Development of Miniaturized Electrochemiluminescence Instrument using Multi‐pixel Photon Counter as the Optical Detector

We developed a miniaturized electrochemiluminescence (ECL) instrument coupled with a light‐emitting diode‐based bipolar electrochemical sensor (LED‐BPES). This instrument composes of a microcontroller circuit, a power supply circuit, a potentiostat, an optical detecting circuit, and a communication circuit. The multi‐pixel photon counter (MPPC), which is low‐cost, small‐size, and wide‐range in optical measurements, is chosen as the optical detector. The LED‐BPES composes of a disposable screen‐printed carbon electrode (SPCE) and a surface‐mount red LED. Depended on the closed bipolar electrode (C‐BPE) structure, the LED‐BPES not only avoids the employment of unstable and complex ECL reactions but also offers a cost‐effective alternative for the over‐priced ECL reagents by using a mini‐size commercial LED as the luminescent producer. The combination of MPPC and LED‐BPES helps to set up the simplified and downsized instrument system with low price and high efficiency. The presented instrument coupled with LED‐BPES works excellent in electroactive molecules detection and has great potential in the application of heavy metal ions detection.     

90° Compton and Rayleigh measurements and imaging

A simple apparatus for measurement and imaging of objects using scattered X-rays was designed and constructed. This is composed of a well-collimated photon beam from an X-ray tube, a CZT thermoelectrically cooled semiconductor detector and an (x, y, ) translation-rotation table containing the object to be studied. First, the output beam was monochromatized; studies on Compton and Rayleigh scattered radiation were then carried out, including the Compton profile. Then direct bremsstrahlung radiation of proper energy was employed, and energy intervals are selected where Rayleigh or Compton effects largely prevail. Compton images were finally obtained.     

Characterization of an energy dispersive X-ray fluorescence imaging system based on a Micropattern Gaseous Detector

An energy dispersive X-ray fluorescence (EDXRF) imaging system based on a Micropattern Gas Detector has already shown good results for different applications. An X-ray tube, a pinhole camera and a Micro-Hole and Strip Plate (MHSP) based detector are the main components of the experimental system. The detector uses an MHSP in a Xe atmosphere at 1 bar, and acting as a photon counting device, i.e., it is capable to record each single event retaining the energy and the interaction position (2D-sensitive detector) information of the incident photon, demonstrating to be a promising device for EDXRF imaging applications. This work presents studies of energy resolution, energy linearity and spatial resolution/elemental mapping as a function of image magnification of the system.     

Synthesis and Properties of a New Two—Photon—absorbed Material DMAEAS

IntroductionSubstitutedstilbeneshavesignificantpotentialapplica tionssuchasfluorescencemicroscopy ,two photonphotody namictherapy ,opticalpowerlimiting ,three dimensionalstorage,andthree dimensionalmicrofabrication .1 4 Thesedyeshavestrongtendencyofintra molecularchargetransferundertheexcitedstate.Asaresult,theyusuallyexhibitlargetwo photonabsorption (TPA) ,inthemeanwhileemitstrongup convertedfluorescence .Ontheotherhand ,theirsolutionsgenerallydisplaylineartransmissionof >90 %atwavelengthof…     

Profile changes in barium Lα X-ray emission spectra due to excitation photon energies

New X-ray fluorescence satellites which are inside the natural width of the parent lines are observed in barium Lα_1,2 X-ray spectra. The measurements were performed with a double-crystal X-ray fluorescence spectrometer. Three X-ray tube anodes (Cr, W, Rh) were used in order to vary the excitation photon energy. As the photon energy of chromium Kα is between the L_III and the L_II threshold energies of barium, only an L_II electron of barium can be excited by the chromium anode tube. The narrowest profile was observed for Cr Kα excitation. Tungsten Lα and rhodium Kα photon energies are high enough to excite any L_I ,L_II or L_III electron of barium atom. Profile analysis shows that the satellite lines were produced by the excitation of W Lα or Rh Kα. It is concluded that the appearances of X-ray line-width satellites depend on primary photon energies, and that these satellites cause to smear the profiles of parent lines.     

