Accurate determination of ultra-trace levels of Ti in blood serum using ICP-MS/MS

Ti is frequently used in implants and prostheses and it has been shown before that the presence of these in the human body can lead to elevated Ti concentrations in body fluids such as serum and urine. As identification of the exact mechanisms responsible for this increase in Ti concentrations, and the risks associated with it, are not fully understood, it is important to have sound analytical methods that enable straightforward quantification of Ti levels in body fluids (for both implanted and non-implanted individuals). Until now, only double-focusing sector field ICP-mass spectrometry (SF-ICP-MS) offered limits of detection that are good enough to deal with the very low basal levels of Ti in human serum. This work reports on the development of a novel method for the accurate and precise determination of trace levels of Ti in human serum samples, based on the use of ICP-MS/MS. O₂ and NH₃/He have been compared as reaction gases. While the use of O₂ did not enable to overcome all spectral interferences, it has been shown that conversion of Ti⁺ ions into Ti(NH₃)₆⁺ cluster ions by using NH₃/He as a reaction gas in an ICP-QQQ-MS system, operated in MS/MS mode, provided interference-free conditions and sufficiently low limits of detection, down to 3 ng L⁻¹ (instrumental detection limit obtained for the most abundant Ti isotope). The accuracy of the method proposed was evaluated by analysis of a Seronorm Trace Elements Serum L-1 reference material and by comparing the results obtained with those achieved by means of SF-ICP-MS. As a proof-of-concept, the newly developed method was successfully applied to the determination of Ti in serum samples obtained from individuals with and without Ti-based implants. All results were found to be in good agreement with those obtained by means of SF-ICP-MS. The typical basal Ti level in human serum was found to be <1 μg L⁻¹, while values in the range of 2–6 μg L⁻¹ were observed for implanted patients.     

Corrosion resistance and bioactivity of titanium after surface treatment by three different methods: ion implantation,alkaline treatment and anodic oxidation

The paper compares the effects of various surface modifications, ion implantation, alkaline treatment and anodic oxidation, upon the corrosion resistance and bioactivity of titanium. The chemical composition of the surface layers thus produced was determined by XPS, SIMS and EDS coupled with SEM. The structure of the layers was examined by TEM, and their phase composition by XRD. The corrosion resistance was determined by electrochemical methods after the samples were exposed to the test conditions for 13 h. The bioactivity of titanium was evaluated in a simulated body fluid at a temperature of 37°C after various exposure time.     

A spectrophotometric method for estimation of titanium alkoxide,a catalytically active form of titanium in oligomer/ polymers

A spectrophotometric method was developed for the selective estimation of titanium in alkoxide form in the presence of TiO₂. Polymers like polybutylene terephthalate have been synthesized by using homogeneous catalyst such as titanium tetra-isopropoxide (TTIP). These types of catalysts are susceptible to moisture and convert to inactive TiO_2. Hence, it is essential to have analytical method for selective estimation of alkoxide form of titanium. In this study, we have used O-cresol to convert TTIP to tetra O- cresyl titanate, a colored compound, which was quantitatively analyzed by spectrophotometric technique. Polymer matrix was used in standard solution to compensate the effect of matrix during UV-VIS measurements. Method validation was successfully carried out for linearity, reproducibility, recovery, specificity and the observed acceptable results as per ICH guidelines. 2-sample t-test was performed to check the variation observed between two analysts and the observed p-value indicated the results were statistically similar to each other. Mechanism of color formation was established by synthesis of colored complex called tetra O-cresyl titanate. The structure was supported by ICP, CHNS and NMR analysis. The method is simple and easy to implement at manufacturing plant for initial monitoring of active catalyst concentration in polymer/oligomer samples.     

