Laser desorption/ionization mass spectrometry on porous silica and alumina for peptide mass fingerprinting

We investigated a variant of desorption/ionization on porous silicon (DIOS) mass spectrometry utilizing an aqueous suspension of either porous silica gel or porous alumina (pore size of 60 and 90 A, respectively). Laser desorption/ionization (LDI) from samples directly deposited on a stainless steel surface without any inorganic substrates was also achieved. Synthetic peptides designed to cover large sequence diversity constituted our model compounds. Sample preparation, including material conditioning, peptide solubilization, and deposition protocol onto standard matrix-assisted laser desorption/ionization (MALDI) probe, as well as ionization source tuning were optimized to perform sensitive reproducible LDI analyses. The addition of either a cationizing agent or an alkali metal scavenger to the sample suspension allowed modification of the ionization output. Comparing hydrophilic silica gel to hydrophobic reversed-phase silica gel as well as increasing material pore size provided further insights into desorption/ionization processes. Furthermore, mixtures of peptides were analyzed to probe the spectral suppression phenomenon when no interfering organic matrix was present. The results gathered from synthetic peptide cocktails indicated that LDI mass spectrometry on silica gel or alumina constitutes a promising complementary method to MALDI in proteomics for peptide mass fingerprinting.     

6-Iodo-2-isopropyl-4H-3,1-benzoxazin-4-one as building block in heterocyclic synthesis

As a part of ongoing studies in the synthesis of a variety of heterocycles of biological importance, we report here an efficient and convenient method for the synthesis of novel compounds from 6-iodo-2-isopropyl-4H-3,1-benzoxazin-4-one 1 as building block. The reaction of benzoxazinone 1 with various reagents such as diethylmalonate, sodium azide, and phosphorus pentasulfide yielded the compounds 2–5. The behavior of benzothiazin-4-thione 5 toward formamide and hydrazine hydrate was investigated, forming the compounds 6 and 7. The reaction of quinazolinone derivative 8 with β-D-glucose pentaacetate, ethyl 2-methyl-5-((1S,2R,3R)-1,2,3,4-tetrahydroxybutyl)furan-3-carboxylate, epichlorohydrin and benzenesulphonyl chloride afforded quinazolinone derivatives 9, 10, 12, and 13 respectively. The reaction of quinazolinone derivative 10 with acetic anhydride resulted in formation of the acylated compound 11. The behavior of quinazolinylacetohydrazide derivative 14 toward carbon electrophiles^[16 El-Hashash, M. A.; El-Naggar, A. M.; El-Bordany, E. A.; Marzouk, M. I.; Nawar, T. M. S. Regioselectivity and regiospecificity of benzoxazinone (2-isopropyl4H-3,1-benzoxazinone) derivatives toward nitrogen nucleophiles and evaluation of antimicrobial activity. Synth. Commun. 2016, 46(14), 1230–1241.[Taylor & Francis Online], [Web of Science ®] , [Google Scholar]^] has been investigated by its reaction with ethyl benzoylacetate, potassium thiocyanate, and phenyl isothiocyanate, affording the quinazolinone derivatives 15, 16, and 18, respectively. Treatment of compound 16 with sodium hydroxide followed by hydrochloric acid yielded the mercapto-triazole derivative 17. The structures of the newly synthesized compounds were confirmed by elemental analysis, infrared (IR), ¹H NMR, ¹³C NMR, and mass spectra. The antimicrobial activities of some of the synthesized compounds were preliminarily evaluated.     

Multiphase flow modeling and optimization for online wash systems of gas turbines

Compressor blade fouling in gas turbines could lead to significant loss in power and efficiency. Online wash systems are used to remove fouling without having to shut down the gas turbine. Hence, the design of efficient online wash systems could lead to significant recovery of performance. The present study aims at developing a generalized numerical approach for the optimization of online wash systems for gas turbines. The procedure utilizes a Lagrangian particle-tracking multiphase flow model combined with constrained multi-objective optimization to develop design charts for selecting the optimal nozzle diameter, location, mass flow rate and half-cone angle. The developed approach is used to optimize the design of the online wash system for the General Electric MS5002 gas turbine model. Comparisons and differences between the optimized design and the existing design are highlighted and presented.     

Comparison of LID versus CID activation modes in tandem mass spectrometry of peptides

We report our contribution to the systematic investigation of peptide fragmentations performed on high‐performance Tof equipment, operating in MS and MS/MS modes, such as ESI‐QqTof and MALDI‐Tof/Tof instruments that are commonly available today in proteomic laboratories. Whereas the former analyzer's configuration provides low‐energy collision‐induced dissociations (CID), the latter allows tunable activation methods of the selected parent ion to induce either metastable laser‐induced dissociations (LID) or high‐energy CID (‘gas on spectra LID’). Fragmentation of the monoprotonated ion of 53 peptides (FW 807–2853 g/mol) was undertaken upon low‐energy CID on an ESI‐QTof mass spectrometer (Waters) as well as high‐energy CID and LID conditions on a MALDI Ultraflex mass spectrometer (Bruker). Systematic comparison of MS/MS spectra provided useful information on the performance of each piece of equipment for efficient peptide sequencing and also insights into the observed fragmentation behaviors. Copyright © 2008 John Wiley & Sons, Ltd.     

