Identification and quantification of phosphatidylcholines containing very-long-chain polyunsaturated fatty acid in bovine and human retina using liquid chromatography/tandem mass spectrometry

The retina is one of the vertebrate tissues with the highest content in polyunsaturated fatty acids (PUFA). A large proportion of retinal phospholipids, especially those found in photoreceptor membranes, are dipolyunsaturated molecular species. Among them, dipolyunsaturated phosphatidylcholine (PC) molecular species are known to contain very-long-chain polyunsaturated fatty acids (VLC-PUFA) from the n-3 and n-6 series having 24-36 carbon atoms (C24-C36) and four to six double bonds. Recent interest in the role played by VLC-PUFA arose from the findings that a protein called elongation of very-long-chain fatty acids 4 (ELOVL4) is involved in their biosynthesis and that mutations in the ELOVL4 gene are associated with Stargardt-like macular dystrophy (STD3), a dominantly inherited juvenile macular degeneration leading to vision loss. The aim of the present study was to develop an HPLC-ESI-MS/MS method for the structural characterisation and the quantification of dipolyunsaturated PC molecular species containing VLC-PUFA and validate this methodology on retinas from bovines and human donors. Successful separation of phosphatidylethanolamine (PE), phosphatidylinositol (PI), phosphatidylserine (PS), PC, lyso-phosphatidylcholine (LPC) and sphingomyelin (SM) was achieved using a silica gel column and a gradient of hexane/isopropanol/water containing ammonium formate as a mobile phase. A complete structural characterisation of intact phosphatidylcholine species was obtained by collision-induced dissociation (CID) in the negative mode. Fatty acid composition and distribution can be clearly assigned based on the intensity of sn-2/sn-1 fragment ions. The PC species were characterised on bovine retina, 28 of which were dipolyunsaturated PC species containing one VLC-PUFA (C24-C36) with three to six double bonds. VLC-PUFA was always in the sn-1 position while PUFA at the sn-2 position was exclusively docosahexaenoic acid (DHA, C22:6n-3). Most of these VLC-PUFA-containing dipolyunsaturated PCs were detected and quantified in human retinas. The quantitative analysis of the different PC molecular species was performed in the positive mode using precursor ion scanning of m/z 184 and 14:0/14:0-PC and 24:0/24:0-PC as internal standards. The relationship between the MS peak intensities of different PC species and their carbon chain length was included for calibration. The main compounds represented were those having VLC-PUFA with 32 carbon atoms (C32:3, C32:4, C32:5 and C32:6) and 34 carbon atoms (C34:3, C34:4, C34:5 and C34:6). Dipolyunsaturated PCs with 36:5 and 36:6 were detected but in smaller quantities. In conclusion, this new HPLC-ESI-MS/MS method is sensitive and specific enough to structurally characterise and quantify all molecular PC species, including those esterified with VLC-PUFA. This technique is valuable for a precise characterisation of PC molecular species containing VLC-PUFA in retina and may be useful for a better understanding of the pathogenesis of STD3.     

Thermal quenching of thermoluminescence in TLD-200, TLD-300 and TLD-400 after β-irradiation

The dosimetric characteristics of many TL materials are influenced by changes in location, size and shape of the glow curves due to changes in the heating rate. In this study, the effect of heating rate on the integrated peak areas of CaF₂:Dy (TLD-200), CaF₂:Tm (TLD-300) and CaF₂:Mn (TLD-400) crystals have been investigated after β-irradiation. It was observed that the peak temperatures of all peaks shifted to the high temperature sides and the integrated peak areas decrease as the heating rate increases due to thermal quenching, whose efficiency increases as temperature increases.     