A comparison of double-focusing sector field ICP-MS, ICP-OES and octopole collision cell ICP-MS for the high-accuracy determination of calcium in human serum

Human serum is routinely measured for total calcium content in clinical studies. A definitive high-accuracy and low-uncertainty method is required for reference measurements to underpin medical diagnoses. This study presents a novel octopole collision cell ICP-MS, high-accuracy, methodology and comparison of that technique with double-focusing sector field ICP-MS and an ICP-OES method. Double-matched isotope dilution mass spectrometry (IDMS) was employed for ICP-MS techniques and an exact matching bracketing technique using scandium as an internal standard was used for ICP-OES analysis. Medium resolution mode was utilised for double-focusing sector field ICP-MS analysis to resolve the dominant interferences on the ⁴⁴Ca/⁴²Ca isotope pair. Hydrogen reaction gas was employed to chemically resolve a number of polyatomic interferences predominantly through charge transfer reactions in the octopole collision cell. Comparison data presented for NIST CRM 909b human serum analysis from all three techniques demonstrates highest accuracy (99.6%) and lowest uncertainty (1.1%) for octopole collision cell ICP-MS. Data from ICP-OES using a non-IDMS technique produces comparably accurate data and low-uncertainties. The much higher total expanded uncertainties for double-focusing sector field ICP-MS compared with octopole collision cell data are explained by lower precision on the measurement of the ⁴⁴Ca/⁴²Ca isotope ratio. Data for octopole collision cell ICP-MS submitted for an international blind trial comparison (CCQM K-14) demonstrated excellent agreement with the mean of all participants with a low expanded uncertainty.     

Benzalkonium chloride/titanium dioxide as an effective corrosion inhibitor for carbon steel in a sulfuric acid solution

In this study, the corrosion performance of carbon steel samples in 0.5 M sulfuric acid by the addition of novel inhibitors, 200 ppm of (25% and 50%) titanium dioxide nanoparticles in benzalkonium chloride, was thoroughly investigated. Gravimetric measurements, cyclic and linear potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and hydrogen collection by water displacement evaluated inhibition performance. Analogously, TiO₂/ILB (50%), TiO₂/ILB (75%), and ILB inhibitors enhanced corrosion protection with over 80% inhibition efficiency in electrochemical tests. In addition, weight loss and hydrogen collection measurements reached comparable results. According to potentiodynamic polarization curves, inhibitors exhibited dual behavior, but cathodic protection was more predominant. Scanning electron microscopy (SEM) was employed to examine the surface morphology before and after immersion using corrosion tests. The correlation between electronic properties and inhibition efficiencies of tilted inhibitors was determined by simple linear regression. Electronic properties were calculated for neutral and protonated forms using a polarizable continuum model by the DFT method at the B3LYP/6-311+G (d, p) level of theory. The active adsorbed sites of HM1-HM3 on the metal surface were determined by analyzing their corresponding electrostatic surface potentials (ESP). Furthermore, molecular dynamics simulations were performed to illustrate the most conceivable adsorption configuration between the inhibitors and metal surfaces.     

Titanium as a chemical modifier for the determination of cobalt in marine sediments

The determination of cobalt in marine sediments by electrothermal atomic absorption spectrometry was studied using no modifier and magnesium and titanium as modifiers. Titanium is one of the major sediment constituents, which widely affects the cobalt determination and it was studied as a chemical modifier since it was the only concomitant that increased the cobalt signal in the concentration range usually found in sediments. The performance of Mg and Ti as chemical modifiers was compared relative to maximum pyrolysis and atomization temperatures, linear calibration range, sensitivity and matrix effects. The pyrolysis curves showed that the analyte could be stabilized up to 1400 °C when either Ti or Mg(NO₃)₂ was present, while only 1000 °C could be used in the absence of a modifier. The optimum atomization temperature was 2500 °C in all cases. Analytical curves were compared using no modifier, 5 μg Ti and 100 μg Mg(NO₃)₂ as modifiers, and the linear range found was up to approximately 4 ng Co whether a modifier was used or not. With Ti as a chemical modifier, analytical curves for cobalt in aqueous solution and in a synthetic matrix resulted in the same sensitivity (m₀=55 pg), whereas the use of Mg led to characteristic mass values of 59 and 72 pg in aqueous solution and in a synthetic matrix, respectively, showing some matrix effect. The detection limits (3σ, n=10) were 0.4 μg g⁻¹ using no modifier and 0.3 μg g⁻¹ with Ti as a modifier in the original matrix. A reference estuarine sediment NIST 1646 with a non-certified content of 10.5 μg g⁻¹ Co was analyzed and the found value of 10.9±2.4 μg g⁻¹, (n=3), using Ti as chemical modifier and calibration against aqueous standards, was in good agreement with the recommended value.     

