Influence of laser irradiation on the optical and structural properties of poly(ethylene terephthalate) fibres

Laser irradiation has been previously investigated for achieving uniform heating of polyethylene terephthalate (PET) fibres in the hot-drawing stage of the production process, so as to obtain better fibre mechanical properties. The optical properties and dye uptake of PET fibres also depend on the polymer chain orientation and crystallinity within the fibre structure. This paper reports an investigation of a concept whereby laser irradiation and interferometry could be used to modify and trace a small change in the optical properties of a PET monofilament fibre, but the corresponding change in the dye uptake would not be detected visually. A copper vapour laser (550-580 nm wavelengths) was used to expose consecutive 4 mm lengths along a running length of monofilament to 39.8 W cm⁻², at a pulse rate of 9.89 kHz in order to modify, in a controlled way, the polymer crystallinity and orientation. A 3D finite element simulation, based on uncoupled heat-transfer analysis, indicated that rapid heating and cooling could be obtained with the laser to give the small changes required. Irradiated and untreated samples were analysed by interferometry and a 0.16% change was detected in the birefringence profiles, corresponding to a small reduction in the degree of orientation and crystallinity of the irradiated samples. Density measurements and wide-angle X-ray scattering (WAXS) analysis confirmed the change in crystallinity. Tests conducted for dye adsorption and tensile strength showed a small increase in the former and only a very small decrease in the latter. It was concluded that these changes in property provide the opportunity for a laser-irradiated PET monofilament fibre to be used as a subtle tracer element in brand labels for textile garments as an anti-counterfeit measure.     

Reactivity of dioxoruthenium(VI) porphyrins toward amines. Synthesis and characterization of bis(arylamine)ruthenium(II), bis(arylamido)- and bis(diphenylamido)ruthenium(IV), and oxo(tert-butylimido)ruthenium(VI) porphyrins

Reactions of dioxoruthenium(VI) porphyrins, [Ru(VI)O2(Por)], with p-chloroaniline, trimethylamine, tert-butylamine, p-nitroaniline, and diphenylamine afforded bis(amine)ruthenium(II) porphyrins, [Ru(II)(Por)(L)2] (L-p-ClC6H4NH2, Me3N, Por=TTP, 4-Cl-TPP; L=tBuNH2, Por = TPP, 3,4,5-MeO-TPP, TTP, 4-Cl-TPP, 3,5-Cl-TPP) and bis(amido)ruthenium(IV) porphyrins, [Ru(IV)(Por)(X)2] (X=p-NO2C6H4NH, Por=TTP, 4-Cl-TPP; X = Ph2N, Por = 3,4,5-MeO-TPP, 3,5-Cl-TPP), respectively. Oxidative deprotonation of [Ru(II)(Por)(NH2-p-C6H4Cl)2] in chloroform by air generated bis(arylamido)ruthenium(IV) porphyrins, [RuIV(Por)(NH-p-C6H4Cl)2] (Por=TTP. 4-Cl-TPP). Oxidation of [RuII(Por)-(NH2tBu)2] by bromine in dichloromethane in the presence of tert-butylamine and traces of water produced oxo(imido)ruthenium(VI) porphyrins, [RuVI-O(Por)(NtBu)] (Por=TPP, 3,4,5-MeO-TPP, TTP, 4-Cl-TPP, 3,5-Cl-TPP). These new classes of ruthenium complexes were characterized by 1H NMR, IR, and UV/visible spectroscopy, mass spectrometry, and elemental analysis. The structure of [Ru(IV)(TTP)(NH-p-C6H4Cl)2 . CH2Cl2 was determined by X-ray crystallography. The Ru-N bond length and the Ru-N-C angle of the Ru-NHAr moiety are 1.956(7) A and 135.8(6) degrees, respectively.     

Bis axial ligation of simple imine and methyleneamido groups by ruthenium porphyrins

Bis(N-ethylideneethanamine)ruthenium(ii) porphyrins, [Ru11(Por)(N(Et)=CHMe)2] (Por=TTP, 4-Cl-TPP), were prepared by the reaction of dioxoruthenium(VI) porphyrins with triethylamine in approximately 85% yields. The reaction between dioxoruthenium(VI) porphyrins and benzophenone imine afforded bis(diphenylmethyleneamido)ruthenium(IV) porphyrins, [Ru(IV)(Por)(N=CPh2)2] (Por=TTP, 3,4,5-MeO-TPP), in approximately 65% yields. These new classes of metalloporphyrins were characterized by 1H NMR, UV/Vis, and IR spectroscopy as well as by mass spectrometry and elemental analysis. The X-ray crystallographic structures of [Ru(II)(TTP)(N(Et)=CHMe)2] and [Ru(IV)(3,4,5-MeO-TPP)(N=CPh2)2] revealed an axial Ru-N bond length of 2.115(6) A for the imine complex and 1.896(8) A for the methyleneamido complex. Each of the N=CPh2 axial groups in [Ru(IV)(3,4,5-MeO-TPP)(N=CPh2)2] adopts a linear coordination mode with a corresponding Ru-N-C angle of 175.9(9)degrees. Spectral and structural studies revealed essentially single bonding character for the bis(imine) complexes but a multiple bonding character for the bis(methyleneamido) complexes with respect to their axial Ru-N bonds.     