Topological,morphological and optical properties of Gamma irradiated Ni (II) tetraphenyl porphyrin thin films

Thermal evaporation technique was used to prepare NiTPP Thin films at room temperature. The prepared films were divided into two groups; the first group was as-deposited films, and the second group was irradiated in gamma cell type ⁶⁰Co source at room temperature with total absorbed dose of 150 kGy in air. All films were identified by X-ray diffraction (XRD), Fourier-transform infrared (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM) and transmission electron microscopy (TEM) before and after exposed to gamma radiation. The spectrophotometric measurement of transmittance and reflectance were used to investigate the optical properties at normal incidence of light in the wavelength range 200–2500 nm for as-deposited and gamma-irradiated films. Optical constants (refractive index n, and absorption index k) of as-deposited and irradiated films have been obtained in the wavelength range 200–2500 nm for all the samples. The single oscillator energy (E_o), the dispersion energy (E_d), the high frequency dielectric constant (ε_∞), the lattice dielectric constant (ε_L) and the ratio of the free charge carrier concentration to the effective mass (N/m^?) were estimated for each group. The absorption analysis has been also performed to determine the type of electronic transition and the optical energy gap.     

Comparative Studies of Some Novel Cu2+ and Fe3+ Chelates Derived From Tricine (L1) by Single Crystal X‐ray,Spectroscopic and Biological Data: Applications to Investigate Antitumor Activity

Novel Cu ²⁺ and Fe ³⁺ chelates derived from L ¹ were synthesized and characterized by single crystal X‐ray diffraction. The results indicate that the Fe (III) crystal, [Fe(L¹‐H)Cl₂], has an orthorhombic structure of the type pc2b while the dimeric Cu (II) crystal, [Cu(L¹‐H)Cl … ClCu(L¹‐H)], has a monoclinic with space group Cc. X‐ray diffraction and spectroscopic studies revealed that L ¹ acts as monobasic tetradentate with octahedral geometry in Fe (III) crystal while it behaves as dibasic tetradentate with distorted‐octahedral in the Cu (II) crystal. Also, the two chelates were characterized by spectral, magnetic and thermal analyses. DFT parameters were used to prove the liberation of a proton from COOH rather than NH groups. The kinetic and thermodynamic parameters of Fe (III) chelate were determined by Coats‐Redfern and Horowitz‐Metzger methods. Cyclic voltammogram provides information about the oxidation states of Cu (II) and Fe (III) chelates. Antitumor activity against Epitheliod carcinoma (Hela), breast cancer (MCF‐7) and antibacterial activities of chelates were investigated.     

Mono- and binuclear Schiff base complexes derived from glycine, 3-acetylpyridine and transition metal ions

Binuclear Schiff base complexes derived from glycine (Gly) and 3-acetylpyridine (3-APy) in the presence of M(OAc)₂ [M = Co^II, Ni^II, Cu^II, Zn^II and Cd^II] have been synthesized. The role of pH in promoting the condensation of glycine and 3-acetylpyridine, as well as the substitution of acetates by hydroxide ion, has been discussed. Also, the reaction of glycine with 3-acetylpyridine in the presence of MCl₂ [M = Co^II and Ni^II] and MCl₃ [M = Fe^III and Cr^III] yields mono- and/or binuclear complexes containing both of glycine and 3-acetylpyridine without condensation. Both types of complex were isolated and characterized by chemical analysis, conductance, spectral (u.v.–vis., i.r., and ¹H-n.m.r.), magnetic and thermal measurements.     

Comparison of inert supports in laser desorption/ionization mass spectrometry of peptides: pencil lead,porous silica gel,DIOS‐chip and NALDI™ target

In the search for alternative inert surfaces replacing silicon chips in Desorption/Ionization On porous Silicon (DIOS)‐like mass spectrometry analyses, nanostructured silicon‐based NALDI? chips were evaluated in Laser Desorption/Ionization (LDI) of peptides. Comparisons were made using commercially available DIOS chips (MassPREP?‐DIOS‐target?), amorphous carbon powder from lead pencil and porous silica gel used for chromatographic purposes as reference supports. A set of synthetic model peptides presenting variable amino acid sequences of various lengths was analyzed under all conditions. The LDI responses of the four ‘matrix‐free’ techniques were compared, especially in terms of peptide detection sensitivity and overall experiment robustness. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrical and photoresponse characteristics of 8-(1H-indol-3-ylazo)-naphthalene-2-sulfonic acid/n-Si photodiode

In this paper, of primary interest is to synthesis 8-(1H-indol-3-ylazo)-naphthalene-2-sulfonic acid (INSA) and to evaluate the main parameters of Au/INSA/n-Si/Al diode in dark and under illumination. Different techniques are used for interpreting the proposed INSA chemical structure. The dark current-voltage measurements were achieved in the temperature range of 293?413 K. It is noticed that INSA films modify the interfacial barrier height of classical Au/n-Si junction. At low applied voltages, the I–V relation shows exponential behavior. The values ideality factor, n, and the barrier height, φ, are improved by heating. The abnormal trend of n and φ is discussed, and a homogenous barrier height of 1.45 eV is evaluated. The series resistance is also calculated using Norde's function and it changes inversely with temperature. The space charge limited current ruled with exponential trap distribution dominates at relatively high potentials, trap concentration and carriers mobility are extracted. The reverse current of the diode has illumination intensity dependence with a good photosensitivity indicating that the device is promising for photodiode applications.     

Structural acoustic silencers--design and experiment

The effectiveness of introducing flexible structural layers into air conveying ducts for controlling noise is investigated through theoretical and experimental means, focusing at low frequencies where conventional passive silencing technology is least effective. Previous theoretical work has shown that using flexible rather than rigid walls has the potential to achieve high transmission losses. The physical mechanisms responsible for structural acoustic silencing, including the relation between transmission loss peaks and structural resonance corresponding to different transverse structural modes, are presented. Sensitivity of the performance to acoustic and structural boundary conditions is discussed. To eliminate radiated noise from these walls (breakout noise), a rigid walled cavity is introduced under the flexible plate. The challenge is to find means to reject plane waves in the two-duct system. Designs that overcome these issues and achieve appreciable transmission loss are investigated. Results based on three-dimensional finite element simulations are compared with experimental results.