生物体中微量钛的测定——邻硝基苯基荧光酮直接光度法

研究了用邻硝基苯基荧光酮显色测酞时,酒石酸钾钠和氟化铵的影响。从而能直接测定生物体中微量钛。检出限为0.05μg.     

Titanium Dioxide as a Mild and Efficient Catalyst for Conversion of Epoxides to Thiiranes

Abstract

Titanium dioxide (TiO₂) efficiently catalyze the reaction of a variety of epoxides with ammonium thiocyanate in refluxing acetonitrile to afford the corresponding thiirane in high to excellent yields.     

In vitro corrosion study of different TiO2 nanotube layers on titanium in solution with serum proteins

Titanium oxide nanotubes prepared by anodization have received considerable attention in the biomaterials domain. The objective of this study was to demonstrate the electrochemical behavior of different diameter TiO(2) nanotube layers on titanium in phosphate buffered saline (PBS) and Dulbecco's minimum essential medium+10% fetal calf serum (D-FCS) using open circuit potentials (OCP), electrical impedance spectroscopy (EIS), and a potentiodynamic polarization test. The results showed that the nanotubes had higher OCP, higher resistance of the inter barrier layer (R(b)), and lower I(pass) in the two test solutions compared to the smooth Ti, especially the 30 nm diameter nanotubes. The corrosion resistance of the nanotubes in D-FCS was higher than in PBS because of protein adsorption from the D-FCS solution as suggested by scanning electron microscope (SEM) images. In addition, protein aggregates of 30 nm diameter nanotubes caused the model of EIS spectra to transform from two-layer to three-layer. The corrosion behavior of the nanotubes for use as a dental implant material is discussed.     

Selective stopped-flow sequential injection method for the spectrophotometric determination of titanium in dental implant and natural Moroccan phosphate rock

The present work reports the first sequential injection (SI) method for the spectrophotometric determination of Ti(IV). The method is based upon the reaction of Ti(IV) with chromotropic acid (CA) in acidic medium to form a water-soluble complex (λ_max = 420 nm). The chemical and instrumental variables of the system that affected the reaction were studied. Selectivity was greatly enhanced using ascorbic acid. A linear calibration graph was obtained in the range 0.2-10.0 mg l⁻¹ Ti(IV) at a sampling frequency of 24 h⁻¹. The precision was satisfactory (s_r = 1.5% at 5.0 mg l⁻¹ Ti(IV), n = 12) and the 3σ limit of detection, c_L, was 0.7 mg l⁻¹ (n = 10). The developed method proved to be adequately selective and was applied successfully to the analysis of real samples (dental implant and natural Moroccan phosphate rock) giving accurate results based on recovery studies (98-105%).     

Titanium dioxide nanowires as green and heterogeneous catalysts for the synthesis of novel pyranocoumarins

Titanium dioxide nanowires were employed as novel, recyclable and safe catalysts in a one-pot three-component condensation of aldehydes, malononitrile, and 4-hydroxycoumarin to produce new and known pyrano[2,3-c]chromenes as potent biologically active compounds. A possible catalytic mechanism was also proposed based on the interaction of reactants with TiO₂ nanowires. This expedient new route has advantages, such as the use of a safe and reusable catalyst, simple operation, short reaction times and good to excellent yields.     