ÜBER PHOSPHAZO-VERBINDUNGEN AUS NITRILEN V.1 DIE REAKTIONEN VON ACETONITRIL,PHENYLACETONITRIL UND MALONSÄUREDINITRIL MIT [C13P˭N‒PC13]C1

Abstract

Acetonitrile reacts with P₂NC1₇ to give a mixture of the ring compounds CC1?CC1?N?PC1₂?N?PC1₂ (1) and CC?CC1?N?PC1₂?N?PC1₂ (2), phenyl acetonitrile to give C(C₆H₅)?CC1?N?PC1₂?N?PC1₂ (3). Malonic acid dinitrile and P₂NC1₇ in dichloroethane yield a mixture of the ring compound C(CN)?CC1?N?PC1₂?N?PC1₂ (4) and the chain compound PC1₃?N?PC1₂?N?CC1?CH?CN (5), while the latter compound is exclusively formed when the reaction is carried out in PC1₃. Preparation, nmr and mass spectra of the new compound are described and discussed.

Acetonitrile reacts with P₂NC1₇ zu einem Gemisch der ringförmigen Verbindungen CC1?CC1?N?PC1₂?N?PC1₂ (1) und CC?CC1?N?PC1₂?N?PC1₂ (2), Phenylacetonitril zu C(C₆H₅)?CC1?N?PC1₂?N?PC1₂ (3). Aus Malonsäuredinitril und P₂NC1₇ entsteht in Dichloräthan ein Gemisch des Heterocyclus C(CN)?CC1?N?PC1₂?N?PC1₂ (4) und der kettenförmigen Verbindung PC1₃?N?PC1₂?N-CC1?CH?CN (5), wöhrend in PC1₃ als Reaktionsmedium ausschlieβlich die Verbindung 5 gebildet wird. Darstellung, NMR- und Massenspektren der neuen Verbindungen sind beschrieben und diskutiert.     

Fabrication of Tubular Structure Agglomerates of Calcium Carbonate by Using Collodion Film

A novel and simple method for preparing tubular structure agglomerates of calcium carbonate (CC-tube) is described. Calcium chloride and sodium carbonate aqueous solutions were used as reactants separated by a collodion film (a nitrocellulose material) in aqueous solution. The effects of the concentrations of calcium chloride and sodium carbonate aqueous solutions on the morphology and phase structure of the as-obtained samples were investigated. The CC-tube growth was prevented with the increase of reactant concentration from 0.5 to 1.0 mol•L－1. Compared with Na2CO3 aqueous solution, it is favourable to grow calcite crystals in CaCl2 aqueous solution. The products were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron- microscopy.     

Influence of the distance between a spectrometer and sample on the intensity of X-ray fluorescence

Expressions for calculating the extreme point coordinates of focal spots of X-ray tubes and a detector’s sensitive area are found. These coordinates are used in calculations of the sample area. The dependence of the X-ray fluorescence intensity on the distance between a spectrometer and an analyzed sample is studied experimentally. The intensities of the FeK _α spectral lines in iron-containing materials are calculated at different geometric parameters of a spectrometer. It is found that the distance between a sample and detector at which the maximum of the measured intensity is observed depends on the size and position of the detector and X-ray tube collimators, as well as on the relative position of the X-ray tube and detector. Recommendations on how to achieve the maximum intensity of X-ray fluorescence are proposed. The results of the present work can be used for the development of X-ray fluorescence analysis techniques applicable for free-flowing materials directly in technological processes.     

Development of high-sensitivity radio gas chromatography--specific characteristics of a long path internal gas flow proportional counter (author's transl)

A long path internal gas flow proportional counter was devised was to be used as a high sensitivity detector for radio gas chromatography, and its performance characteristics were investigated. The long path counter tube used for this detector has a sufficiently long passage in comparison with the diameter. The counter tube for general use is made of brass or copper tube 1 cm in diameter, 100 cm in length with a mirror finish on all internal surface, and the center electrode is of tungsten wire 0.05 mm in diameter. For actual use, several of these counter tubes are connected in series in assembly to hold the total volume of a gas sample in the counting system over a desired counting period. Thus this flow detector as an integral type one and gives directly a counting rate. Experiments showed that the dynamic counting efficiencies of tritium and carbon-14 were about 90% and equal to the static counting efficiencies. Furthermore, with this detector, the counting rate does not appear to be affected by minor variations of the effective inner volume of the counter tube and the flow rate of counting gas.     

