Electrochemistry of Heteroleptic Tris(phthalocyaninato) Rare Earth(III) Complexes

The electrochemical characteristics of a series of heteroleptic tris(phthalocyaninato) complexes with identical rare earths or mixed rare earths (Pc)M(OOPc)M(OOPc) [M = Eu...Lu, Y; H2Pc = unsubstituted phthalocyanine, H2(OOPc) = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] and (Pc)Eu(OOPc)Er(OOPc) have been recorded and studied comparatively by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetrabutylammonium perchlorate (TBAP). Up to five quasi-reversible one-electron oxidations and four one-electron reductions have been revealed. The half-wave potentials of the first, second and fifth oxidations depend on the size of the metal center, but the fifth changes in the opposite direction to that of the first two. Moreover, the difference in redox potentials of the first oxidation and first reduction for (Pc)M(OOPc)M(OOPc), 0.85−0.98 V, also decreases linearly along with decreasing rare earth ion radius, clearly showing the rare earth ion size effect and indicating enhanced π−π interactions in the triple-deckers connected by smaller lanthanides. This order follows the red-shift seen in the lowest energy band of triple-decker compounds. The electronic differences between the lanthanides and yttrium are more apparent for triple-decker sandwich complexes than for the analogous double-deckers. By comparing triple-decker, double-decker and mononuclear [ZnII] complexes containing the OOPc ligand, the HOMO−LUMO gap has been shown to contract approximately linearly with the number of stacked phthalocyanine ligands.

The ageing of alumina hydrolysates synthesized from sec-butoxyaluminium(III)

A combination of X-ray diffraction, thermal analysis and Raman spectroscopy was employed to characterise the ageing of alumina hydrolysates synthesised from the hydrolysis of anhydrous tri-sec-butoxyaluminium(III). X-Ray diffraction showed that the alumino-oxy(hydroxy) hydrolysates were pseudoboehmite. For boehmite the lamellar spacings are in the b direction and multiple d(020) peaks are observed for the un-aged hydrolysate. After 4 h of ageing, a single d(020) peak is observed at 6.53 Å. Thermal analysis showed five endotherms at 70, 140, 238, 351 and 445°C. These endotherms are attributed to the dehydration and dehydroxylation of the boehmite-like hydrolysate. Raman spectroscopy shows the presence of bands for the washed hydrolysates at 333, 355, 414, 455, 475, 495, 530 and 675 cm–1. These bands are attributed to pseudoboehmite. Ageing of the hydrolysates results in an increase in the crystallite size of the pseudoboehmite.

Comparative Electrochemical Study of Unsubstituted and Substituted Bis(phthalocyaninato) Rare Earth(III) Complexes

The electrochemistry of homoleptic substituted phthalocyaninato rare earth double-decker complexes M(TBPc)2 and M(OOPc)2 [M = Y, La...Lu except Pm; H2TBPc = 3(4),12(13),21(22),30(31)-tetra-tert-butylphthalocyanine, H2OOPc = 3,4,12,13,21,22,30,31-octakis(octyloxy)phthalocyanine] has been comparatively studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH2Cl2 containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). Two quasi-reversible one-electron oxidations and three or four quasi-reversible one-electron reductions have been revealed for these neutral double-deckers of two series of substituted complexes, respectively. For comparison, unsubstituted bis(phthalocyaninato) rare earth analogues M(Pc)2 (M = Y, La...Lu except Pm; H2Pc = phthalocyanine) have also been electrochemically investigated. Two quasi-reversible one-electron oxidations and up to five quasi-reversible one-electron reductions have been revealed for these neutral double-decker compounds. The three bis(phthalocyaninato)cerium compounds display one cerium-centered redox wave between the first ligand-based oxidation and reduction. The half-wave potentials of the first and second oxidations and first reduction for double-deckers of the tervalent rare earths depend on the size of the metal center. The difference between the redox potentials of the second and third reductions for MIII(Pc)2, which represents the potential difference between the first oxidation and first reduction of [MIII(Pc)2]−, lies in the range 1.08−1.37 V and also gradually diminishes along with the lanthanide contraction, indicating enhanced π−π interactions in the double-deckers connected by the smaller, lanthanides. This corresponds well with the red-shift of the lowest energy band observed in the electronic absorption spectra of reduced double-decker [MIII(Pc′)2]− (Pc′ = Pc, TBPc, OOPc).

