Probing the surface oxidation of chemically synthesised gold nanospheres and nanorods

In this study, the electrochemical behaviour of commercially available gold spheres and rods stabilised by carboxylic acid and cetyl trimethyl ammonium bromide (CTAB) moieties, respectively, are investigated. The cyclic voltammetric behaviour in acidic electrolyte is distinctly different with the nanorods exhibiting unusual oxidative behaviour due to an electrodissolution process. The nanospheres exhibited responses typical of a highly defective surface which significantly impacted on electrocatalytic activity. A repetitive potential cycling cleaning procedure was also investigated which did not improve the activity of the nanorods and resulted in deactivating the gold spheres due to decreasing the level of surface defects.

A mass spectrometry study of XCO+, X = Si, Ge : Is SiCO+ a main group carbonyl? Comments on the bonding in ground state SiCO and the Si,C,O (+) potential energy surface

The cation\[Si,C,O](+) has been generated by 1) the electron ionisation (EI) of tetramethoxysilane and 2) chemical ionisation (CI) of a mixture of silane and carbon monoxide. Collisional activation (CA) experiments performed for mass-selected \[Si,C,O](+), generated by using both methods, indicate that the structure is not inserted OSiC+; however, a definitive structural assignment as Si+-CO, Si+-OC or some cyclic variant is impossible based on these results alone. Neutralisation-reionisation (+NR+) experiments for EI-generated \[Si,C,O](+) reveal a small peak corresponding to SiC+, but no detectable SiO+ signal, and thus establishes the existence of the Si+-CO isomer. CCSD(T)//B3LYP calculations employing a triple-zeta basis set have been used to explore the doublet and quartet potential-energy surfaces of the cation, as well as some important neutral states The results suggest that both Si+-CO and Si+ - OC isomers are feasible; however, the global minimum is (2)Pi SiCO+. Isomeric (2)Pi SiOC+ is 12.1 kcal mol(-1) less stable than (2)Pi SiCO+, and all quartet isomers are much higher in energy. The corresponding neutrals Si-CO and Si-OC are also feasible, but the lowest energy Si - OC isomer ((3)A") is bound by only 1.5 kcal mol(-1). We attribute most, if nor all, of the recovery signal in the +NR' experiment to SiCO+ survivor ions. The nature of the bonding in the lowest energy isomers of Si+ -(CO,OC) is interpreted with the aid of natural bond order analyses, and the ground stale bonding of SiCO+ is discussed in relation to classical analogues such as metal carbonyls and ketenes.

Secreted products and extracellular matrix from testicular peritubular myoid cells influence androgen-binding protein secretion by Sertoli cells in culture

Metabolic cooperation mediated by secreted factors between Sertoli cells and peritubular myoid cells has been well documented. We have confirmed that factors secreted by peritubular myoid cells modulate androgen-binding protein (ABP) secretion by Sertoli cells and shown further that this can also be achieved with peritubular myoid cell extracellular matrix (ECM). While peritubular myoid cell ECM potentiated the stimulatory effect of dibutyryl cyclic AMP on Sertoli cell ABP secretion, secreted factors did not, suggesting that the two components influence Sertoli cells through distinct mechanisms. We also tested other factors and other cell lines for effects on ABP production by Sertoli cells. The addition of human plasma fibronectin or conditioned medium from the basement membrane-producing Englebreth-Holm- Swarm sarcoma also stimulated ABP secretion by Sertoli cells. Cocultures of epithelial Sertoli cells with the cells of mesenchymal origin, such as testicular peritubular myoid cells, embryonic skin fibroblasts, and bladder smooth muscle cells, significantly stimulated ABP secretion by Sertoli cells, but co-culture with the epithelial-derived Martin-Darby canine kidney cell line had no effect on Sertoli cell-secreted ABP levels. Our data further define the epithelial-mesenchymal cell interaction that exists between Sertoli cells and peritubular myoid cells in the mammalian testis.