Simple, stable and sensitive electrogenerated chemiluminescence detector for high-performance liquid chromatography and its application in direct determination of multiple fluoroquinolone residues in milk

A simple, stable and sensitive electrogenerated chemiluminescence (ECL) detector was developed. It was based on tris(2,2-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺) immobilized on the surface of a Pt wire with Nepem-105D ion exchange solution. The detector was prepared by inserting a Pt wire with immobilized Ru(bpy)₃²⁺ (working electrode) into a capillary tube, followed by inserting another Pt wire (counter electrode) in this tube and sealing. ECL behavior was investigated using ofloxacin as an analyte. Under optimal conditions, stable ECL intensity was obtained. This detector has been used in HPLC-ECL for the determination of multiple target fluoroquinolone residues in milk. There is no post column reagent addition, which would dilute the analytes, potentially leading to chromatographic band-broadening. The system is very simple with low dead volume, low baseline and background noise, together with high sensitivity and stability. The as-prepared ECL detector, when was used for the determination of ofloxacin, pefloxacin, enrofloxacin and difloxacin in milk, demonstrated adequate sensitivity to allow quantification of trace FQ levels in commercial milk samples. One or more of the target FQ analytes were present at levels above the LOD of the new ECL detector in each and every one of the 22 milk samples analysed.     

Construction of a windowless Si-anode X-ray tube for a more efficient excitation of low Z elements on Si-wafer surfaces in total reflection fluorescence analysis

To improve the achievable detection limits of low Z element with TXRF, a commercially available 2 kW X-ray tube (SEIFERT Type SF 60, Ahrensburg) with a 40 μm×8 mm fine focus has been modified. A windowless X-ray tube has been realized by removing the Be window out of the tube. The original Cu anode block has been changed to Al, because of sputtering reasons. A 4–6 μm thick pure silicon layer has been sputtered on the Al substrate. The geometry of the anode has been constructed in a specific way in order to optimize the photon flux of the X-ray beam concerning self-absorption and brilliance. Direct vacuum tight coupling to the measuring chamber and operation at 10⁻⁶ mbar vacuum was successfully shown. First measurements have been perfomed with a detector suitable for the detection of low energy photons in total reflection XRF geometry. Sodium has been analyzed on a Si-wafer surface and detection limits of 36 pg (corresponds to 3E9 atoms/cm²) have been achieved and are 10 times better than the detection limits for Na excited with a 1.3 kW Cr standard tube of 330 pg. With this developed X-ray tube the detection limits required by the Semiconductor industry for Si wafer surface contamination quality control are fulfilled.     

X线平片和CT扫描在外伤性脊椎骨折部位及解剖学改变诊断中的应用

分析X线平片和CT扫描对外伤性脊椎骨折部位的检出情况、骨折部位解剖学改变的显示情况,并对治疗效果进行评价。本研究选取2018年1月~2019年6月于我院进行手术治疗的外伤性脊椎骨折患者90例,所有患者均行X线平片和CT扫描检查,以手术结果为参考,观察X线平片和CT扫描对外伤性脊椎骨折部位(前柱、中柱、后柱)的检出情况、骨折部位解剖学改变(小关节滑脱、骨碎片、椎体移位、椎管狭窄)的显示情况,以及对术后椎弓根未完全到达椎体的检出情况。结果显示,CT扫描对中柱骨折、后柱骨折的诊断符合率均明显高于X线平片(P<0.05);对前柱骨折的诊断符合率与X线平片比较无差异(P>0.05)。CT扫描对小关节滑脱、骨碎片、椎体移位、椎管狭窄的诊断符合率均明显高于X线平片(P<0.05);对术后椎弓根未完全到达椎体检出率为88.89%,高于X线平片的77.78%,但差异无统计学意义(P>0.05)。CT扫描对外伤性脊椎骨折部位检出率及骨折部位解剖学改变的显示均优于X线平片,有利于临床治疗方案的制定,可作为外伤性脊椎骨折的首选诊疗检查方法。     