Current-mode continuous-time fully-integrated universal filterusing CDBAs

The authors propose a new, fully-integrated universal filter using a current differencing buffered amplifier, a recently introduced active element. It has been shown that the use of the current differencing buffered amplifier in fully-integrated filter design is attractive in that it simplifies the implementation and makes possible the use of a minimum number of grounded capacitors, compared to those using second generation current conveyers and current feedback amplifiers     

Urea dimethacrylates functionalized with bisphosphonate/bisphosphonic acid for improved dental materials

Incorporation of bisphosphonate/bisphosphonic acid groups in dental monomer structures should increase interaction of these monomers with dental tissue as these groups have strong affinity for hydroxyapatite. Therefore, new urea dimethacrylates functionalized with bisphosphonate (1a, 1b) and bisphosphonic acid (2a, 2b) groups are synthesized and evaluated for dental applications. Monomers 1a and 1b are synthesized from 2‐isocyanatoethyl methacrylate (IEM) and two bisphosphonated amines (BPA1 and BPA2), prepared as reported elsewhere. Selective dealkylation of the bisphosphonate ester groups of 1a and 1b using trimethylsilyl bromide (TMSBr) gives monomers (2a and 2b) with bisphosphonic acid functionality. X‐ray diffractometer (XRD), Raman spectroscopy, and X‐ray photoelectron spectroscopy (XPS) analyses of monomer‐treated HAP particles show that 2a induces formation of stable monomer‐calcium salts, similar to 10‐methacryloyloxydecyl dihydrogen phosphate (MDP), with higher chemical interaction than 2b. The photopolymerization studies indicate good copolymerizability with commercial dental monomers. In vitro studies on NIH 3T3 mouse embryonic fibroblast cells have clearly shown that the tested monomers (1b and 2b) are not toxic according to the MTT standards. All these properties make these monomers suitable as biocompatible cross‐linkers/adhesives for dental applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3195–3204     

Universal current-mode filter with reduced number of active andpassive components

A new current-mode (CM) universal active filter with single-input and three-outputs (SITO) employing only four CCIIs and a minimum number of passive components is presented. The proposed filter based on an RLC shunt circuit, has a good sensitivity performance and achieves the desired filter characteristics without any component matching     

Construction of a new family of Bernstein‐Kantorovich operators

In the present paper, we construct a new sequence of Bernstein‐Kantorovich operators depending on a parameter α. The uniform convergence of the operators and rate of convergence in local and global sense in terms of first‐ and second‐order modulus of continuity are studied. Some graphs and numerical results presenting the advantages of our construction are obtained. The last section is devoted to bivariate generalization of Bernstein‐Kantorovich operators and their approximation behaviors.     

Analysis of Slot Orientation in Shear-Compression Specimen (SCS)

This paper presents an analytical treatment as well as experimental measurement of the plastic deformation field in shear-compression specimen (SCS) by using digital image processing (DIC) technique. The results provide a set of useful expressions that relates externally applied displacement and load quantities to the equivalent stress and equivalent plastic strain within the gage section. Based on the analysis, we propose modifying the slot angle of SCS geometry from its original value of 45º to 35.26º in order to enhance the uniformity of stress and strain fields in gage section. It is shown by analysis that this enhancement is essentially because the compatibility and boundary conditions that yield a homogeneous deformation field is naturally satisfied for the particular slot orientation of ???=?35.26°. This conclusion is also supported by experimental evidence that comparatively shows the edge effects for varying slot angles.     

Study of Physically Transient Insulating Materials as a Potential Platform for Transient Electronics and Bioelectronics

Controlled degradation and transiency of materials is of significant importance in the design and fabrication of degradable and transient biomedical and electronic devices and platforms. Here, the synthesis of programmable biodegradable and transient insulating polymer films is reported, which have sufficient physical and chemical properties to be used as substrates for the construction of transient electronics. The composite structure can be used as a means to control the dissolution and transiency rate of the polymer composite film. Experimental and computational studies demonstrate that the addition of gelatin or sucrose to a PVA polymer matrix can be used as a means to program and either slow or enhance the transiency of the composite. The dissolution of the polymer composites are fitted with inverse exponential functions of different time constants; the lower time constants are an indication of faster transiency of the polymer composite. The addition of gelatin results in larger time constants, whereas the addition of sucrose generally results in smaller time constants.