Control strategies for laser separation of carbon isotopes

Laser isotope separation (LIS) by infrared laser chemistry of polyatomic molecules has come a long way since its discovery. The last decade has seen considerable efforts in scaling up of the process for light elements like carbon, oxygen and silicon. These efforts aim at ways to improve both the enrichment factor and the throughput. The achievement is quite significant especially for carbon isotope separation wherein macroscopic operating scales have been realized. We report our studies on the IR laser chemistry of two promising systems, viz. neat CF₂HCl and CF₃Br/Cl₂. We have investigated conditions for optimizing the dissociation yield and selectivity using natural samples containing l.l%C-13.Wealso highlight our current efforts for scaling up the process. These include the design aspects of a photochemical reactor with multipass refocusing Herriott optics for efficient photon utilization, development of a cryogenic distillation set up and a preparative gas chromatograph for large scale separation/collection of the isotopically enriched photoproduct in the post-irradiation stage.     

硅橡胶(PDMS)—聚砜(PS)复合渗透膜的氧氮透气性和渗透过程

用扫描电镜观察了多孔PS膜和PDMS—PS复合膜的断面结构形态,认为复合膜中的PS柱状孔是支撑层,PS界面的微孔层和PMDS的均质涂层组成的双层结构是影响复合膜透气性的主要结构。提出了理论分析的模型与透气量的计算公式,计算结果与实测值基本相符。测定了氧、氮、空气在不同温度下透过PDMS均质膜和PDMS—PS复合膊的透过系数P或透气速率J,给出了lgP或lgJ与1/T符合Arrhenius公式的线性关系。研究了操作参数对复合膜富集空气中氧的影响规律。     

PARTICULATE CONCENTRATION ENRICHMENT OF PRIMARY AIR IN PULVERIZED COAL BOILERS

Particulate concentration enrichment (PCE) of primary air favors flame ignition and stabilization, and the reduction of NOx emission in pulverized coal combustion. The methods used for PCE are summarized in five categories:Cyclone PCE, Elbow PCE, Blunt-body PCE, Hydrodynamic PCE and Swirling PCE. Practice of each PCE method is illustrated with typical burners and the associated pros and cons are discussed. It is found that the same principle prevails in all PCE methods, that is, due to inertial difference, solid particles preferentially decelerate and separate from the gas stream when the main flow deviates in flow orientation. From analysis of various P-C burners, PCE design is deemed to yet comprise “rule of thumb” practice. Some discussions regarding PCE application are given.     

Die Gewinnung von trägerarmem 114mIn durch Szilard-Chalmers-Anroicherung aus den Metallphthalocyaninen

Unter Verwendung von Indiumphthalocyanin als Target wurde der Anreicherung von ^114mIn durch den Szilard-Chalmers-Prozeβ untersucht. Bei Bestrahlung in der Spaltzone des Kernreaktors gelang es, spezifische Aktivitäten zu erzielen, die ohne Anreicherung nur durch sehr lange Bestrahlungszeiten erreicht werden können. Die Abhängigkeit der spezifischen Aktivität der spezifischen Aktivität von der Bestrahlungs zeit, von der Art und der Vorbehandlung der Targetverbindung, von der Dauer der Lagerung der bestrahlten Proben und von der Abtrennmethode wird angegeben.     

Enrichment of Lithium,Potassium, Copper,and Uranium Isotopes by Electromigration in a Cation Exchange Membrane

The ion exchange membrane can be used as an effective medium of electromigration for the separation of isotopes by the following reasons.     

A novel methodological approach for δ18O analysis of sugars using gas chromatography-pyrolysis-isotope ratio mass spectrometry

Although the instrumental coupling of gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) for compound-specific δ¹⁸O analysis has been commercially available for more than a decade, this method has been hardly applied so far. Here we present the first GC-Py-IRMS δ¹⁸O results for trimethylsilyl-derivatives of plant sap-relevant sugars and a polyalcohol (glucose, fructose, sucrose, raffinose and pinitol). Particularly, we focus on sucrose, which is assimilated in leaves and which is the most important transport sugar in plants and hence of utmost relevance in plant physiology and paleoclimate studies. Replication measurements of sucrose standards and concentration series indicate that the GC-Py-IRMS δ¹⁸O measurements are not stable over time and that they are amount (area) dependent. We, therefore, suggest running sample batch replication measurements in alternation with standard concentration series of reference material. This allows for carrying out (i) a drift correction, (ii) a calibration against reference material and (iii) an amount (area) correction. Tests with ¹⁸O-enriched water do not provide any evidence for oxygen isotope exchange reactions affecting sucrose and raffinose. We present the first application of GC-Py-IRMS δ¹⁸O analysis for sucrose from needle extract (soluble carbohydrate) samples. The obtained δ¹⁸O_{sucrose/ Vienna Standard Mean Ocean Water (VSMOW)} values are more positive and vary in a wider range (32.1–40.1 ‰) than the δ¹⁸O_{bulk/ VSMOW} values (24.6–27.2 ‰). Furthermore, they are shown to depend on the climate parameters maximum day temperature, relative air humidity and cloud cover. These findings suggest that δ¹⁸O_sucrose of the investigated needles very sensitively reflects the climatically controlled evaporative ¹⁸O enrichment of leaf water and thus highlights the great potential of GC-Py-IRMS δ¹⁸O_sucrose analysis for plant physiology and paleoclimate studies.     

