Protein identification by peptide mass fingerprinting and peptide sequence tagging with alternating scans of nano-liquid chromatography/infrared multiphoton dissociation Fourier transform ion cyclotron resonance mass spectrometry

We have developed a method for protein identification with peptide mass fingerprinting and sequence tagging using nano liquid chromatography (LC)/Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). To achieve greater sensitivity, a nanoelectrospray (nano-ES) needle packed with reversed-phase medium was used and connected to the nano-ES ion source of the FTICR mass spectrometer. To obtain peptide sequence tag information, infrared multiphoton dissociation (IRMPD) was carried out in nano-LC/FTICR-MS analysis. The analysis involves alternating nano-ES/FTICR-MS and nano-ES/IRMPD-FTICR-MS scans during a single LC run, which provides sets of parent and fragment ion masses of the proteolytic digest. The utility of this alternating-scan nano-LC/IRMPD-FTICR-MS approach was evaluated by using bovine serum albumin as a standard protein. We applied this approach to the protein identification of rat liver diacetyl-reducing enzyme. It was demonstrated that this enzyme was correctly identified as 3-alpha-hydroxysteroid dehydrogenase by the alternating-scan nano-LC/IRMPD-FTICR-MS approach with accurate peptide mass fingerprinting and peptide sequence tagging.     

Photo-Induced Dihydroxylation of Alkenes with Diacetyl,Oxygen, and Water

Herein reported is a photo-induced production of vicinal diols from alkenes under mild reaction conditions. The present dihydroxylation method using diacetyl (= butane-2,3-dione), oxygen, and water dispenses with toxic reagents and intractable waste generation.     

藉高锰酸钾氧化双乙酰的化学发光反应测定微量锰

研究了高锰酸钾氧化双乙酰的化学发光反应。根据微量Ｍｎ６２＋对上述体系化学发光山峰时间的影响，建立了测定Ｍｎ６２＋的分析方法。该法线性范围为１．０×１０＾－４－８．０×１０＾－６７ｍｏｌ／Ｌ，相对标准偏差为３．５％，检出限为６．０×１０＾－８ｍｏｌ／Ｌ。应用于合金中锰的测定，结果良好。     

Single crystal X-ray of 1-[(1,2,4-triazole-4-yl)imino]diacetyl monoxime (L) as a novel triazole and the characterization and biological studies of its chelates of Co2+, Pd2+, and Fe3+

A novel and efficient synthesis of 1-[(1,2,4-triazole-4-yl)imino]diacetyl monoxime ( L ) is described. The advantages of this method are that it is inexpensive, the starting reactants are readily available, and it has good yield and short reaction times. The hull of the product was suggested by elemental analyses, spectral and single crystal X-ray. Novel Co ²⁺ , Pd²⁺, and Fe ³⁺ chelates derived from L were characterized by Fourier transform infrared spectroscopy, suggesting that L acts as bidentate via the two azomethine groups. Tetrahedral geometry for Fe³⁺ and Co²⁺ and square-planar geometry around the Pd²⁺ chelate were suggested depending on the spectral and magnetic data. The results of density functional theory were applied to illustrate the geometry of L towards the metal ions. Coats–Redfern and Horowitz–Metzger methods were applied to investigate the kinetic and thermodynamic parameters of the chelates. Cyclic voltammetry was carried out to study the stability of the Co²⁺ and Fe³⁺ chelates. L and its complexes were tested against three types of cancer cells, antibacterial and antifungal.     

Water Soluble Gold(I)‐diacetyl‐1,3,5‐triaza‐7‐phosphaadamantane‐arylazoimidazole Complexes: Synthesis and Spectroscopic Study

Reaction of [Au(DAPTA)(Cl)] with RaaiR’ in CH2Cl2 medium following ligand addition leads to [Au(DAPTA)(RaaiR’)](Cl) [DAPTA＝diacetyl-1,3,5-triaza-7-phosphaadamantane, RaaiR’＝p-R-C6H4-N＝N- C3H2-NN-1-R’, (1—3), abbreviated as N,N’-chelator, where N(imidazole) and N(azo) represent N and N’, respectively; R＝H (a), Me (b), Cl (c) and R’＝Me (1), CH2CH3 (2), CH2Ph (3)]. The 1H NMR spectral measurements in D2O suggest methylene, CH2, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets. 13C NMR spectrum in D2O suggest the molecular skeleton. The 1H-1H COSY spectrum in D2O as well as contour peaks in the 1H-13C HMQC spectrum in D2O assign the solution structure.     

