Cucurbit[7]uril complexations of bis(isoquinolinium)alkane dications in aqueous solution

The 1:1 and 2:1 host–guest complexation of a series of 1,n-bis(isoquinolinium)alkane dications (Iq(CH₂)_nIq²⁺, n = 2, 4, 5, 6, 8, 9, 10 and 12, and Iq(p-xylene)Iq²⁺) by cucurbit[7]uril (CB[7]) in aqueous solution has been investigated by ¹H NMR spectroscopy and ESI mass spectrometry. The site of binding of the first CB[7] is dependent on the nature of the central linker group, with encapsulation of the p-xylene group or the polymethylene chain when n = 6–10.With shorter (n = 2–5) or longer (n = 12) chains, the first CB[7] binds over an isoquinolinium group. With a second CB[7], the binding of the central group is abandoned in favour of the CB[7] hosts encapsulating the two cationic isoquinolinium termini. The 1:1 and 2:1 host–guest stability constants are related to modes of binding and the nature of the central linkers, and are compared with dicationic guests bearing different terminal groups.     

Synthesis of Oligomeric Mannosides and Their Structure‐Binding Relationship with Concanavalin A

Small glycodendrimers with α‐mannosyl ligands were synthesized by using copper‐catalyzed azide–alkyne coupling chemistry and some of these molecules were used as multivalent ligands to study the induction of concanavalin A (Con A) precipitation. The results showed that the monovalent mannose ligand could induce the precipitation of Con A. This unexpected finding initiated a series of studies to characterize the molecular basis of the ligand–lectin interaction. The atypical precipitation is found to be specific to the mannose, fluorescein moiety (FITC), and Con A. Apparently the mannose ligand binds to Con A through hydrogen‐bonding interactions, whereas the binding of FITC is mediated by hydrophobic forces.     

Synthesis,Structure, Photoluminescence,and Electroluminescence of Siloles that Contain Planar Fluorescent Chromophores

Herein, a new series of siloles that were 2,5‐substituted with planar fluorescent chromophores (PFCs), including fluorene, fluoranthene, naphthalene, pyrene, and anthracene, were synthesized and characterized. These compounds showed weak emission in the solution state, owing to active intramolecular rotation (IMR), but the synergistic effect from electronic coupling between the PFC and the silole ring compensated for the emission quenching by the IMR process to some extent, thereby affording higher emission efficiencies than those of 2,3,4,5‐tetraphenylsiloles in solution. These new siloles showed enhanced emission efficiencies in the aggregated state. The electroluminescence (EL) color and efficiency of new siloles were sensitive towards the PFC. Siloles containing naphthalene moieties showed green EL emission, whilst those containing anthracene moieties showed orange EL emission. The siloles containing pyrene moieties exhibited yellow EL emission at 546 nm, with a peak luminance of 49000 cd cm^?2 and a high current efficiency of 9.1 cd A^?1.     

Observation of singlet cycloreversion of thymine oxetanes by direct photolysis

An ultrafast broadband transient absorption spectroscopic study of the direct photolysis of oxetane DMT-BP [which is the oxetane adduct of 1,3-dimethylthymine (DMT) with benzophenone (BP)] is presented. Previous nanosecond time-resolved absorption studies by other researchers observed that direct photolysis of such oxetanes results in a rare, adiabatic photochemical reaction to produce a triplet excited-state carbonyl species. However, the mechanism for this adiabatic photochemical reaction remained unclear for the reaction sequence of the bond scission and the intersystem crossing (ISC) because of the time resolution for the experiments, and this prompted us to further study its mechanism with ultrafast time-resolution. The ultrafast time-resolved spectra presented here indicate that the cycloreversion reaction occurs in a stepwise manner on a singlet excited-state, and then intersystem crossing (ISC) occurs to produce the triplet carbonyl product observed in the previously reported nanosecond time-resolved experiments.     

Detection of singly- and doubly-charged quaternary ammonium drugs in equine urine by liquid chromatography/tandem mass spectrometry

Quaternary ammonium drugs (QADs) are anticholinergic agents some of which are known to have been abused or misused in equine sports. A recent review of literature shows that the screening methods reported thus far for QADs mainly cover singly-charged QADs. Doubly-charged QADs are extremely polar substances which are difficult to be extracted and poorly retained on reversed-phase columns. It would be ideal if a comprehensive method can be developed which can detect both singly- and doubly-charged QADs. This paper describes an efficient liquid chromatography/tandem mass spectrometry (LC/MS/MS) method for the simultaneous detection and confirmation of 38 singly- and doubly-charged QADs at sub-parts-per-billion (ppb) to low-ppb levels in equine urine after solid-phase extraction.     

Nested PCR in magnetically actuated circular closed-loop PCR microchip system

We demonstrate a new and sensitive amplification technique (referred to as Nested Polymerase Chain Reaction; nPCR). It based on a magnetically actuated circular closed-loop PCR microchip system. nPCR involves the use of two sets of primers in two successive PCR runs, and allows the amplification of a single locus from a minute quantity of template DNA. Two sets of primers are specially designed to a target 500-bp region of the bacteriophage lambda template DNA in the first PCR run, and a 247-bp region of the targeted 500-bp first PCR product in the second PCR run. PCR is run on the microchip system and concurrently in regular thermocycler for comparison. The products are analyzed by conventional agarose gel electrophoresis. The detection limit for the initial template DNA is 1.63?×?10⁵ copies per μL (or 8.67?pg) for the first PCR run, and 1.63 copies per μL (or 0.0867?fg) for the second run. The results are comparable to a regular thermocycler. This preliminary study opens a new gateway to future development of specialized nPCR on chip.