Calcium isotope fractionation in liquid chromatography with crown ether resin in methanol medium

Breakthrough mode liquid chromatography was employed to investigate calcium (Ca) isotope fractionation in methanol medium. Highly porous silica beads, the inner pores of which were embedded with a benzo-18-crown-6 ether resin, were used as column packing material. Enrichment of heavier isotopes of Ca was observed in the frontal part of the respective Ca chromatograms. The values of the isotope fractionation coefficient (?) were in the order of 10^?3 at 25 °C. Use of methanol as solvent has little advantage over the aqueous system as far as the values of ? are concerned. However, a substantial improvement was observed concerning the adsorption capacity of the crown ether resin for Ca ions. Molecular orbital calculations supported the present isotopic results in a qualitative fashion.     

在线富集/高效液相色谱与电感耦合等离子体质谱联用测定玩具中超痕量可迁移六价铬

采用在线富集/高效液相色谱(HPLC)与电感耦合等离子体质谱(ICP-MS)联用技术,建立了玩具中超痕量可迁移六价铬的测定方法。以10 mmol/L硝酸铵为流动相,样品在Agilent BIO WAX NP5阴离子交换柱(4.6 mm×50 mm,5μm)中富集,再通过阀切换,以75 mmol/L硝酸铵将六价铬洗脱至Dionex AG7阴离子柱(4.0 mm×50 mm,10μm)中分离,最后经ICP-MS进行分析。优化得到在线富集时间为4 min,进样量为900μL,富集流速为0.4 mL/min,洗脱流速为0.6 mL/min。结果显示,六价铬在2～20 ng/L范围内线性良好,检出限为1.93 ng/L,相对标准偏差(RSD)为3.9%。与直接进样相比,浓缩因子约为8.1倍,富集效率约为90%。对欧盟玩具安全指令2009/48/EC规定的3类玩具材料在5、10 ng/L的浓度水平下进行加标回收,回收率为93.4%～111%。     

Selective enrichment of glycopeptides based on copper tetra(N‐carbonylacrylic) aminephthalocyanine and iminodiacetic acid functionalized polymer monolith

Efficient separation and enrichment of low‐abundance glycopeptides from complex biological samples is the key to the discovery of disease biomarkers. In this work, a new material was prepared by coating copper tetra(N‐carbonylacrylic) aminephthalocyanine and iminodiacetic acid onto poly(glycidyl methacrylate‐pentaerythritol triacrylate) monolith. The monolith was applied to polymer monolithic microextraction for specific capture of glycopeptides coupled with matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. The developed monolith exhibited satisfactory efficiency for glycopeptide enrichment with high selectivity and detection sensitivity. When the tryptic digest of immunoglobulin G was used as the sample, total 24 glycopeptides were identified and the detection limit was determined as 5 fmol. When the approach was applied to the analysis of glycopeptides in the mixture of bovine serum albumin and immunoglobulin G (100:1, m/m) digests, 16 glycopeptides could still be observed. Moreover, the monolith was successfully applied to the selective enrichment of glycopeptides from human serum digests, exhibiting great practicability in identifying low‐abundance glycopeptides in complex biological samples.     

Poly(amidoamine) dendrimer‐coated magnetic nanoparticles for the fast purification and selective enrichment of glycopeptides and glycans

Glycosylated proteins modulate various important functions of organisms. To reveal the functions of glycoproteins, in‐depth characterization studies are necessary. Although mass spectrometry is a very efficient tool for glycoproteomic and glycomic studies, efficient sample preparation methods are required prior to analyses. In the study, poly(amidoamine) dendrimer‐coated magnetic nanoparticles were presented for the specific enrichment and fast purification of glycopeptides and glycans. The enrichment and purification performance of the developed method was evaluated both at the glycopeptide, and the glycan level using several standard glycoprotein digests and released glycan samples. The poly(amidoamine) dendrimer‐coated magnetic nanoparticles not only showed selective affinity (Immunoglobulin G/Bovine Serum Albumin, 1/10 by weight) to glycopeptides and released glycans but also good sensitivity (0.4 ng/µL for Immunoglobulin G) for glycoproteomic and glycomic applications. Thirty‐five glycopeptides of Immunoglobulin G were detected after enrichment with poly(amidoamine) dendrimer‐coated magnetic nanoparticles. In addition, 55 ¹⁸O tagged deamidated glycopeptides belonging to human plasma glycoproteome were confirmed. Finally, fifty 2‐aminobenzoic acid, and 30 procainamide‐labelled human plasma N‐glycans released from human plasma glycoproteins were determined after purifications. The results indicate that the proposed enrichment and purification method using poly(amidoamine) dendrimer‐coated magnetic nanoparticles could be simply adjusted to sample preparation methods.