Oxygen Vacancy Induced Structural Distortions in Black Titania: A Unique Approach using Soft X-ray EXAFS at the O–K Edge

Unknown changes in the crystalline order of regular TiO₂ result in the formation of black titania, which has garnered significant interest as a photocatalytic material due to the accompanying electronic changes. Herein, the nature of the lattice distortion caused by an oxygen vacancy was determined that in turn results in the formation of mid-band-gap states found in previous studies of black titania. An innovative technique is introduced using a state-of-the-art silicon drift detector, which can be used in conjunction with extended X-ray absorption fine structure (EXAFS) to measure bulk interatomic distances. Also discussed is how the energy dispersive nature of such a detector can allow for an unimpeded signal, indefinitely in energy space, thereby sidestepping the hurdles of more conventional EXAFS, which is often impeded by other absorption edges.     

Synthesis and Nonlinear Optical Characterization of a New Twophoton Absorbing Organic Dye：DMAHAS

IntroductionThepotentialforuseoftwo photonabsorbingmoleculesinapplicationsrangingfromopticallimiting1 3tothreedimensional (3D)fluorescencemicroscopy4 and 3Dmicrofabricationandopticaldatastorage5,6 hasstimulatedresearchonthedesign ,synthesis ,andcharacterizationofnewmoleculeswithlargetwo photonabsorptivities .7,8Thetwo photonabsorption (2PA)processconsideredherein volvesthesimultaneousabsorptionoftwophotons ,eitherdegeneratingornondegenerating ,atwavelengthswellbe yondthelinearabsorptionspectr…     

Determination of itopride hydrochloride by high-performance liquid chromatography with Ru(bpy)3 electrogenerated chemiluminescence detection

In this work, a stable electrogenerated chemiluminescence (ECL) detector was developed. The detector was prepared by packing cation-exchanged resin particles in a glass tube, followed by inserting Pt wires (working electrode) in this tube and sealing. The leakage of Ru(bpy)₃²⁺ can be compensated by adding a small amount of Ru(bpy)₃²⁺ into solution phase. Coupled with high-performance liquid chromatography separation, the detector has been used for determination of itopride hydrochloride in human serum. Under the optimal conditions, the ECL intensity has a linear relationship with the concentration of itopride hydrochloride in the range of 1.0 × 10⁻⁸ g mL⁻¹ to 1.0 × 10⁻⁶ g mL⁻¹ and the detection limit was 3 × 10⁻⁹ g mL⁻¹ (S/N = 3). The as-prepared ECL detector displayed good sensitivity and stability.     

Separation of betacyanins from flowers of Amaranthus cruentus L. in a polar solvent system by high‐speed counter‐current chromatography

Betacyanin extract of Amaranthus cruentus L. flowers was fractionated by semi‐preparative high‐speed counter‐current chromatography in a highly polar solvent system: propan‐1‐ol/acetonitrile/(NH₄)₂SO_{4satd. soln}/H₂O (1.0:0.5:1.2:1.0, v/v/v/v) in tail‐to‐head mode with 76% retention of the stationary phase. The crude extract as well as the fractions containing betacyanins were analyzed by liquid chromatography with tandem mass spectrometry as well as by high‐resolution ion‐trap time‐of‐flight mass spectrometry detection technique for the molecular formulae and multi‐step fragmentation pattern elucidation. Four betacyanins; namely, amaranthin, betanin, 6′‐O‐formyl‐amaranthin, and 6′‐O‐malonyl‐amaranthin as well as their diastereomeric forms differing in the configuration of the C‐15 carbon atom were identified in the fractions. Amaranthin was the dominant pigment in the extract and was additionally analyzed by nuclear magnetic resonance correlation techniques after the counter‐current chromatographic and high‐performance liquid chromatographic isolation. Betacyanins were highly enriched during a single high‐speed counter‐current chromatographic step; therefore, the tentative identification of new compounds for the whole Amaranthaceae family, 6′‐O‐formyl‐amaranthin and 6′‐O‐malonyl‐amaranthin was possible. Different elution profiles of the pigments observed in the counter‐current chromatographic system in comparison to high‐performance liquid chromatography system confirm a complementarity of both the techniques especially in the separation of diastereomeric pairs of betacyanins.     