Experimental studies on comparison of microwave curing and thermal curing of epoxy resins used for alternative mould materials

In this present work attempts have been made to study the glass transition temperature of alternative mould materials by using both microwave heating and conventional oven heating. In this present work three epoxy resins, namely R2512, R2515 and R2516, which are commonly used for making injection moulds have been used in combination with two hardeners H2403 and H2409. The magnetron microwave generator used in this research is operating at a frequency of 2.45 GHz with a hollow rectangular waveguide. In order to distinguish the effects between the microwave and conventional heating, a number of experiments were performed to test their mechanical properties such as tensile and flexural strengths. Additionally, differential scanning calorimeter technique was implemented to measure the glass transition temperature on both microwave and conventional heating. This study provided necessary evidences to establish that microwave heated mould materials resulted with higher glass transition temperature than the conventional heating. Finally, attempts were also made to study the microstructure of microwave-cured materials by using a scanning electron microscope in order to analyze the morphology of cured specimens.

Evaluation of piezoelectric PVDF polymers for use in space environments. III. Comparison of the effects of vacuum UV and gamma radiation

Films of piezoelectric PVDF and P(VDF-TrFE) were exposed to vacuum UV (115-300 nm VUV) and -radiation to investigate how these two forms of radiation affect the chemical, morphological, and piezoelectric properties of the polymers. The extent of crosslinking was almost identical in both polymers after -irradiation, but surprisingly, was significantly higher for the TrFE copolymer after VUV-irradiation. Changes in the melting behavior were also more significant in the TrFE copolymer after VUV-irradiation due to both surface and bulk crosslinking, compared with only surface crosslinking for the PVDF films. The piezoelectric properties (measured using d33 piezoelectric coefficients and D-E hysteresis loops) were unchanged in the PVDF homopolymer, while the TrFE copolymer exhibited more narrow D-E loops after exposure to either - or VUV-radiation. The more severe damage to the TrFE copolymer in comparison with the PVDF homopolymer after VUV-irradiation is explained by different energy deposition characteristics. The short wavelength, highly energetic photons are undoubtedly absorbed in the surface layers of both polymers, and we propose that while the longer wavelength components of the VUV-radiation are absorbed by the bulk of the TrFE copolymer causing crosslinking, they are transmitted harmlessly in the PVDF homopolymer.

Application of autologous periosteal cells for the regeneration of class III furcation defects in Beagle dogs

The aim of this study was to evaluate the healing of class III furcation defects following transplantation of autogenous periosteal cells combined with b-tricalcium phosphate (b-TCP). Periosteal cells obtained from Beagle dogs’ periosteum explant cultures, were inoculated onto the surface of b-TCP. Class III furcation defects were created in the mandibular premolars. Three experimental groups were used to test the defects’ healing: group A, b-TCP seeded with periosteal cells were transplanted into the defects; group B, b-TCP alone was used for defect filling; and group C, the defect was without filling materials. Twelve weeks post surgery, the tissue samples were collected for histology, immunohistology and X-ray examination. It was found that both the length of newly formed periodontal ligament and the area of newly formed alveolar bone in group A, were significantly increased compared with both group B and C. Furthermore, both the proportion of newly formed periodontal ligament and newly formed alveolar bone in group A were much higher than those of group B and C. The quantity of cementum and its percentage in the defects (group A) were also significantly higher than those of group C. These results indicate that autogenous periosteal cells combined with b-TCP application can improve periodontal tissue regeneration in class III furcation defects.