Glycerol acetylation considering competing dimerization

Glycerol acetylation is a very interesting reaction for studies of consecutive kinetics. In this short communication, we present a pseudo-homogeneous model for the synthesis of triacetyl glycerol from the reaction of glycerol and acetic acid over strongly acidic Amberlyst-15 and Amberlyst-70 catalysts, considering a dimerization of diacetyl glycerol (DAG) into diglycerol tetraacetate as a parallel reaction and compare the results with a model without side reactions. The best fits were obtained for apparent zeroth-order dimerization and first-order consecutive reactions in the presence of acetic acid in excess and with removal of water. An adaptation was made for DAG. The proposed model shows that the formation of DAG is faster than the consumption of glycerol, which could be an explanation for the occurrence of DAG dimerization instead of other parallel reactions in acetylation.     

Diacetyl production mechanism by a strain ofLactococcus lactis spp.lactis bv.diacetylactis

Diacetyl production via alpha-acetolactic acid (ALA) extracellular decarboxylation inLactococcus lactis spp.lactis bv.diacetylactis SD 933 cultures has been assessed under anaerobiosis both in batch and continuous fermentations at pH 5.5 and 8.0 by studying the effects of alpha-acetolactate decarboxylase (ADC) addition in the culture broth. This enzyme, favoring the formation of acetoin instead of diacetyl, was added extracellularly and did not disturb diacetyl production. Moreover, oxidation experiments on extracellular culture media did not reveal any increase in diacetyl amount caused by extracellular ALA oxidative decarboxylation. These observations confirm previous assertions concerning the mechanism and localization of diacetyl synthesis by theSD 933 strain.     

荧光分析法测定痕量丁二酮

本文报道了邻苯二胺与丁二酮在１ｍｏｌ／ＬＨ２ＳＯ４介质中反应生成２，３－二甲基喹喔啉。该化合物具有较强的荧光（λｘ／λｅｍ＝３４０ｎｍ／４９０ｎｍ）其荧光量子产率ΦＦ＝０．１０１。丁二酮浓度在４．０×１０＾－７～５．２×１０＾－５ｍｏｌ／Ｌ范围内与转化成产物的相对荧光强度呈线性关系，相对标准偏差为１％，检出限为１．３×１０＾－７ｍｏｌ／Ｌ，考察了３０种物质表明，该法选择性好，用于实际啤酒样品中丁二     

气相色谱法测定电子烟烟液及气溶胶中双乙酰和乙酰丙酰

建立气相色谱法氢火焰离子化检测器测定电子烟烟液和气溶胶中双乙酰和乙酰丙酰含量的方法。样品以20 mL乙醇为萃取剂,涡旋振荡萃取10 min,采用气相色谱外标法进行定量分析。双乙酰和乙酰丙酰质量浓度在0.5~50 μg/mL范围内与色谱峰面积呈良好的线性关系,相关系数分别为0.999 6、0.999 4,方法检出限分别为0.044、0.052 μg/mL。烟液中双乙酰和乙酰丙酰测定结果的相对标准偏差为2.5%~4.3%(n=6),样品加标回收率为95.0%~102.5%;气溶胶中双乙酰和乙酰丙酰测定结果的相对标准偏差为3.1%~4.6%(n=6),样品加标回收率为92.7%~102.3%。气溶胶中双乙酰和乙酰丙酰理论浓度与实测浓度具有较强的相关性(对于双乙酰r~2=0.990 1,对于乙酰丙酰r~2=0.994 7),说明双乙酰、乙酰丙酰烟液通过雾化直接转移至气溶胶中。该方法准确度高,重现性好,检出限低,可满足电子烟样品的检测需求。     

The crystal structure of hexaammonium diacetyl‐octa‐molybdate tetrahydrate

The crystal structure of hexaammonium diacetyl‐octa‐molybdate tetrahydrate, (NH₄)₄₂[Mo₁₃₂O₃₇₂ (CH₃COO)₃₀(H₂O)₇₂] is documented. The crystals are triclinic, space group P‐1, with a=8.1018(16) Å, b=10.334(2) Å, c=12.238(2) Å, α=68.20(3)°, β=74.98(3)°, γ=67.25(3)°, V=869.3(3) ų, Z=1. The structure was solved by direct methods and refined by least squares methods to a Final R1 = 0.0374 and wR2 = 0.1074 for 3805 observed reflections with I > 2σ(I). The structure contains ammonium cations and isolated acetyl octamolybdate(6‐) anions, [Mo₈O₂₈(CH₃CO)₂]^6‐. The crystallographic data of the structure was deposited with the Cambridge Data Center as No. CCDC 249565. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)