Photoinduced iron-cyclopentadienyl (Fe-Cp) bond cleavage reactions and photocontrolled polymerizations of strained [1]ferrocenophanes

Although extensive previous studies have shown that strained [1]ferrocenophanes predominantly undergo ring-opening chemistry at the bridging atom E-cyclopentadienyl (E-Cp) bond, recent reports have highlighted that reactivity at the Fe-Cp bond can also occur, especially on photoactivation. We provide an overview of recent results from our group and those of other researchers. In addition, the development of photocontrolled living polymerizations of sila[1]ferrocenophanes using Fe-Cp bond cleavage chemistry is described.     

Influence of parent graphite particle size on the electrochemistry of thermally reduced graphene oxide

Electrochemical applications of graphene are of very high importance. For electrochemistry, bulk quantities of materials are needed. The most common preparation of bulk quantities of graphene materials is based on oxidation of graphite to graphite oxide and subsequent thermal exfoliation of graphite oxide to thermally reduced graphene oxide (TR-GO). It is important to investigate to which extent a reaction condition, that is, composition of the oxidation mixture and size of graphite materials, influences the properties of the resulting materials. We characterised six graphite materials with a range of particle sizes (0.05, 11, 20, 32, 35 and 41 μm) and the TR-GO products prepared from them by use of scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Cyclic voltammetric performance of the TR-GO samples was compared using ferro/ferricyanide and ascorbic acid. We observed no correlation between size of initial graphite and properties of the resultant TR-GO such as density of surface defects, amount of oxygen-containing groups, or rate of heterogeneous electron transfer (HET). A positive correspondence between HET rate and high defect density as well as low amounts of oxygen functionalities was noted. Our findings will have profound influence upon practical fabrication of graphene for applications in sensing and energy storage devices.     

Generation-independent dimerization behavior of quadruple hydrogen-bond-containing oligoether dendrons

[reaction: see text] A new series of self-assembling G1-G3 dendronized dimers bearing oligoether dendrons and a dimeric 2-ureido-4-pyrimidinone (UPy) quadruple hydrogen-bonding core were prepared and characterized. It was found that the nonpolar microenvironment created by the dendrons preserved the UPy unit in its DDAA tautomeric form. As a result, the stabilities of the dimers were exceptionally strong for all three generations (K(dim) > 2 x 10(7) M(-)(1) in CDCl(3) at 25 degrees C). Furthermore, the steric size of the dendrons did not exhibit a significant effect on their dimerization behavior.     

Nanoimprint Lithography‐Directed Self‐Assembly of Bimetallic Iron–M (M=Palladium,Platinum) Complexes for Magnetic Patterning

Self‐assembly of d⁸ metal polypyridine systems is a well‐established approach for the creation of 1D organometallic assemblies but there are still challenges for the large‐scale construction of nanostructured patterns from these building blocks. We describe herein the use of high‐throughput nanoimprint lithography (NIL) to direct the self‐assembly of the bimetallic complexes [4′‐ferrocenyl‐(2,2′:6′,2′′‐terpyridine)M(OAc)]⁺(OAc)^? (M=Pd or Pt; OAc=acetate). Uniform nanorods are fabricated from the molecular self‐organization and evidenced by morphological characterization. More importantly, when top‐down NIL is coupled with the bottom‐up self‐assembly of the organometallic building blocks, regular arrays of nanorods can be accessed and the patterns can be controlled by changing the lithographic stamp, where the mold imposes a confinement effect on the nanorod growth. In addition, patterns consisting of the products formed after pyrolysis are studied. The resulting arrays of ferromagnetic FeM alloy nanorods suggest promising potential for the scalable production of ordered magnetic arrays and fabrication of magnetic bit‐patterned media.     

Search for antibacterial agents from Malaysian rainforest and tropical plants

The world's rainforests hold untold potential for drug discovery. Rainforest plants are thought to contain evolved defensive active metabolites of greater diversity compared to plants from temperate regions. In recent years, the interest and overall output from pharmaceutical companies on novel antibacterial agents has diminished at a time when there is a critical need for them to fight the threat of resistance. In this study, we have investigated the antimicrobial properties of 21 flowering plants from 16 different families against six bacterial strains consisting of two Gram negative and four Gram positive. Using the pour plate disc diffusion technique, almost all extracts from these plants were found to be active against some of the bacterial strains tested. The most interesting and active plants with broad spectrum activities include Duabanga grandiflora, Acalypha wilkesiana and Pseuduvaria macrophylla where the minimum inhibitory concentration, minimum bactericidal concentration and phytochemical analysis were carried out. This is the first report describing the antimicrobial and phytochemical properties of D. grandiflora and P. macrophylla. Our findings support the utilisation of higher plant species in the search for new antimicrobial molecules to combat new emerging infective diseases and the problem of drug resistant pathogens.     

Solid phase microextraction with matrix assisted laser desorption/ionization introduction to mass spectrometry and ion mobility spectrometry

Solid phase microextraction (SPME) with matrix assisted laser desorption/ionization (MALDI) introduction was coupled to mass spectrometry and ion mobility spectrometry. Nicotine and myoglobin in matrix 2,5-dihydroxybenzonic acid (DHB), enkephalin and substance P in alpha-cyano-4-hydroxy cinnaminic acid were investigated as the target compounds. The tip of an optical fiber was silanized for extraction of the analytes of interest from solution. The optical fiber thus served as the sample extraction surface, the support for the sample plus matrix, and the optical pipe to transfer the laser energy from the laser to the sample. The MALDI worked under atmospheric pressure, and both an ion mobility spectrometer and a quadrupole/time-of-flight mass spectrometer were used for the detection of the SPME/MALDI signal. The spectra obtained demonstrate the feasibility of the SPME with MALDI introduction to mass spectrometry instrumentation.     

Zeta-potential measurement using the Smoluchowski equation and the slope of the current-time relationship in electroosmotic flow

The zeta -potential of a solid-liquid interface is an important surface characterization quantity for applications ranging from the development of biomedical polymers to the design of microfluidic devices. This study presents a novel experimental technique to measure the zeta -potentials of flat surfaces. This method combines the Smoluchowski equation with the measured slope of current-time relationship in electroosmotic flow. This method is simple and accurate in comparison with the traditional streaming potential and electrophoresis techniques. Using this method the zeta -potentials of glass and poly(dimethylsiloxane) (PDMS) coated surfaces in KCl and LaCl3 aqueous solutions were measured using several flow channels ranging from 200 to 300 microm in height. The zeta -potential was found to vary from -88 to -66 mV for glass surface and -110 to -68 mV for PDMS surfaces depending on the electrolyte and the ionic concentration. The measured values of the zeta -potential are found to be independent of the channel size and the applied driving voltage and generally are repeatable within +/-6%.