Channel plasmon-polariton modes in V grooves filled with dielectric

We investigated the effect of dielectric filling in a V groove on the propagation parameters of channel plasmon-polariton (CPP) modes. In particular, existence conditions and critical groove angles, mode localization, field structure, dispersion, and propagation distances of CPP modes are analyzed as functions of dielectric permittivity inside the groove. It is demonstrated that increasing dielectric permittivity in the groove results in a rapid increase of mode localization near the tip of the groove and increase of both the critical angles that determine a range of groove angles for which CPP modes can exist. Detailed analysis of the field structure has demonstrated that the maximum of the field in a CPP mode is typically reached at a small distance from the tip of the groove. The effect of rounded tip is also investigated.

An ultraviolet selective photodetector based on a nanocrystalline TiO2 photoelectrochemical cell

Solar ultraviolet (UV) radiation causes a range of skin disorders as well as affecting vision and the immune system. It also inhibits development of plants and animals. UV radiation monitoring is used routinely in some locations in order to alert the population to harmful solar radiation levels. There is ongoing research to develop UV-selective-sensors [1–3]. A personal, inexpensive and simple UV-selective-sensor would be desirable to measure UV intensity exposure. A prototype of such a detector has been developed and evaluated in our laboratory. It comprises a sealed two-electrode photoelectrochemical cell (PEC) based on nanocrystalline TiO2. This abundant semiconducting oxide, which is innocuous and very sta-ble, is the subject of intense study at present due to its application in dye sensitized solar cells (DSSC) [4]. Since TiO2 has a wide band gap (EG = 3.0 eV for rutile and EG = 3.2 eV for anatase), it is inher-ently UV-selective, so that UV filters are not required. This further reduces the cost of the proposed photodetector in comparison with conventional silicon detectors. The PEC is a semiconductor–electrolyte device that generates a photovoltage when it is illuminated and a corresponding photocur-rent if the external circuit is closed. The device does not require external bias, and the short circuit current is generally a linear function of illumination intensity. This greatly simplifies the elec-trical circuit needed when using the PEC as a photodetector. DSSC technology, which is based on a PEC containing nanocrystalline TiO2 sensitized with a ruthenium dye, holds out the promise of solar cells that are significantly cheaper than traditional silicon solar cells. The UV-sensor proposed in this paper relies on the cre-ation of electron–hole pairs in the TiO2 by UV radiation, so that it would be even cheaper than a DSSC since no sensitizer dye is needed. Although TiO2 has been reported as a suitable material for UV sensing [3], to the best of our knowledge, the PEC configuration described in the present paper is a new approach. In the present study, a novel double-layer TiO2 structure has been investigated. Fabrication is based on a simple and inexpensive technique for nanostructured TiO2 deposition using microwave-activated chemical bath deposition (MW-CBD) that has been reported recently [5]. The highly transparent TiO2 (anatase) films obtained are densely packed, and they adhere very well to the transparent oxide (TCO) substrate [6]. These compact layers have been studied as contacting layers in double-layer TiO2 structures for DSSC since improvement of electron extraction at the TiO2–TCO interface is expected [7]. Here we compare devices incorporating a single mesoporous nanocrystalline TiO2 structure with devices based on a double structure in which a MW-CBD film is situated between the TCO and the mesoporous nanocrystalline TiO2 layer. Besides improving electron extraction, this film could also help to block recombination of electrons transferred to the TCO with oxidized species in the electrolyte, as has been reported in the case of DSSC for compact TiO2 films obtained by other deposition tech-niques [8,9]. The two types of UV-selective sensors were characterized in detail. The current voltage characteristics, spectral response, inten-sity dependence of short circuit current and response times were measured and analyzed in order to evaluate the potential of sealed mesoporous TiO2-based photoelectrochemical cells (PEC) as low cost personal UV-photodetectors.

