melts, i.e. the effect of CaF₂ becomes predominant at bCaF₂ > 0.32 in ternary 0.20TbF₃-aLiF-bCaF₂ mixtures and at bCaF₂ > 0.12 in ternary 0.50TbF₃-aLiF-bCaF₂ mixtures.     

Tetramethylphosphonium fluoride: "naked" fluoride and phosphorane

Me(4)PF was investigated in the solid state, in the gas phase, and in solutions. Vibrational spectra of the solid and a single-crystal structure show an ionic tetramethylphosphonium fluoride. The compound crystallizes in the space group Pbca with a = 1016.0(1), b = 1018.0(1), c = 1205.8(4) pm, and Z = 8. The fluoride ion is nearly trigonal planar surrounded by three Me(4)P+ cations forming six H...F contacts between 218 and 240 pm. The compound is stable below 120 degrees C and sublimes in a vacuum. It possesses a phosphorane structure in the gas phase that was studied by electron diffraction and vibrational spectra, and additionally by theoretical calculations. The Me(4)PF molecule has a trigonal bipyramidal structure with one methyl group and the fluorine atom in axial positions and bond lengths of d(PC(eq)) = 182.6(4) pm, d(PC(ax)) = 188.4(8) pm, and d(PF) = 175.3(6) pm. The compound is remarkably soluble in acetonitrile, water, and alcohols, and slightly soluble in benzene, dimethyl ether, and diethyl ether. The solutions were studied by (1)H, (13)C, (19)F, and (31)P NMR spectroscopy. The hygroscopic Me(4)PF forms a tetrahydrate which crystallizes in the space group I4(1)/a with a = 1106.1(1) pm, c = 816.3(1) pm, and Z = 4. The fluoride ion in Me(4)PF.4 H(2)O is surrounded by four water molecules. These units form a three-dimensional network in which the Me(4)P+ cations are embedded without any contacts.     

The potentiometric titration of fluoride without fluoride ion-selective electrodes

Graphite and platinum sensors were investigated as indicators in the potentiometric titration of fluoride vs lanthanum(III) and thorium(IV). In every case a partially nonaqueous medium yielded larger breaks than in aqueous solution, similar to the fluoride electrode. All the sensors yielded endpoint breaks which were smaller than those obtained with a fluoride ion-selective electrode. The largest breaks were obtained with the vitreous carbon, pyrolytic graphite, and platinum sensors. Conditioning in neutral permanganate solution significantly enhanced the breaks for all types of graphite, except vitreous carbon. The break obtained with the platinum electrode can be enhanced by application of a polarizing current of 2.0 μA in the reducing direction.     

Anhydrous tetrabutylammonium fluoride

Tetrabutylammonium fluoride (TBAF) is prepared at low temperature by nucleophilic aromatic substitution of hexafluorobenzene with tetrabutylammonium cyanide. Adventitious water is scavenged during this synthesis by the generated hexacyanobenzene, which readily adds water under basic conditions. Contrary to expectations, TBAF is stable to Hofmann elimination in polar aprotic solvents under anhydrous conditions. Added hydroxylic solvents are shown to catalyze the decomposition of TBAF and to catalyze proton exchange with DMSO. The synthetic utility of this salt is described briefly.     

The fluoride dilemma

The implications of environmental contamination by fluoride on human health call upon the need for the development of monitoring systems for the ‘in situ’ detection of fluoride in contaminated sources and new technologies approaches for their removal. This paper reports recent work on the design of calixpyrrole receptors selective for the fluoride anion. The various steps undertaken for the thermodynamic characterization of these receptors and their anionic complexes are discussed. Thus based on thermodynamic data, the medium and ligand effects on selectivity are quantitatively assessed using representative calixpyrrole derivatives.     

Bismuth-containing fluoride glasses

The example of bismuth-containing glasses based on InF₃ and ZrF₄ is used to consider the effect of bismuth on glass formation, properties, and structure and the appearance of broadband luminescence at low wavelengths in the IR spectra of fluorozirconate glasses.     

Bioavailability of fluoride administered as sodium fluoride or monofluorophosphate to humans

A double-bind cross-over study was conducted on four healthy subjects, aged 19-29 years, in order to determine the relative bioavailability and other pharmacokinetics features of fluoride (F) after single oral administration in fasting conditions of 2 mg F as sodium F (NaF) or sodium monofluorophosphate (MFP). The bioavailability was evaluated on the basis of the plasma levels and of the urinary excretion of F. Blood was sampled before and during the 8 h after the administration of the test solutions. For F excretion urine was sampled 12 h before the study and over the 8 h after the administration. Data were tested for statistically significant differences by ANOVA and Tukey's post hoc tests, and also by Student's t-test (p < 0.05). For the two formulations, the pharmacokinetics of F in plasma was characterized by a rapid absorption and by a peak (C_max = 0.1 μg/mL) which was reached 20 min after administration, followed by a biphasic elimination. In the 8 h following the administration the urinary excretion of F accounted for 35-41% of the administered dose, without significant differences between the two formulations. The AUCs (±S.D.) for NaF and MFP were 21.15 (±0.58) and 19.04 (±1.75) min μg mL⁻¹, respectively, and were not significantly different (p = 0.079). Based on the AUC and C_max of F in plasma and on the urinary excretion of F during the 8 h following administration, the relative bioavailabilities of the two F formulations were equivalent.