Synthesis and Characteristics of a New Fluorogenic Substrate for Horseradish Peroxidase

N,N′-Dicyanomethyl-o-phenylenediamine was synthesized with a 90% yield by a reaction ofo-phenylenediamine with chloroacetonitrile in triethylamine. Our experimental results showed that it was the effective fluorogenic substrate for horseradish peroxidase (HRP) and hemin. TheK_mfor the HRP system was 48 μM,and that for hemin was 1.3 μM.Properties of the substrate were evaluated from the detection limits of enzymes and H₂O₂. The linear ranges for the determination of HRP and hemin were 21–150 pMand 2–20 nM,respectively. The linear range for the determination of H₂O₂using HRP or hemin was 18–140 and 60–1000 nM,respectively. The structural elucidation of the fluorescent product using NMR and mass spectral techniques was proposed to be 1,2-dihydro-2-imido-imidazo[1,2-a] quinoxaline. Based on the product structure and earlier reports, the possible reaction mechanism of HRP and the substrate was also proposed, i.e., two steps for ring closures, one step of isomerization, and a final step of oxidative dehydrogenation.     

Ultrathin polymer film formation by collision-induced cross-linking of adsorbed organic molecules with hyperthermal protons

A new synthetic approach for the formation of ultrathin polymer films with customizable properties was developed. In this approach, the kinematic nature of proton collisions with simple organic molecules condensed on a substrate is exploited to break C-H bonds preferentially. The subsequent recombination of carbon radicals gives a cross-linked polymer thin film, and the selectivity of C-H cleavage preserves the chemical functionalities of the precursor molecules. The nature and validity of the method are exemplified with theoretical results from ab initio molecular dynamics calculations and experimental evidence from a variety of characterization techniques. Its applicability is demonstrated by the synthesis of ultrathin polymer films with precursor molecules such as dotriacontane, docosanoic acid, poly(acrylic acid) oligomer, and polyisoprene. The approach is fundamentally different from conventional chemical synthesis as it involves an unusual mix of physical and chemical processes including charge exchange, projectile penetration, kinematics, collision-induced dissociation, inelastic energy transfer, chain transfer, and chain cross-linking.     

Carbonyldinitrosyltris(fluorosulfato)tungstate(II) and ‐Molybdate(II) Anions: Synthesis,Spectroscopy, and Density Functional Theory Calculations

Carbonyldinitrosyltris(fluorosulfato)tungstate(II) and ‐molybdate‐(II) anions, [fac‐M(CO)(NO)₂(SO₃F)₃]^? (M=W, Mo), which are novel weakly coordinating anions that contain a metal carbonyl/nitrosyl moiety, have been generated in fluorosulfonic acid and completely characterized by multinuclear NMR, IR, and Raman spectroscopy as well as ESI mass spectrometry. ESI MS measurements performed for the first time on a superacidic solution system unambiguously reveal the formation of the monoanionic, mononuclear W and Mo complexes formulated as [M(CO)(NO)₂(SO₃F)₃]^? (M=W, Mo). Multinuclear NMR spectroscopic studies at natural abundance and ¹³C and ¹⁵N enrichment clearly indicate the presence of one CO ligand, two equivalent NO ligands, and two types of nonequivalent SO₃F^? groups in a 2:1 ratio. The IR and Raman spectra reveal that the two equivalent NO ligands have a cis conformation, thus indicating a fac structure. Density functional calculations at the B3LYP level of theory predict that these anions have a singlet ground state (¹A′) with a C_s symmetry along with C–O and N–O vibrational frequencies that are in agreement with the experimental observations. Mulliken population analysis shows that the monovalent negative charge is dispersed on the bulky sphere, the surface of which is covered by all the negatively charged O and F atoms with charge densities much lower than SO₃F^?, suggesting that [fac‐M(CO)(NO)₂(SO₃F)₃]^? (M=W, Mo) are weakly nucleophilic and poorly coordinating anions.     

Application of the slotted quartz tube in flow-injection flame atomic-absorption spectrometry

The slotted quartz has been applied to flow-injection flame atomic-absorption spectrometry (FI-FAAS) showing several important advantages. The tube life was improved by a factor of 5-6 compared to conventional continuous aspiration. Flow impact systems were found not to be necessary in the applications so that larger enhancement factors may be achieved without sacrifice in precision. For 1.0 mg/l. copper, 1.0 mg/l. lead, 0.1 mg/l. cadmium and 1.0 mg/l. gold sensitivity enhancement factors of 3.1, 5.5, 5.3 and 4.0 were obtained with precisions of 1.3%, 1.1%, 1.6% and 1.7% RSD (n = 11) respectively. Application of the slotted quartz tube FI-FAAS method to the determination of heavy metals in urine has shown improved tolerance to interfering matrices. Recoveries obtained by spiking undiluted urine samples with 0.1 mg/l. copper and lead, and 0.01 mg/l. cadmium were in the range 100-102%.     