Fibroin-based materials support cultivation of limbal stromal cells

Purpose: The silk protein fibroin provides a potential substrate for use in ocular tissue reconstruction. We have previously demonstrated that transparent membranes produced from fibroin support cultivation of human limbal epithelial cells (Tissue Eng A. 14(2008)1203-11). We presently extend this body of work to studies of human limbal stromal cell (HLS) growth on fibroin in the presence and absence of serum. Methods: Primary cultures of HLS cells were established in DMEM/F12 medium supplemented with either 10% fetal bovine serum (FBS) or 2% B27 supplement. Defined keratinocyte serum-free medium (DK-SFM, Invitrogen) was also tested. The resulting cultures were analysed by flow cytometry for expression of CD34, CD90, CD45, and CD141. Cultures grown under each condition were subsequently passaged either onto transparent fibroin membranes prepared from purified fibroin or within 3D scaffolds prepared from partially-solubilised fibroin. Results: HLS cultures were successfully established under each condition, but grew more slowly and passaged poorly in the absence of serum. Cultures grown in 10% FBS were <0.5% CD34+ (keratocytes) and >97% CD90+ (fibroblasts). Cultures established in 2% B27 formed floating spheres and contained >8% CD34+ cells and reduced CD90 expression. Cultures established in DK-SFM displayed traces of epithelial cell growth (CD141), but mostly consisted of CD90+ cells with <1% CD34+ cells. Cells of bone marrow lineage (CD45) were rarely observed under any conditions. Cultures grown in 10% FBS were able to adhere to and proliferate on silk fibroin 3-D scaffolds and transparent films while those grown serum-free could not. Adhesion of HLS cells to fibroin was initially poorer than that displayed on tissue culture plastic. Conclusions: HLS cultures containing cells of predominantly fibroblast lineage can be grown on fibroin-based materials, but this process is dependent upon additional ECM factors such as those provided by serum.

Comments on the phase diagrams and crystallisation paths of Y-Ba-Cu-O materials

Our micro structural characterisation of Y-Ba-Cu-O quenched partial melts shows that the BaCuO2 (BC1) phase is crystalline at temperatures as high as 1100°C, and that the partial melt self-establishes a micro structural gradient from the surface towards the interior of the samples, which can be associated with a gradient in an equivalent partial pressure of O2 (pO2). The extension of the Y2BaCuO5-YBa2Cu3O7-x (Y211-Y123) tie-line intersects the primary crystallisation field of BC1 first. The actual peritectic reaction that takes place is Y2BaCuO5(s) + BaCuO2(s) + 2BaCu2O2(L) + 1/2O2 → 2YBa2Cu3O6(s). Two schematic representations which allow an analysis of the pO2 dependence are given. The gradient in micro structure self-established by the sample acts as a driving force for texturing. With this new perspective gained about the actual peritectic reaction and mechanisms of melt-texturing of Y123, it is possible to explain most of the aspects about partial melt-texturing. In addition, it seems possible to devise heat treatments that may allow for the production of well-oriented single domains with very large diameters. © 1999 Elsevier Science B.V.

Hybrid antibacterial fabrics with extremely high aspect ratio Ag/AgTCNQ nanowires

This study reports the synthesis of extremely high aspect ratios (>3000) organic semiconductor nanowires of Ag–tetracyanoquinodimethane (AgTCNQ) on the surface of a flexible Ag fabric for the first time. These one-dimensional (1D) hybrid Ag/AgTCNQ nanostructures are attained by a facile, solution-based spontaneous reaction involving immersion of Ag fabrics in an acetonitrile solution of TCNQ. Further, it is discovered that these AgTCNQ nanowires show outstanding antibacterial performance against both Gram negative and Gram positive bacteria, which outperforms that of pristine Ag. The outcomes of this study also reflect upon a fundamentally important aspect that the antimicrobial performance of Ag-based nanomaterials may not necessarily be solely due to the amount of Ag+ ions leached from these nanomaterials, but that the nanomaterial itself may also play a direct role in the antimicrobial action. Notably, the applications of metal-organic semiconducting charge transfer complexes of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) have been predominantly restricted to electronic applications, except from our recent reports on their (photo)catalytic potential and the current case on antimicrobial prospects. This report on growth of these metal-TCNQ complexes on a fabric not only widens the window of these interesting materials for new biological applications, it also opens the possibilities for developing large-area flexible electronic devices by growing a range of metal-organic semiconducting materials directly on a fabric surface.