Patent-investment games under asymmetric information

This paper analyzes preemptive patenting in a two-stage real options game where an incumbent firm competes with a potential entrant firm for the patent of a substitute product in a product market with profit flow uncertainty. The incumbent suffers loss of monopoly in the product market if the entrant acquires the patent of a substitute product and later commercializes the product. Our patent-investment game model assumes that the entrant has complete information on the incumbent’s commercialization cost while the incumbent only knows the distribution of the entrant’s cost. We investigate the impact of information asymmetry on the preemption strategies adopted by the two competing firms on patenting the substitute product by comparing the optimal preemption strategies and the real option value functions of the two competing firms under complete information and information asymmetry. Our analysis reveals that the informationally disadvantaged incumbent always suffers from loss in its real option value of investment since it tends to act more aggressively in competing for the patent. On the other hand, the real option value of investment of the informationally advantaged entrant may be undermined or enhanced. The incumbent’s aggressive response under information asymmetry may lead to reversal of winner in the patent race. We also examine how information asymmetry may affect the occurrence of sleeping patent and the corresponding expected duration between the two stages of patenting and product commercialization.     

Optical label switching of DRZ/DPSK orthogonal signal generated by photonic-crystal fiber

We demonstrate orthogonal label switching by using a dark-return-to-zero (DRZ) payload and differential phase-shift keying (DPSK) label generated by a dispersion-flattened photonic-crystal fiber. The high extinction ratio of both the payload and label improves the receiver margin. The DRZ payload introduces little cross talk to the DPSK label due to the RZ-like output of the demodulated DPSK. Simulations are performed to study the eye-closure penalty of the payload and label at different DRZ pulse widths. We compare the DRZ/DPSK with the RZ and DPSK signals numerically at the same data rate and show that the DRZ/DPSK has a strong tolerance to the polarization-mode dispersion. The DRZ/DPSK has a more compact spectrum suitable for the strong filtering requirements in WDM systems.     

A new cross-linking route via the unusual collision kinematics of hyperthermal protons in unsaturated hydrocarbons: the case of poly(trans-isoprene)

The bombardment of a approximately 18 nm film of poly(trans-isoprene) molecules (approximately 300,000 carbon atoms per molecule) with a mass-separated proton beam at 10 eV has been shown to induce highly efficient cross-linking of several macromolecules per incident proton. In this new method using physical means to conduct synthetic chemistry, the hyperthermal protons preferentially cleave C-H bonds because of their unusual kinematics in hydrocarbons, and the carbon radicals thus created initiate a polymerization chain reaction of the isoprene C[double bond, length as m-dash]C bonds. The method produces ultrathin polymeric films via cross-linking with a dry process having high chemical selectivity and reactivity but requiring no thermal cost and no chemical additives, conditions that are commonly required in the fabrication of microelectronics and photonics.     

Femtosecond time- and wavelength-resolved fluorescence and absorption spectroscopic study of the excited states of adenosine and an adenine oligomer

By employing broadband femtosecond Kerr-gated time-resolved fluorescence (KTRF) and transient absorption (TA) techniques, we report the first (to our knowledge) femtosecond combined time- and wavelength-resolved study on an ultraviolet-excited nucleoside and a single-stranded oligonucleotide (namely adenosine (Ado) and single-stranded adenine oligomer (dA)(20)) in aqueous solution. With the advantages of the ultrafast time resolution, the broad spectral and temporal probe window, and a high sensitivity, our KTRF and TA results enable the real time monitoring and spectral characterization of the excited-state relaxation processes of the Ado nucleoside and (dA)(20) oligonucleotide investigated. The temporal evolution of the 267 nm excited Ado KTRF spectra indicates there are two emitting components with lifetimes of approximately 0.13 ps and approximately 0.45 ps associated with the L(a) and L(b) pipi* excited states, respectively. These Ado results reveal no obvious evidence for the involvement of the npi* state along the irradiative internal conversion pathway. A distinct mechanism involving only the two pipi* states has been proposed for the ultrafast Ado deactivation dynamics in aqueous solution. The time dependence of the 267 nm excited (dA)(20) KTRF and TA spectra reveals temporal evolution from an ultrafast "A-like" state (with a approximately 0.39 ps decay time) to a relatively long-lived E(1) "excimer" (approximately 4.3 ps decay time) and an E(2) "excimer-like" (approximately 182 ps decay time) state. The "A-like" state has a spectral character closely resembling the excited state of Ado. Comparison of the spectral evolution between the results for Ado and (dA)(20) provides unequivocal evidence for the local excitation character of the initially photoexcited (dA)(20). The rapid transformation of the locally excited (dA)(20) component into the delocalized E(1) "excimer" state which then further evolves into the E(2) "excimer-like" state indicates that base stacking has a high ability to modify the excited-state deactivation pathway. This modification appears to occur by suppressing the internal conversion pathway of an individually excited base component where the stacking interaction mediates efficient interbase energy transfer and promotes formation of the collective excited states. This feature of the local excitation that is subsequently followed by rapid energy delocalization into nearby bases may occur in many base multimer systems. Our results provide an important new contribution to better understanding DNA photophysics.