UV-vis spectrophotometric titrations and vibrational spectroscopic characterization of meso-(p-hydroxyphenyl)porphyrins

Sequentially spectrophotometric titrations by sodium hydroxide of meso-tetraphenylporphyrin derivatives bearing one, two, three, or four p-hydroxyl groups result in new types of spectra. The strong new bands appear in the visible region with splitting or broadening of the Soret band and its significant loss of oscillator strength. To understand the molecular origin of these phenomena, the Resonance Raman (RR) and Fourier Transform Infrared (FTIR) experiments are carried out. The results demonstrate that the charges of the deprotonated para-hydroxy substituted meso-tetraphenylporphyrins are localized on the substituents, not delocalized into the pi system of the porphyrin macrocycles and that the ground states of the macrocycles remain essentially unperturbed. Both the related behavior of diprotonated tetrakis(p-(dimethylamino)phenyl) porphyrin and protonated Schiff base porphyrins show that the new bands considered as hyperporphyrin spectra are due to pi(phenoxide anion) --> pi*(porphyrin) transitions, where pi is an orbital on the phenoxide anion substitutent and pi* is a LUMO on the porphyrin.

Effect of poly(propylene carbonate) on the crystallization and melting behavior of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate)

The crystallization and melting behavior of poly(beta-hydroxybutyrate-co-beta-hydroxyvalerate) (PHBV) and a 30/70 (w/w) PHBV/poly(propylene carbonate) (PPC) blend was investigated with differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR). The transesterification reaction between PHBV and PPC was detected in the melt-blending process. The interaction between the two macromolecules was confirmed by means of FTIR analysis. During the crystallization process from the melt, the crystallization temperature of the PHBV/PPC blend decreased about 8 degreesC, the melting temperature was depressed by 4 degreesC, and the degree of crystallinity of PHBV in the blend decreased about 9.4%; this was calculated through a comparison of the DSC heating traces for the blend and pure PHBV. These results indicated that imperfect crystals of formed, crystallization was inhibited, and the crystallization ability of PHBV was weakened in the blend. The equilibrium melting temperatures of PHBV and the 30/70 PHBV/PPC blend isothermally crystallized were 187.1 and 179 degreesC, respectively.

VIV-UV excited luminescent properties of LnCa4O(BO3)3 : RE3+(Ln = Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa(4)O(BO3)(3):RE3+ (LnCOB:RE, Ln = Y, La, Gd, RE = Eu, Tb, Dy, Cc) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos' and J phi rgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. J phi rgensen. Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E-ct were calculated and compared with their excitation spectra.Eu3+ and Tb3+ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce3+ ions do not show efficient luminescence and quench the luminescence of Tb3+ ions when Tb3+ and Ce3+ ions are co-doped into LnCOB. GdCOB doped with Dy3+ shows yellowish white light under irradiation of 254 nm light for the reason that Gd ions transfer the energy from itself to Dy.

Multiple melting and crystallization behavior of nylon 1212

The wide-angle X-ray diffraction (WAXD) patterns of isothermally crystallized Nylon 1212 show that gamma-form crystals form below 90 degrees C and the alpha-form crystals call exist above 140 degrees C. In the temperature range of 90-140 degrees C, the a-form gamma-form crystals coexist. Variable-temperature WAXD exhibits that the nylon 1212 gamma-form does not show crystal and transition on heating, while a-form isothermally crystallized at 160 degrees C exhibits Brill transition at a little higher than 180 degrees C on heating. The multiple melting behaviors of Nylon 1212 isothermally crystallized from melt come from a complex mechanism of different crystal structures, dual lamellar population and melting-recrystallization. In polarized optical microscope (POM) observations, Nylon 1212 isothermally crystallized at 175 degrees C shows the ringed banded spherulites. However, at temperatures below 160 degrees C the ringed handed image disappears, and cross-extinct spherulites are formed.

Melting behaviors, isothermal and non-isothermal crystallization kinetics of nylon 1212

Isothermal crystallization, subsequent melting behavior and non-isothermal crystallization of nylon 1212 samples have been investigated in the temperature range of 160-171 degreesC using a differential scanning calorimeter (DSC). Subsequent DSC scans of isothermally crystallized samples exhibited three melting endotherms. The commonly used Avrami equation and that modified by Jeziorny were used, respectively, to fit the primary stage of isothermal and non-isothermal crystallizations of nylon 1212. The Avrami exponent n was evaluated, and was found to be in the range of 1.56-2.03 for isothermal crystallization, and of 2.38-3.05 for non-isothermal crystallization. The activation energies (DeltaE) were determined to be 284.5 KJ/mol and 102.63 KJ/mol, respectively, for the isothermal and non-isothermal crystallization processes by the Arrhenius' and the Kissinger's methods.