Determination of Trace Titanium by Solid Substrate－Room Temperature Phosphorimetry with 4,5－Dibromophenylfluorone as Luminescent Ligand and Triton X－100 as Sensitizer

A new highly sensitive solid substrate room temperature phosphorimetry for the determination of trace titanium is proposed based on the sensitization of Triton X-100 to the SS-RTP intensity of 4, 5-dibro-mophenylfluorone-titanium complex adsorbed on the filter paper substrate modified by gelatin. When Triton X-100 was added into the luminescence system, the RTP intensity was raised 3 times stronger than that of the system without Triton X-100. The linear dynamic range of the new method is 0. 64 ～ 3.2 fg/spot (0. 4 μL) with a detection limit of 12.8 ag/spot, and the regression equation of the working curve is △Ip = 482. 0 119.5mTi（Ⅳ) (fg/spot), the correlation coefficient r= 0. 9992, n = 6. The phosphorescence lifetime (r= 0. 85 ms) was also determined. The recoveriesCand RSD) for the determinations of titanium in human hair and tea samples were 101.0% (3. 0%) and 99. 97% (4. 2%), respectively.     

Adsorption of fibrinogen on tantalum oxide, titanium oxide and gold studied by the QCM-D technique

The adsorption of human fibrinogen on tantalum oxide, titanium oxide and gold surfaces has been studied by quartz crystal microbalance with dissipation (QCM-D) at 37 degrees C. Two different protein concentrations have been used, one close to physiological concentration (1 mg/ml) and one significantly lower (0.033 mg/ml). To further characterize the adsorbed fibrinogen layer, the subsequent binding of both polyclonal and monoclonal antibodies of fibrinogen is studied. We found that the viscoelastic properties of the fibrinogen layer depends strongly on the initial protein concentration. The trend is generally seen for all three surfaces. The fibrinogen layer on gold and tantalum oxide is found to have the same viscoelastic properties, which are different from those found for the fibrinogen layer adsorbed on titanium oxide. The dependency of the surface chemistry on the viscoelastic properties of the fibrinogen layer is observed directly for the 0.033 mg/ml solution, and indirectly through the antibody response for the 1 mg/ml solution. From this we conclude that the orientation and/or denaturation of fibrinogen on a surface depends on the surface chemistry and the protein concentration in the solution, and that the binding of antibodies is a useful way to detect this difference.     

Photocatalytic Reaction of Sulfur Dioxide with Heptane in the Gas-phase Over Titanium Dioxide

IntroductionA broad range of orgainc compounds[1 ,2 ]can be oxidized by means of semiconductor pho-tocatalysis with a primary focus on Ti O2 as a durable photocatalyst in recent years.WhenTi O2 is illuminated with the light of energy greater than the semiconductor band gap,elec-tron- hole pairs(e-- h ) are formed in the conduction and thevalence bandsof thesemiconduc-tor,respectively.These charge carriers,which migrate to the semiconductor surface,are ca-pable of activating oxygen species,et…     

Preparation and catalytic activity of titanium silicalite-1 zeolite membrane with TPABr as template

The preparation of the supported titanium silicalite-1 (TS-1) zeolite membrane with inexpensive tetrapropylammonium bromide (TPABr)/weak base synthesis system was studied by three methods, and the catalytic activity of the obtained TS-1 zeolite membrane was evaluated with the oxidation of 2-propanol (IPA) under pervaporation condition. It was found that TS-1 zeolite membrane could be successfully prepared with “seeding” or “seeding in situ” method, but could not be achieved with “in situ” method. Adding a little amount of promoter ions of PO₄³⁻ into the synthesis gel was of benefit to the catalytic activity of the prepared TS-1 zeolite membrane, but had no obvious effect on the membrane layer formation on the mullite porous support. For “seeding” method, the membrane prepared with the synthesis gel having molar composition of SiO₂:0.1TPABr:0.9Et₂NH:0.03TiO₂:80H₂O:0.06H₃PO₄ at 150 °C for 48 h showed the highest oxidation conversion of IPA of 72% accompanied by a flux of 0.35 kg/m² h. Further more, much higher IPA oxidation conversion of 76% accompanied by a flux of 0.65 kg/m² h was obtained for the TS-1 zeolite membrane prepared with the same synthesis gel by “seeding in situ” method at 150 °C for 72 h.     