Equilibrium studies of the sorption of Cu(II) ions onto chitosan

Chitosan is a polymer that can be obtained from the shells of seafood such as prawns, crabs, and lobsters. Chitosan has free amino groups, which can attract metal ions, and has been used as an adsorbent for the removal of metal ions from effluents. In this research, the sorption of copper ions from solution onto chitosan at two pHs has been investigated. DSC, TGA, surface area, SEM, and NMR studies have been used to report the pure physical states of chitosan and the chitosan-copper complex. The experimental isotherm data were analyzed using the Langmuir, Freundlich, and Redlich-Peterson equations. Correlation coefficients were determined for each isotherm analysis. Error functions have been used to determine the alternative single component parameters by nonlinear regression due to the inherent bias in using the correlation coefficient resulting from linearization. The error function method provided the best parameters for the isotherm equations in this system and is demonstrated for error comparison purposes.     

Structure selective complexation of cyclodextrins with five polyphenols investigated by capillary electrokinetic chromatography

The complexation of five polyphenols, namely trans‐resveratrol, astilbin, taxifolin, ferulic acid, and syringic acid (guest molecules) with α‐, β‐, and γ‐cyclodextrin (host molecules), was investigated by capillary electrokinetic chromatography. The binding constants were calculated based on the effective electrophoretic mobility change of guests with the addition of cyclodextrins into the background electrolyte. Because of cavity size, cyclodextrins showed structure‐selective complexation property to different guest. The stability of the trans‐resveratrol complexes was in the order of β‐ > α‐ > γ‐cyclodextrin. The cavity size of α‐cyclodextrin was too small for astilbin and taxifolin molecules, and thus they could not form complexes. The molecular size of syringic acid was too big for all cyclodextrins cavity, and no cyclodextrin could form complexes with it. Temperature studies showed that the binding constants decreased with the rise of temperature. Enthalpy and entropy values were calculated and the negative values of these parameters indicated that the complexation process was enthalpy‐controlled. Van der Waals force and release of high‐enthalpy water molecules from the cyclodextrins cavity played important roles in the process.     

PDMS-based microfluidic device with multi-height structures fabricated by single-step photolithography using printed circuit board as masters

We have developed a method for fabricating microfluidic devices with multi-height structures using single step photolithography. The whole fabrication process is executed by conventional printed circuit board (PCB) technology without the need of having access to clean room facilities. Specifically designed "windows" and "rims" architectures were printed on films that were used as photomasks. Different levels of protruding features on the PCB master were produced by exposing a photomask followed by chemical wet etching. Poly(dimethylsiloxane) (PDMS) was then moulded against the positive relief master to generate microfluidic structures. In this report, we described the fabrication of a microfluidic device featured with a multi-height "sandbag" structure for particle entrapment and peripheral microchannels. Controlled immobilization of biological cells and immunocytochemcial staining assays were performed to demonstrate the applicability of the microfluidic device for cellular analysis. The integrity of the microdevice remained stable under applied pressure, indicating the robustness of the elastic PDMS structures for analytical operation. The simple microfabrication process requires only low-cost materials and minimal specialized equipment and can reproducibly produce mask lines of about 20 microm in width, which is sufficient for most microfluidic applications.     

Enantio- and diastereodifferentiating cis,trans-photoisomerization of 2beta,3beta-diphenylcyclopropane-1alpha-carboxylic acid derivatives in organized media

[reaction: see text] Four methods of asymmetric induction in the cis, trans-photoisomerization of 2beta, 3beta-diphenylcyclopropane-1alpha-carboxylic acid derivatives were studied. Best results (ca. 80% de) were obtained by irradiation of chiral esters, amides, and salts in NaY and LiY zeolites and in the pure crystalline state.     

High throughput fluorescence-based assays for cyclic ADP-ribose,NAADP, and their metabolic enzymes

Cyclic ADP-ribose (cADPR) and nicotinic acid adenine dinucleotide phosphate (NAADP) are two novel Ca(2+) messengers derived respectively from NAD and NADP. Since their discovery in sea urchin eggs, both have now been shown to serve messenger functions in a wide range of cells from plant to human. In this article, a series of fluorimetric assays for cADPR, NAADP and their metabolic enzymes is compiled. The enzyme assay makes use of an analog of NAD, nicotinamide guanine dinucleotide, which is non-fluorescent but is cyclized by the enzymes to a fluorescent analog of cADPR, cyclic GDP-ribose. Other NAD utilizing enzymes are not capable of catalyzing the cyclization and thus produce no interference. The fluorimetric assays for cADPR and NAADP make use of coupled-enzyme amplification and can readily detect nanomolar concentrations of either messenger. All the assays described can be performed in multi-well format, allowing ready automation and use in high throughput screening. An added advantage of these assays is that all the required reagents are commercially available, facilitating general adoption of the techniques by all those who are interested in the physiology and enzymology of the novel Ca(2+) signaling pathways mediated by cADPR and NAADP.