Design of Adaptive Procedures for Fault Detection and Isolation

An algorithm is presented for designing minimum-expected-cost test trees for detecting and isolating single faults in a system. A test is specified by the subset of components that must be good for the test to pass, and with each test is associated a fixed cost. Each component is assumed to have an a priori probability of failure. The test tree specifies an adaptive testing procedure that detects a failure and isolates the faulty component while minimizing the expected cost of testing.     

Thermosensitivity of Bile Acid‐Based Oligo(ethylene glycol) Stars in Aqueous Solutions

Amphiphilic star‐shaped oligo(ethylene glycol)s with a hydrophobic bile acid core and varying number of hydrophilic arms have been made. Their thermal behavior in aqueous solutions depends on the number rather than the length of the arms. The two‐armed lithocholate derivative showed the strongest tendency for association and exhibited the lowest cloud point (79 °C) of the oligomers made, as well as another phase separation at a lower temperature (31 °C). The “double thermosensitivity” arising both from the salt‐dependent LCST of the oligo(ethylene glycol) segments and the temperature‐responsive self‐assembly of amphiphilic bile acid derivative provides an interesting path in the design of bile acid‐based smart materials.

     

Pi-bonded quinonoid transition-metal complexes

Coordination of the carbocyclic ring of hydroquinones to electrophilic transition-metal fragments such as Mn(CO)3+ and Rh(COD)+ produces stable pi-bonded eta6-complexes that are activated to facile reversible deprotonation of the -OH groups. The deprotonations are accompanied by electron transfer to the transition metal, which acts as an internal oxidizing agent or electron sink. With manganese as the metal, the resulting eta5-semiquinone and eta4-quinone complexes have been used to synthesize one- two- and three-dimensional polymeric metal-organometallic coordination networks. With rhodium as the metal, the pi-quinonoid complexes have been demonstrated to play a unique role in multifunctional C-C coupling catalysis and in the synthesis of new organolithium reagents. Both classes of pi-quinonoid complexes appear to have significant applications in nanochemistry by providing an excellent vehicle for templating the directed self-assembly of nanoparticles into functional materials.     

Detection of chemical warfare simulants by phosphorylation of a coumarin oximate

The detection of chemical warfare simulants is attained by the PET mechanism that gives an "off-on" fluorescent response with a half-life of approximately 50 ms upon phosphorylation of a reactive oximate functionality; the X-ray crystal structure of the oximate was also obtained and is discussed.     

Organometallic crystal engineering of [(1,4- and 1,3-hydroquinone)Rh(P(OPh)3)2]BF4 by charge assisted hydrogen bonding

The ionic complexes [(1,4- and 1,3-hydroquinone)Rh(P(OPh)3)2]BF4 form porous organometallic structures dictated by charge assisted hydrogen bonding.     

Rational Design of Charge‐Neutral,Near‐Infrared‐Emitting Osmium(II) Complexes and OLED Fabrication

A new series of charge neutral Os(II) isoquinolyl triazolate complexes ( 1 – 4 ) with both trans and cis arrangement of phosphine donors are synthesized, and their structural, electrochemical and photophysical properties are established. In sharp contrast to the cis‐arranged complexes 2 – 4 , the trans derivative 1 , which shows a planar arrangement of chromophoric N‐substituted chelates, offers the most effective extended π‐delocalization and hence the lowest excited state energy gap. These complexes exhibit phosphorescence with peak wavelengths ranging from 692–805 nm in degassed CH₂Cl₂ at room temperature. Near‐infrared (NIR)‐emitting electroluminescent devices employing 6 wt % of 1 (or 4 ) doped in Alq₃ host material are successfully fabricated. The devices incorporating 1 as NIR phosphor exhibit fairly intense emission with a peak wavelength at 814 nm. Forward radiant emittance reaches as high as 65.02 µW cm^?2, and a peak EQE of ～1.5% with devices employing Alq₃, TPBi and/or TAZ as electron‐transporting/exciton‐blocking layers. Upon switching to phosphor 4 , the electroluminescence blue shifts to 718 nm, while the maximum EQE and radiance increase to 2.7% and 93.26 (μW cm^?2) respectively. Their performances are optimized upon using TAZ as the electron transporting and exciton‐blocking material. The OLEDs characterized represent the only NIR‐emitting devices fabricated using charge‐neutral and volatile Os(II) phosphors via thermal vacuum deposition.     

Redox Communication within Multinuclear Iron–Sulfur Complexes Related to Electronic Interplay in the Active Site of [FeFe]Hydrogenase

The one‐electron oxidations of a Fe₂ complex lead to the formation of a persistent metal‐stabilized thiyl radical Fe₂ species, mixed‐valent Fe₄, and Fe₈ complexes. The unpaired spin in the Fe₂ radical species delocalizes over the Fe₂ and the aromatic dithiolate, mostly on the terminal sulfur. The subsequent dimerization of the singly oxidized Fe₂ to the Fe₄ retains the partial thiyl radical character. For an analogue with less steric hindrance, the π–π stacking interaction between the dithiolato aromatic rings induces generation of the Fe₈, in which process electronic structures of the species are modulated through reducing the thiyl radical to the thiolate. Electronic reorganization repeats when the Fe₈ is converted to Fe₄. Electronic interplay in the complexes decreases the energy gap of frontier MOs and buffers electronic impacts upon redox events. Easier accessible redox potentials and increased stability of the species are facilitated. The results demonstrate that electronic versatility of the benzenedithiolate exerts pronounced influences on electronic and coordination structure of the metal complexes.