Failure of discontinuous railhead edges due to plastic strain accumulation

Railhead is perhaps the highest stressed civil infrastructure due to the passage of heavily loaded wheels through a very small contact patch. The stresses at the contact patch cause yielding of the railhead material and wear. Many theories exist for the prediction of these mechanisms of continuous rails; this process in the discontinuous rails is relatively sparingly researched. Discontinuous railhead edges fail due to accumulating excessive plastic strains. Significant safety concern is widely reported as these edges form part of Insulated Rail Joints (IRJs) in the signalling track circuitry. Since Hertzian contact is not valid at a discontinuous edge, 3D finite element (3DFE) models of wheel contact at a railhead edge have been used in this research. Elastic–plastic material properties of the head hardened rail steel have been experimentally determined through uniaxial monotonic tension tests and incorporated into a FE model of a cylindrical specimen subject to cyclic tension load- ing. The parameters required for the Chaboche kinematic hardening model have been determined from the stabilised hysteresis loops of the cyclic load simulation and imple- mented into the 3DFE model. The 3DFE predictions of the plastic strain accumulation in the vicinity of the wheel contact at discontinuous railhead edges are shown to be affected by the contact due to passage of wheels rather than the magnitude of the loads the wheels carry. Therefore to eliminate this failure mechanism, modification to the contact patch is essential; reduction in wheel load cannot solve this problem.

Experiences with control of evaporators using extensive vapour bleeding

FOR SUGAR factories with cogeneration plants major changes to the process stations have been undertaken to reduce the consumption of exhaust steam from the turbines and maximise the generated power. In many cases the process steam consumption has been reduced from greater than 52% on cane to ~40% on cane. The main changes have been to install additional evaporation area at the front of the set, operate the pan stages on vapour from No 1 or No 2 effects and undertake juice heating using vapour bleed from evaporators as far down the set as the penultimate stage. Operationally, one of the main challenges has been to develop a control system for the evaporators that addresses the objectives of juice processing rate (throughput) and steam economy, while producing syrup consistently at the required brix and providing an adequate and consistent vapour pressure for the pan stage operations. The cyclic demand for vapour by batch pans causes process disturbances through the evaporator set and these must be regulated in an effective manner to satisfy the above list of objectives for the evaporator station. The impact of the cyclic pan stage vapour demand has been modelled to define the impact on juice rate, steam economy, syrup brix and head space pressures in the evaporators. Experiences with the control schemes used at Pioneer and Rocky Point Mills are discussed. For each factory the paper provides information on (a) the control system used, the philosophy behind the control system and experiences in reaching the current system for control (b) the performance of the control system to handle the disturbances imposed by the pan stage and operate within other constraints of the factory (c) deficiencies in the current system and plans for further improvements. Other processing changes to boost the performance of the evaporators are also discussed.

Discharge mode transitions in low-frequency inductively coupled plasmas with internal oscillating current sheets

Transitions between the two discharge modes in a low-frequency (∼460 kHz) inductively coupled plasma sustained by an internal oscillating radio frequency (rf) current sheet are studied. The unidirectional rf current sheet is generated by an internal antenna comprising two orthogonal sets of synphased rf currents driven in alternately reconnected copper litz wires. It is shown that in the low-to-intermediate pressure range the plasma source can be operated in the electrostatic (E) and electromagnetic (H) discharge modes. The brightness of the E -mode argon plasma glow is found remarkably higher than in inductively coupled plasmas with external flat spiral "pancake" coils. The cyclic variations of the input rf power result in pronounced hysteretic variations of the optical emission intensity and main circuit parameters of the plasma source. Under certain conditions, it appears possible to achieve a spontaneous E→H transition ("self-transition"). The observed phenomenon can be attributed to the thermal drift of the plasma parameters due to the overheating of the working gas. The discharge destabilizing factors due to the gas heating and step-wise ionization are also discussed. © 2005 American Vacuum Society.

An experimental based assessment of the deviation of the bearing characteristic frequencies

Slippage in the contact roller-races has always played a central role in the field of diagnostics of rolling element bearings. Due to this phenomenon, vibrations triggered by a localized damage are not strictly periodic and therefore not detectable by means of common spectral functions as power spectral density or discrete Fourier transform. Due to the strong second order cyclostationary component, characterizing these signals, techniques such as cyclic coherence, its integrated form and square envelope spectrum have proven to be effective in a wide range of applications. An expert user can easily identify a damage and its location within the bearing components by looking for particular patterns of peaks in the output of the selected cyclostationary tool. These peaks will be found in the neighborhood of specific frequencies, that can be calculated in advance as functions of the geometrical features of the bearing itself. Unfortunately the non-periodicity of the vibration signal is not the only consequence of the slippage: often it also involves a displacement of the damage characteristic peaks from the theoretically expected frequencies. This issue becomes particularly important in the attempt to develop highly automated algorithms for bearing damage recognition, and, in order to correctly set thresholds and tolerances, a quantitative description of the magnitude of the above mentioned deviations is needed. This paper is aimed at identifying the dependency of the deviations on the different operating conditions. This has been possible thanks to an extended experimental activity performed on a full scale bearing test rig, able to reproduce realistically the operating and environmental conditions typical of an industrial high power electric motor and gearbox. The importance of load will be investigated in detail for different bearing damages. Finally some guidelines on how to cope with such deviations will be given, accordingly to the expertise obtained in the experimental activity.