光学解偏振法测定高聚物的结晶速度

制成了光学解偏振法测定高聚物结晶过程的仪器,测试了聚丙烯、尼龙6等几种试样。本方法的优点是:样品用量少,测试温度范围宽,可以测定较快的结晶过程。由于设计了透射光强度自动控制电路,实验结果可靠,重复性好,并能自动记录。     

Self-gelatinizable copolymer immobilized glucose biosensor based on prussian blue modified graphite electrode

A novel poly(vinyl alcohol) grafting 4-vinylpyridine self-gelatinizable copolymer was adapted to immobilize glucose oxidase. The reduction of hydrogen peroxide (H2O2) was detected at a Prussian Blue (PB) modified graphite electrode. A stable and sensitive glucose amperometric biosensor is described. The copolymer is a good biocompatible polymer in which the glucose oxidase retains high activity. Moreover, the copolymer can adhere firmly to the inorganic PB membrane. The sensor showed an apparent Michaelis-Menten constant of 18 +/- 0.2 mM and a maximum current density of 1.14 microA cm-2 mM-1. The linear range is from 5 microM to 4.5 mM glucose and the detection limit is 0.5 microM glucose. The catalytic efficiency of PB for the reduction of H2O2 is higher than that for the oxidation of H2O2. Glucose concentrations in serum samples from healthy persons and diabetic patients were determined using the sensor. The results compared well with those provided by the hospital using a spectroscopy method.     

Mass spectrometry-based chemical mapping and profiling toward molecular understanding of diseases in precision medicine

Precision medicine has been strongly promoted in recent years. It is used in clinical management for classifying diseases at the molecular level and for selecting the most appropriate drugs or treatments to maximize efficacy and minimize adverse effects. In precision medicine, an in-depth molecular understanding of diseases is of great importance. Therefore, in the last few years, much attention has been given to translating data generated at the molecular level into clinically relevant information. However, current developments in this field lack orderly implementation. For example, high-quality chemical research is not well integrated into clinical practice, especially in the early phase, leading to a lack of understanding in the clinic of the chemistry underlying diseases. In recent years, mass spectrometry (MS) has enabled significant innovations and advances in chemical research. As reported, this technique has shown promise in chemical mapping and profiling for answering “what”, “where”, “how many” and “whose” chemicals underlie the clinical phenotypes, which are assessed by biochemical profiling, MS imaging, molecular targeting and probing, biomarker grading disease classification, etc. These features can potentially enhance the precision of disease diagnosis, monitoring and treatment and thus further transform medicine. For instance, comprehensive MS-based biochemical profiling of ovarian tumors was performed, and the results revealed a number of molecular insights into the pathways and processes that drive ovarian cancer biology and the ways that these pathways are altered in correspondence with clinical phenotypes. Another study demonstrated that quantitative biomarker mapping can be predictive of responses to immunotherapy and of survival in the supposedly homogeneous group of breast cancer patients, allowing for stratification of patients. In this context, our article attempts to provide an overview of MS-based chemical mapping and profiling, and a perspective on their clinical utility to improve the molecular understanding of diseases for advancing precision medicine.

An overview of MS-based chemical mapping and profiling, indicating its contributions to the molecular understanding of diseases in precision medicine by answering "what", "where", "how many" and "whose” chemicals underlying clinical phenotypes.     

Tutorial: Capillary Electrophoresis

In recent years a number of exciting developments have emerged in the area of scientific computational tools for classroom use. Computer Algebra Systems (CASs), for example, Maple, are at the forefront of this arena. Such tools have been long sought by teachers of physical chemistry, inherently a mathematics intensive subject. With a CAS at hand, students can look forward to taking college science courses, like physical chemistry, without the usual mathematics anxiety. These tools can be used to do numerical and symbolic mathematics including calculus and linear algebra. In addition, they have wonderful graphics capabilities that include three-dimensional plots, contour plots, and animations. This paper describes the implementation of Maple in two junior-level physical chemistry courses. The materials used for beginning workshops are presented here and additional examples of Maples graphic and algebraic capabilities are described.     

Synthesis, crystal structure and magnetic property of the novel dinuclear nickel(II) complex with 4-(p-methoxyphenyl)-3,5-bis(pyridine-2-yl)-1,2,4-triazole

A novel dinuclear nickel(II) complex, [Ni₂(MOBPT)₂Cl₂(H₂O)₂]Cl₂ · 7H₂O (MOBPT = 4-(p-methoxyphenyl) −3,5-bis(pyridine-2-yl)-1,2,4-triazole), has been synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction methods. The crystal structure determination shows that the dinuclear Ni₂N₈ unit is almost planer in which each Ni^II ion is coordinated by four nitrogen atoms from MOBPT equatorially and a water molecule and a chloride ion axially in a distorted octahedral geometry. Magnetic measurements reveal a relatively weak antiferromagnetic exchange in the complex.