中药中砷镉汞铅ICP-MS测定值的聚类分析

聚类分析又称集群分析,它是研究“物与类聚”的一种数理统计方法,聚类分析可将一些观察对象依据某些特征加以归类。已经在生物学和医学分类问题[1]以及中药的鉴别与质量评价[2]中获得广泛应用。祁俊生等[3]利用因子分析和聚类分析探讨了微量元素含量与中药药性的相关性。梁逸曾     

磺酰氨基酸钛配合物对Diels-Alder反应的对映选择性催化作用

研究了对甲苯磺酰基-L-缬氨酸、对甲苯磺酰基-L-苯丙氨酸、对甲苯磺酰基-L-亮氨酸、对甲苯磺酰基-L-异亮氨酸、对甲苯磺酰基-L-脯氨酸、1-萘磺酰基-L-缬氨酸、1-萘磺酰基-L-苯丙氨酸、1-萘磺酰基-L-亮氨酸和1-萘磺酰基-L-异亮氨酸与钛的配合物对环戊二烯与丙烯酸甲酯的环加成反应的对映选择性催化作用。萘磺酰基氨基酸钛配合物的对映选择性比对甲苯磺酰基氨基酸钛配合物好,氨基酸与钛比为2:1时比1:1要好得多。1-萘磺酰基-L-异亮氨酸与钛的2:1配合物的对映选择性最好,e.e.值为56%。     

Preparation of nanocrystalline porous titania films on titanium substrates by a sol–gel method with polyethylene glycol as a template

Porous nanocrystalline TiO₂ films have been prepared on cp-Ti substrates for biomedical usage by a sol–gel process from the solutions containing polyethylene glycol (PEG) as a template. Variations of the crystal structure with heat-treatment temperature determined by XRD are different for TiO₂ films and powders, due to the effect of titanium substrate. The surface texture of porous TiO₂ films is analyzed by means of SEM and found to greatly depend on the concentration and molecular weight of PEG. The pore formation mechanism is discussed in relation to the self-assembly of PEG and phase separation between PEG adsorbed on TiO₂ oligomers and ethanol.     

Determination of vanadium and titanium in steel by inductively coupled plasma atomic emission spectrometry with modified use of a tungsten boat furnace atomizer for atomic absorption spectrometry

For electrothermal sample introduction, a commercially available tungsten boat atomizer for atomic absorption spectrometry (AAS) was transferred to a vaporizer for inductively coupled plasma atomic emission spectrometry (ICP-AES). The modification retained as much of the original design of the atomizer as possible, so that the apparatus could be switched easily between conventional tungsten boat furnace (TBF)-AAS and TBF-ICP-AES. By using this system, a procedure for the determination of vanadium and titanium in steel was investigated. The detection limits (S/N=3) of vanadium and titanium were 3.9 and 1.5 ng ml^?1, respectively. The relative standard deviations for five replicate determinations were ca. 3% for both elements. The calibration graphs were linear up to 100 μg ml^?1 vanadium(V) and 10 μg ml^?1 titanium(IV). Results of analyses of some low-alloy steel samples are given.     

邻氯苯基荧光酮-乳化剂OP光度法测定轴承钢中微量钛

在稀硫酸(cH2SO4)0.04~0.06 mol.L-1介质和非离子型表面活性剂OP的存在下,邻氯苯基荧光酮(o-Cl-PF)与钛(Ⅳ)反应生成红紫色络合物,其吸收峰位于540 nm波长处,在此波长条件下,测得其表观摩尔吸光率为1.66×105L.mol-1.cm-1。钛(Ⅳ)的质量浓度在(0~3μg)/25 mL范围内显色体系遵守比耳定律。铁(Ⅲ)及钼(Ⅵ)的干扰借加入盐酸羟胺并在沸水浴中加热15 min可消除。应用此方法分析了轴承钢标准样品(G20Cr2NiMo,含钛wTi=0.004 0%),测定值与标准值相符,并求得其RSD(n=6)为6.1%。