Crystallization and melting behaviors of PPC-BS/PVA blends

The isothermal crystallization and melting behaviors of poly(propylene carbonate) end-capped with benzenesulfonyl/poly (vinyl alcohol) (PPC-BS/PVA) blends over rich PVA composition range were first investigated by differential scanning calorimetry (DSC). PPS-BS/PVA interaction parameter, chi(12), calculated from equilibrium melting temperature depression was -0.44, revealing miscibility of PPC-BS with PVA in the melt and favorable interactions. The temperature dependence of crystallization rate constant at initial crystallization stage was analyzed using the modified Lauritzen-Hoffman expression. The chain width, a(0), the thickness of a monomolecular layer, b(0), the fold and lateral surface-free energies, sigma(e) and sigma, and the work of chain folding, q, for neat PVA were first reckoned to be 4.50 Angstrom, 4.78 Angstrom, 76.0 erg.cm(-2), and 4.70 kcal.mol(-1), respectively. The values of sigma(e) and q for PVA in PPC-BS/PVA blends exhibited a maximum in the neighborhood of 10/90 PPC-BS/PV, respectively.

Assembly of multilayer films containing iron(III)- substituted Dawson-type heteropolyanions and its electrocatalytic properties: cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis spectrometry

Ultrathin multilayer films have been prepared by means of alternate adsorption of iron(Ill)-substituted heteropolytungstate anions and a cationic redox polymer on the 4-aminobenzoic acid modified glassy carbon electrode surface based on electrostatic layer-by-layer assembly. Cyclic voltammetry, electrochemical impedance spectroscopy and UV-Vis absorption spectrometry have been used to easily monitor the uniformity of thus-formed multilayer films. Especially, the electrochemical impedance spectroscopy is successfully used to monitor the multilayer deposition processes and is a very useful technique in the characterization of multilayer films because it provides valuable information about the interfacial impedance features. All these results reveal regular film growth with each layer adsorption. The resulting multilayer films can effectively catalyze the reduction of H2O2,NO2- and BrO3-.

Liposome-mediated conformation transition of DNA detected by molecular probe: methyl green

Recent studies have focused on the structural features of DNA-lipid assemblies. In this paper, we take methyl green (MG) as a probe molecule to detect the conformational change of DNA molecule induced by dimethyldioctadecylammonium bromide (DDAB) liposomes before the condensation process of DNA begins. DDAB-induced DNA topology changes were investigated by cyclic voltammetry (CV), circular dichroism (CD) and UV-VIS spectrometry. We find that upon binding to DNA, positively charged liposomes induce a conformational transition of DNA molecules from the native B-form to the C motif. Conformational transition in DNA results in the binding modes of MG to DNA, changing and being isolated from DNA to the solution. More stable complexes are formed between DNA and DDAB. That is also proved by the melting study of DNA.

Multiple melting behavior of isotactic polypropylene and poly(propylene-co-ethylene) after stepwise isothermal crystallization

The multiple melting behavior of several commercial resins of isotactic polypropylene (iPP) and random copolymer, poly(propylene-co-ethylene) (PPE), after stepwise isothermal crystallization (SIC) were studied by differential scanning calorimeter and wide-angle X-ray diffraction (WAXD). For iPP samples, three typical melting endotherms appeared after SIC process when heating rate was lower than 10 degreesC/min. The WAXD experiments proved that only alpha-form crystal was formed during SIC process and no transition from alpha1- to alpha2-form occurred during heating process. Heating rate dependence for each endotherm was discussed and it was concluded that there were only,two major crystals with different thermal stability. For the PPE sample, more melting endotherms appeared after stepwise isothermal crystallization. The introduction of ethylene comonomer in isotactic propylene backbone further decreased the regularity of molecular chain, and the short isotactic propylene sequences could crystallize into gamma-form crystal having a low melting temperature whereas the long sequences crystallized into alpha-form crystal having high melting temperature.

Liquid crystal alignment generated by linearly polarized UV light on photoactive low molecular mass compounds

Alignment films prepared from low molar mass photo-crosslinkable materials containing the cinnamate group can be used for aligning LCs after irradiating the films with linearly polarized UV light. The high contrast observed in the polarizing optical microscope between dark and bright images indicates that the alignment is quite uniform. As the photoreaction progresses. the average roughness of the films is increased. All the aggregate structures, 'lamellar crystals'. produced by the photo-crosslinking reaction are of a square shape.

