Singlet Oxygen and the Origin of Oxygen Functionalities on the Surface of Carbon Electrodes

The generation of oxygen‐containing functionalities on pristine carbon surfaces is investigated and shown to be light sensitive, specifically to infra‐red radiation. A mechanistic route involving singlet oxygen, ¹O₂, is proposed and evidenced.     

Factors affecting the solid-state structure and dimensionality of mercury cyanide/chloride double salts, and NMR characterization of coordination geometries

In the reaction of organic monocationic chlorides or coordinatively saturated metal-ligand complex chlorides with linear, neutral Hg(CN)(2) building blocks, the Lewis-acidic Hg(CN)(2) moieties accept the chloride ligands to form mercury cyanide/chloride double salt anions that in several cases form infinite 1-D and 2-D arrays. Thus, [PPN][Hg(CN)(2)Cl].H(2)O (1), [(n)Bu(4)N][Hg(CN)(2)Cl].0.5 H(2)O (2), and [Ni(terpy)(2)][Hg(CN)(2)Cl](2) (4) contain [Hg(CN)(2)Cl](2)(2-) anionic dimers ([PPN]Cl = bis(triphenylphosphoranylidene)ammonium chloride, [(n)Bu(4)N]Cl = tetrabutylammonium chloride, terpy = 2,2':6',6' '-terpyridine). [Cu(en)(2)][Hg(CN)(2)Cl](2) (5) is composed of alternating 1-D chloride-bridged [Hg(CN)(2)Cl](n)(n-) ladders and cationic columns of [Cu(en)(2)](2+) (en = ethylenediamine). When [Co(en)(3)]Cl(3) is reacted with 3 equiv of Hg(CN)(2), 1-D [[Hg(CN)(2)](2)Cl](n)(n-) ribbons and [Hg(CN)(2)Cl(2)](2-) moieties are formed; both form hydrogen bonds to [Co(en)(3)](3+) cations, yielding [Co(en)(3)][Hg(CN)(2)Cl(2)][[Hg(CN)(2)](2)Cl] (6). In [Co(NH(3))(6)](2)[Hg(CN)(2)](5)Cl(6).2H(2)O (7), [Co(NH(3))(6)](3+) cations and water molecules are sandwiched between chloride-bridged 2-D anionic [[Hg(CN)(2)](5)Cl(6)](n)(6n-) layers, which contain square cavities. The presence (or absence), number, and profile of hydrogen bond donor sites of the transition metal amine ligands were observed to strongly influence the structural motif and dimensionality adopted by the anionic double salt complex anions, while cation shape and cation charge had little effect. (199)Hg chemical shift tensors and (1)J((13)C,(199)Hg) values measured in selected compounds reveal that the NMR properties are dominated by the Hg(CN)(2) moiety, with little influence from the chloride bonding characteristics. delta(iso)((13)CN) values in the isolated dimers are remarkably sensitive to the local geometry.     

Preparation and benchmarking of novel cellulose nanopaper

Cellulose - Synthetic polymers and plastics which are currently used as barrier materials in packaging applications are neither renewable nor biodegradable. Nanopaper, which is obtained by breaking...     

The effect of pulp type on the performance of microfibrillar lignocellulosic bismuth-based active packaging material

Cellulose - The study aims to investigate the effect of the different lignocellulosic pulp on the composite properties for active packaging application. Microfibrillated cellulose from bleached and...     

An evaluation of infrared microwindows for ozone retrievals using the Eureka Bruker 125HR Fourier transform spectrometer

A Bruker 125HR Fourier transform spectrometer was installed at the Polar Environment Atmospheric Research Laboratory (PEARL) at Eureka, Nunavut, Canada in the summer of 2006 to study atmospheric composition. Using the optimal estimation method, typically over a limited spectral region called a microwindow, information about the vertical distribution of trace gas species that have absorption bands in the mid-infrared spectral range can be retrieved. Total and partial columns can also be determined to show the temporal evolution of the target gas. For ozone in particular, retrievals have been performed using several of its many mid-infrared absorption features, resulting in a lack of consistency in the literature in the microwindows chosen for retrievals. This work focuses on the optimization of the ozone retrieval, assessing a set of 22 microwindows between 780 and 3052 cm⁻¹ to determine which is best suited to conditions at Eureka. The 1000-1004.5 cm⁻¹ spectral interval is shown to be the most sensitive to both the stratosphere and troposphere. This microwindow gives the highest number of degrees of freedom for signal (∼7 for total column), and the smallest total error (4.3%) compared with 21 other spectral regions. Retrievals performed with this microwindow agree well with results obtained from other instruments on-site. Total column ozone measured by the Bruker 125HR in this microwindow agreed to 2% with two other Fourier transform spectrometers, to 0.7% with a Brewer spectrophotometer, to 8% with a SAOZ UV-VIS spectrometer, and to 7% with ozone sondes.     