Improved synchronized accumulating radioisotope detector for gas chromatography

A synchronized accumulating radioisotope detector for radio gas chromatography was developed. It comprised seven gas-flow proportional counters each with an inner volume of 10 ml. Every counter tube was connected by a mutual anti-coincidence circuit to reduce the background. The transit time of gas particles in one counter tube could be set to an optimal value between 1 and 4 s by regulating the flow-rate of the counting gas, according to analytical requirements. The improved detector maintained high chromatographic resolution, which suggested the applicability of the apparatus to capillary gas chromatography.     

Automatic Carbon,Hydrogen, Nitrogen,Sulfur Analyzer Ciiemistry of Sulfur Reactions

Abstract

An automatic analyzer for the simultaneous microdetermination of carbon, hydrogen, nitrogen, and sulfur is described. The method is based on the uncatalyzed, dynamic, flash-combustion of the sample in an oxygen/helium atmosphere in a quartz tube. Separation of the combustion gases, N₂, CO₂, SO₂, and H₂O is accomplished by using gas chromatography and a thermal conductivity detector. Reactions of SO₂ formation are given in detail.     

Study on the application of reduced graphene oxide and multiwall carbon nanotubes hybrid materials for simultaneous determination of catechol,hydroquinone, p-cresol and nitrite

In this paper, the reduced graphene oxide and multiwall carbon nanotubes hybrid materials (RGO–MWNTs) were prepared and a strategy for detecting environmental contaminations was proposed on the basis of RGO–MWNTs modified electrode. The hybrid materials were characterized by the scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and N₂ sorption–desorption isotherms. Due to the excellent catalytic activity, enhanced electrical conductivity and high surface area of the RGO–MWNTs, the simultaneous measurement of hydroquinone (HQ), catechol (CC), p-cresol (PC) and nitrite (NO₂⁻) with four well-separate peaks was achieved at the RGO–MWNTs modified electrode. The linear response ranges for HQ, CC, PC and NO₂⁻ were 8.0–391.0 μM, 5.5–540.0 μM, 5.0–430.0 μM and 75.0–6060.0 μM, correspondingly, and the detection limits (S/N = 3) were 2.6 μM, 1.8 μM, 1.6 μM and 25.0 μM, respectively. The outstanding film forming ability of RGO–MWNTs hybrid materials endowed the modified electrode enhanced stability. Furthermore, the fabricated sensor was applied for the simultaneous determination of HQ, CC, PC and NO₂⁻ in the river water sample.     

Influence of the Metal Ion on the Two‐Photon Absorption Properties of Lanthanide Complexes Including Near‐IR Emitters

The synthesis of tris(2‐thenoyltrifluoroacetonate)lanthanide(III) complexes featuring a diethylaminostyryl‐2,2′‐bipyridine coligand was achieved for lanthanum; the near‐infrared (NIR) emitters neodymium, erbium, and ytterbium; and the transition‐metal yttrium. The photophysical properties were thoroughly studied, and it was demonstrated that the conjugated bipyridine ligand acts as a good antenna for the sensitization of the NIR emitters. The two‐photon absorption (TPA) properties of all five complexes were investigated by using both two‐photon excited fluorescence and the Z‐scan method. We demonstrate that the nature of the rare earth ion has almost no influence on the TPA properties centered on the conjugated bipyridyl ligand. Finally, we show that Yb^III is sensitized by a two‐photon antenna effect, and that Nd^III is mostly sensitized by a one‐photon process involving direct excitation of forbidden f–f transitions.