Tuning second order cyclostationarity parameters for the diagnostics of rolling element bearings

Failures on rolling element bearings usually originate from cracks that are detectable even in their early stage of propogation by properly analyzing vibration signals measured in the proximity of the bearing. Due to micro-slipping in the roller-races contact, damage-induced vibration signals belong to the family of quasi-periodic signals with a strong second order cyclostationary component. Cyclic coherence and its integrated form are widely considered as the most suitable tools for bearing fault diagnostics and their theoretical bases have been already consolidated. This paper presents how to correctly set the parameters of the cyclostationary analysis tool to be implemented in an automatable algorithm. In the first part of the paper some general guidelines are provided for the specific application. These considerations are further verified, applying cyclostationary tools to data collected in an experimental campaign on a specific test-rig.

3D-hybrid networks with controllable electrical conductivity from the electrochemical deposition of terthiophene-functionalized polyphenylene dendrimers

(Figure Presented) Unusual conductivity effects: Suitably functionalized dendrimers (see picture) are capable of forming truly covalent three-dimensional networks with remarkably high conductivity on electrochemical doping. Depending on the charging level of the electroactive components used as building blocks for the dendrimer core and the perimeter, two separated regimes of electrical conductivity can be observed.

Thiophene-based dendronized macromonomers and polymers

The synthesis of thiophene-containing second (G2) and third generation (G3) dendronized macromonomers with methacrylate polymerizable units as well as their corresponding dendronized polymers is reported. The dendrons are prepared from branched thiophene oligomers and are decorated with straight alkyl chains for solubility reasons. The polymerization reactions were done with AIBN as initiator and the polymers were characterized by NMR spectroscopy, elemental analysis and GPC. Molar masses are in the range of 2.2-5.4 × 105 g mol-1 (G2) and 1.3-3.0 × 104 g mol-1 (G3) for different runs. These polymers are investigated by cyclic voltammetry and optical spectroscopy.

Solution processable low bandgap diketopyrrolopyrrole (DPP) based derivatives : novel acceptors for organic solar cells

Novel low bandgap solution processable diketopyrrolopyrrole (DPP) based derivatives functionalized with electron withdrawing end capping groups (trifluoromethylphenyl and trifluorophenyl) were synthesized, and their photophysical, electrochemical and photovoltaic properties were investigated. These compounds showed optical bandgaps ranging from 1.81 to 1.94 eV and intense absorption bands that cover a wide range from 300 to 700 nm, attributed to charge transfer transition between electron rich phenylene-thienylene moieties and the electron withdrawing diketopyrrolopyrrole core. All of the compounds were found to be fluorescent in solution with an emission wavelength ranging from 600 to 800 nm. Cyclic voltammetry indicated reversible oxidation and reduction processes with tuning of HOMO-LUMO energy levels. Bulk heterojunction (BHJ) solar cells using poly(3-hexylthiophene) (P3HT) as the electron donor with these new acceptors were used for fabrication. The best power conversion efficiencies (PCE) using 1:2 donor-acceptor by weight mixture were 1% under simulated AM 1.5 solar irradiation of 100 mW cm-2. These findings suggested that a DPP core functionalized with electron accepting end-capping groups were a promising new class of solution processable low bandgap n-type organic semiconductors for organic solar cell applications.

Comparative behavior of CdS and CdSe quantum dots in poly(3-hexylthiophene) based nanocomposites

CdS and CdSe nanoparticles have been prepared using conducting poly(3-hexylthiophene) (P3HT) matrix with an objective to understand the effect of nanoparticles on the polymer matrix using electrochemical and spectroscopic techniques. The spectroscopic results reveal that the electronic structure of polymer is strongly influenced by the characteristics of embedded semiconducting nanoparticles. SEM and TEM images show the ordered morphology of the CdS and CdSe nanoparticles in presence of the polymer matrix. Cyclic voltammetry performed both in the presence and absence of light enables us to understand the redox changes in P3HT due to CdS and CdSe quantum dots such as the generation of free radical in the excited state and their electrochemical band gaps.