VUV-UV excited luminescent properties of calcium borophosphate doped with rare earth ions

The VUV-UV spectra of rare earth ions activated calcium borophosphate, CaBPO5:RE (RE = Ce3+, sm(3+), Eu2+, Eu3+, Tb3+ and Dy3+) were determined. The bands at about 155 nm in the VUV excitation spectra are attributed to the host lattice absorptions. The bands at 166 and 190 nm for the sample CaBPO5:Sm have been considered as related to the f-d transition and the charge transfer band (CTB) of Sm3+ ions, and the band at 169 nm for the sample CaBPO5:Dy is assumed to be connected with the f-d transition of the Dy3+ ions in CaBPO5. The partial reduction of Eu3+ CaBPO5:Eu prepared by high temperature solid state reaction in air is confirmed by the VUV-UV spectra.

Study on a carbosilane liquid crystalline (LC) dendrimer of the first generation - Containing twelve 4-butoxyazobenzene mesogenic groups in periphery

The divergent synthesis of a new carbosilane liquid-crystalline (LC) dendrimer of the first generation (D1) is described. Twelve 4-butoxyazobenzene groups are used as mesogenic fragments and attached in the periphery of the molecule. Structure and properties of D1 were characterized by element analysis, H-1 NMR, MALDI-TOF-MS, IR, UV-Vis, polarizing optical micrograph, DSC and WAXD. It is argued that mesophase of nematic type is realized. It is shown that the mesophase type of the dendrimer essentially depends on the chemical nature of the mesogenic groups. Phase behavior of D1 is K82N1331132N67K. The melting point of D1 is 30similar to43 degreesC lower than that of M5, its clearing temperature is 9 similar to 11 degreesC higher than that of M5 and its mesophase region is enlarged by 39 similar to 54 degreesC compared to that of M5. Eight extinguished brushes emanating from a stationary point are observed, corresponding to the high-strength disclination of S = + 2 of dendrimer. The clearing enthalpy of D1 is smaller than the value that is commonly found for phase transition n-i in LC and LC polymers. This may be due to the presence of branched dendrimer cores which cannot be easily deformed to fit into the anisotropic LC phase structure.

UV-VUV excited luminescence of SrBPO5 : Sm phosphor prepared in air

The high-resolution luminescent spectrum of divalent samarium excited by 355 nm UV light at 77 K, the VUV excitation spectra, the VUV excited emission spectra and EXAFS at Sm-L-3 edge were reported for samarium doped strontium borophosphate, SrBPO5:Sm prepared by solid state reaction in air at high temperature. The high-resolution luminescent spectrum showed that the divalent samarium ions occupied the C-2upsilon lattice sites. The VUV excitation spectra indicated that the sample exhibited absorption bands with the maxima at 129 and 148 nm, respectively. The performance of EXAFS at Sm-L3 absorption edge suggested that the samarium ions were nine-coordinated and the mean distances of bond Sm-O were 2.38 Angstrom.

VUV-UV photoluminescence spectra of strontium orthophosphate doped with rare earth ions

The measurements of VUV-UV photoluminescence emission (PL) and photoluminescence excitation (PLE) spectra of rare earth ions activated strontium orthophosphate [Sr-3(PO4)(2):RE, RE = Ce, Sm, Eu, Tb] are performed. Whenever the samples are excited by VUV or UV light, the typical emission of Ce-3+,Ce- Sm3+, Eu3+, Eu2+ and Tb3+ ions can be observed in PL spectra, respectively. The charge transfer bands (CTBs) of Sm3+ and Eu3+ are found, respectively, peaking at 206 and 230nm. The absorption bands peaking in the region of 150-160 nm are assigned to the host lattice sensitization bands, i.e., the band-to-band transitions of PO43- grouping in Sr-3(PO4)(2). It is speculated that the first f-d transitions of Sm3+ (Eu3+), and the CTB of Tb3+ are, respectively, located around 165 (14 3) and 167 urn by means of VUV-UV PLE spectra and relational empirical formula, these f-d transitions or CT bands are included in the bands with the maxima at 150-160 nm, respectively. The valence change of europium from trivalent to divalent in strontium orthophosphate prepared in air is observe by VUV-UV PL and PLE spectra.

Synthesis and characterization of a time-resolved fluorescence analysis chelate reagent-BCPDA

In this paper, we report on a solid phase time-resolved fluorescence immunoassay chelate reagent-4,7-bis(chlorosulfophenyl)1, 10-phenanthroline-2,9-dicarboxylic acid (BCPDA), which is suitable as a fluorescent labeling agent. The five step synthesis product of BCPDA was presented for improving the purity of the product based on the three step synthesis product. The approach involves chlorization, hydrolyzing the ester, preparing disodium, carboxylate to diacid, sulfonation. The yield of five step product is 99 %, 45 %, 94 %, 95 %, 80 % respectively. The structure and purity of product was characterized by the melting point, IR,H-1 NMR, UV spectrum, element analysis, and proved to be consistent with the structure predictal.