Phase III study of matrix metalloproteinase inhibitor prinomastat in non-small-cell lung cancer

Purpose: Matrix metalloproteinases (MMPs) degrade extracellular proteins and facilitate tumor growth, invasion, metastasis, and angiogenesis. This trial was undertaken to determine the effect of prinomastat, an inhibitor of selected MMPs, on the survival of patients with advanced non-small-cell lung cancer (NSCLC), when given in combination with gemcitabine-cisplatin chemotherapy. Patients and Methods: Chemotherapy-naive patients were randomly assigned to receive prinomastat 15 mg or placebo twice daily orally continuously, in combination with gemcitabine 1,250 mg/m2 days 1 and 8 plus cisplatin 75 mg/m2 day 1, every 21 days for up to six cycles. The planned sample size was 420 patients. Results: Study results at an interim analysis and lack of efficacy in another phase III trial prompted early closure of this study. There were 362 patients randomized (181 on prinomastat and 181 on placebo). One hundred thirty-four patients had stage IIIB disease with T4 primary tumor, 193 had stage IV disease, and 34 had recurrent disease (one enrolled patient was ineligible with stage IIIA disease). Overall response rates for the two treatment arms were similar (27% for prinomastat v 26% for placebo; P = .81). There was no difference in overall survival or time to progression; for prinomastat versus placebo patients, the median overall survival times were 11.5 versus 10.8 months (P = .82), 1-year survival rates were 43% v 38% (P = .45), and progression-free survival times were 6.1 v 5.5 months (P = .11), respectively. The toxicities of prinomastat were arthralgia, stiffness, and joint swelling. Treatment interruption was required in 38% of prinomastat patients and 12% of placebo patients. Conclusion: Prinomastat does not improve the outcome of chemotherapy in advanced NSCLC. © 2005 by American Society of Clinical Oncology.

A phase III trial of docetaxel/carboplatin versus mitomycin C/ifosfamide/ cisplatin (MIC) or mitomycin C/vinblastine/cisplatin (MVP) in patients with advanced non-small-cell lung cancer : a randomised multicentre trial of the British Thoracic Oncology Group (BTOG1)

Background: Phase III studies suggest that non-small-cell lung cancer (NSCLC) patients treated with cisplatin-docetaxel may have higher response rates and better survival compared with other platinum-based regimens. We report the final results of a randomised phase III study of docetaxel and carboplatin versus MIC or MVP in patients with advanced NSCLC. Patients and methods: Patients with biopsy proven stage III-IV NSCLC not suitable for curative surgery or radiotherapy were randomised to receive four cycles of either DCb (docetaxel 75 mg/m 2, carboplatin AUC 6), or MIC/MVP (mitomycin 6 mg/m 2, ifosfamide 3 g/m 2 and cisplatin 50 mg/m 2 or mitomycin 6 mg/ m 2, vinblastine 6 mg/m 2 and cisplatin 50 mg/m 2, respectively), 3 weekly. The primary end point was survival, secondary end points included response rates, toxicity and quality of life. Results: The median follow-up was 17.4 months. Overall response rate was 32% for both arms (partial response = 31%, complete response = 1%); 32% of MIC/MVP and 26% of DCb patients had stable disease. One-year survival was 39% and 35% for DCb and MIC/MVP, respectively. Two-year survival was 13% with both arms. Grade 3/4 neutropenia (74% versus 43%, P < 0.005), infection (18% versus 9%, P = 0.01) and mucositis (5% versus 1%, P = 0.02) were more common with DCb than MIC/MVP. The MIC/MVP arm had significant worsening in overall EORTC score and global health status whereas the DCb arm showed no significant change. Conclusions: The combination of DCb had similar efficacy to MIC/MVP but quality of life was better maintained. © 2006 European Society for Medical Oncology.