Observations of biological choruses in the Southern California Bight: A chorus at midfrequencies

This paper describes the characteristics of an underwater biological chorus recorded in the midfrequency band (1-10 kHz) in the Southern California Bight. The recordings were made in July, 2002 by a large-vertical-aperture, 131-element, 2D billboard array. The chorus, observed predominantly on two consecutive nights during the 8-day experiment, is composed of two bands of energy centered around 1.5 kHz and between 4 and 5 kHz. It causes a complete reversal in the vertical directional characteristics of the mid-frequency ambient sound field between day and nighttime periods; whereas the vertical structure during the day shows a notch in the horizontal direction with levels more than 10 dB below those at higher angles, the nighttime levels in the horizontal can exceed those at other vertical angles by more than 10 dB. These nighttime sounds also are strongly anisotropic in azimuth; they appear to come mainly from a popular Southern California fishing spot where the water depths exceed 75 m. Vertical beam-to-beam coherence squared estimates suggest the chorus source region exists on spatial scales greater than the multipath interference wavelengths of this environment. Individual sounds comprising the chorus, although difficult to separate from the background din, have a fluttering, rasping character.     

Au(CN)4]- as a supramolecular building block for heterobimetallic coordination polymers

A series of the first coordination polymers using the [Au(CN)(4)](-) anion as a building block has been prepared. The planar tetracyanoaurate anion uses one, two, or four cyano groups to bridge to Ni(II) or Cu(II) centers and exhibits weak Au(III)-N(cyano) interactions between anions. Ni(en)(2)[Au(CN)(4)](2).H(2)O (1, en = ethylenediamine) is a molecular compound with the two [Au(CN)(4)](-) anions coordinating in a trans orientation to Ni(II) without further cyanide coordination. Cu(dien)[Au(CN)(4)](2) (2, dien = diethylenetriamine) forms a similar molecular complex; however, the dimensionality is increased through weak intermolecular Au-N(cyano) interactions of 3.002(14) A to form a 1-D zigzag chain. Cu(en)(2)[Au(CN)(4)](2) (3) also forms a molecular complex similar to 1, but with elongated axial bonds. The complex further aggregates through Au-N(cyano) interactions of 3.035(8) A to form a 2-D array. In [Cu(dmeda)(2)Au(CN)(4)][Au(CN)(4)] (4, dmeda = N,N-dimethylethylenediamine) one [Au(CN)(4)](-) anion coordinates via two cis-N(cyano) donors to the axial sites of two Cu(II) centers to form a 1-D zigzag chain of alternating [Cu(dmeda)(2)](2+) and [Au(CN)(2)](-) units; the other [Au(CN)(4)](-) anion forms a 1-D chain via Au-N(cyano) interactions. In [Cu(bipy)(H(2)O)(2)(Au(CN)(4))(0.5)][Au(CN)(4)](1.5) (5, bipy = 2,2'-bipyridine) one [Au(CN)(4)](-) anion uses all four cyano moieties to bridge four different Cu(II) centers, creating a 1-D chain.     

Preparation and characterization of implantable sensors with nitric oxide release coatings

The widespread use of miniaturized chemical sensors to monitor clinically important analytes such as PO₂, PCO₂, pH, electrolytes, glucose and lactate in a continuous, real-time manner has been seriously hindered by the erratic analytical results often obtained when such devices are implanted in vivo. One major factor that has influenced the analytical performance of indwelling sensors is the biological response they elicit when in contact with blood or tissue (e.g. thrombus formation on the device surface, inflammatory response, encapsulation, etc.). Nitric oxide (NO) has been shown to be a potent inhibitor of platelet adhesion and activation as well as a promoter of wound healing in tissue. Herein, we review recent work aimed at the development of hydrophobic NO-releasing polymers that can be employed to coat catheter-type amperometric oxygen sensors without interfering with the analytical performance of these devices. Such modified sensors are shown to exhibit greatly enhanced hemocompatibility and improved analytical performance when implanted within porcine carotid and femoral arteries for up to 16 h. Further, results from preliminary studies also demonstrate that prototype fluorescent oxygen sensors, catheter-style potentiometric carbon dioxide sensors and subcutaneous needle-type enzyme-based amperometric glucose sensors can also be fabricated with new NO-release outer coatings without compromising the analytical response characteristics of these devices. The NO-release strategy may provide a solution to the lingering biocompatibility problems encountered when miniature chemical sensors are implanted in vivo.     

Quantum Phase Diagram of an Exactly Solved Mixed Spin Ladder

We investigate the quantum phase diagram of the exactly solved mixed spin-(1/2,1) ladder via the thermodynamic Bethe ansatz (TBA). In the absence of a magnetic field the model exhibits three quantum phases associated with su(2), su(4), and su(6) symmetries. In the presence of a strong magnetic field, there is a third and full saturation magnetization plateaux within the strong antiferromagnetic rung coupling regime. Gapless and gapped phases appear in turn as the magnetic field increases. For weak rung coupling, the fractional magnetization plateau vanishs and the model undergoes new quantum phase transitions. However, in the ferromagnetic coupling regime, the system does not have a third saturation magnetization plateau. The critical behaviour in the vicinity of the critical points is also derived systematically using the TBA.