Thiophene-benzothiadiazole-thiophene (D-A-D) based polymers : Effect of donor/acceptor moieties adjacent to D-A-D segment on photophysical and photovoltaic properties

New push-pull copolymers based on thiophene (donor) and benzothiadiazole (acceptor) units, poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co- thiophene] (PT3B1) and poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] (PT2B2), are designed and synthesized via Stille and Suzuki coupling routes respectively. Gel permeation chromatography shows the number average molecular weights are 31100 and 8400 g mol-1 for the two polymers, respectively. Both polymers have shown absorption throughout a wide range of the UV-vis region, from 300 to 650 nm. A significant red shift of the absorption edge is observed in thin films compared to solution of the copolymers; the optical band gap is in the range of 1.7 to 1.8 eV. Cyclic voltammetry indicates reversible oxidation and reduction processes with HOMO energy levels calculated to be in the range of 5.2 to 5.4 eV. Upon testing both materials for organic field-effect transistors (OFETs), PT3B1 showed a hole mobility of 6.1 × 10-4 cm2 V-1 s -1, while PT2B2 did not show any field effect transport. Both copolymers displayed a photovoltaic response when combined with a methanofullerene as an electron acceptor. The best performance was achieved when the copolymer PT3B1 was blended with [70]PCBM in a 1:4 ratio, exhibiting a short-circuit current of 7.27 mA cm-2, an open circuit voltage of 0.85 V, and a fill factor of 41% yielding a power conversion efficiency of 2.54% under simulated air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm-2). Similar devices utilizing PT2B2 in place of PT3B1 demonstrated reduced performance with a short-circuit current of 4.8 mA cm -2, an open circuit voltage of 0.73 V, and a fill factor of 30% resulting in a power conversion efficiency of roughly 1.06%.

Experimental evidence for competitive N–O and O–C bond homolysis in gasphase alkoxyamines

The extensive use of alkoxyamines in controlled radical polymerisation and polymer stabilisation is based on rapid cycling between the alkoxyamine (R1R2NO–R3) and a stable nitroxyl radical (R1R2NO•) via homolysis of the labile O–C bond. Competing homolysis of the alkoxyamine N–O bond has been predicted to occur for some substituents leading to production of aminyl and alkoxyl radicals. This intrinsic competition between the O–C and N–O bond homolysis processes has to this point been difficult to probe experimentally. Herein we examine the effect of local molecular structure on the competition between N–O and O–C bond cleavage in the gas phase by variable energy tandem mass spectrometry in a triple quadrupole mass spectrometer. A suite of cyclic alkoxyamines with remote carboxylic acid moieties (HOOC–R1R2NO–R3) were synthesised and subjected to negative ion electrospray ionisation to yield [M – H]− anions where the charge is remote from the alkoxyamine moiety. Collision-induced dissociation of these anions yield product ions resulting, almost exclusively, from homolysis of O–C and/or N–O bonds. The relative efficacy of N–O and O–C bond homolysis was examined for alkoxyamines incorporating different R3 substituents by varying the potential difference applied to the collision cell, and comparing dissociation thresholds of each product ion channel. For most R3 substituents, product ions from homolysis of the O–C bond are observed and product ions resulting from cleavage of the N–O bond are minor or absent. A limited number of examples were encountered however, where N–O homolysis is a competitive dissociation pathway because the O–C bond is stabilised by adjacent heteroatom(s) (e.g., R3 = CH2F). The dissociation threshold energies were compared for different alkoxyamine substituents (R3) and the relative ordering of these experimentally determined energies is shown to correlate with the bond dissociation free energies, calculated by ab initio methods. Understanding the structure-dependent relationship between these rival processes will assist in the design and selection of alkoxyamine motifs that selectively promote the desirable O–C homolysis pathway.

Between rocks and hard places

A travel article about the Aland Islands, Finland, that discusses the mix of Swedish, Finnish, and Russian cultural influences in the area. On the map, Finland seems to end in fragments. The gods have stomped their heels on the southwestern corner, and between the cities of Helsinki and Turku it is jagged, rocky islands that form the final landmarks...