Bipyridine‐Modulated Palladium‐Catalyzed Oxidative Heck‐Type Reactions of Arylboronic Acids with Olefins

We have demonstrated that 4,4′‐dimethyl 2,2′‐bipyridine as ligand for Pd(II) catalysts was very efficient for oxidative Heck‐type coupling reaction of arylboronic acids with olefins in DMA or CH₃CN under atm air at 80 °C. The presence of chelated bipyridine ligand isindispensable to achieve high reaction yields and to suppress the formation of biphenyl as homocoupled byproduct.     

Real Time Electrochemical Monitoring of DNA/PNA Dissociation by Melting Curve Analysis

An immobilization‐free electrochemical method is reported for real‐time monitoring of the DNA hybrid dissociation between a ferrocene labeled peptide nucleic acid (PNA) and a fully‐complementary or single‐base‐mismatched DNA. This method takes advantages of electrostatic charge characteristics and interactions among the neutrally charged PNA, the negatively charged DNA and the negatively charged electrode surface made of indium tin oxide (ITO). When a ferrocene labeled PNA (Fc‐PNA) sequence is hybridized to a complementary DNA strand, electrostatic repulsion between the negatively charged PNA/DNA hybrid and the negative ITO surface retards the diffusion of the electroactive Fc to the electrode, resulting in a much reduced electrochemical signal. On the other hand, when the Fc‐PNA is dissociated from the hybrid at elevated temperatures, the neutrally charged Fc‐PNA easily diffuses to the electrode with an enhanced electrochemical signal. Therefore, an electrochemical melting curve of the Fc‐PNA/DNA hybrid can be obtained by measuring the Fc signal with the increasing temperature. This strategy allows monitoring of the dissociation of the DNA hybrid in real time, which might lead to a simple detection method for single nucleotide polymorphism (SNP) analysis.     

Electrochemical real-time polymerase chain reaction

In this work, we report the first electrochemistry-based real-time polymerase chain reaction technique for sequence-specific nucleic acid detection. This new technique builds upon the advantages of the well-established fluorescence-based counterpart, such as short assay time (simultaneous target DNA amplification and detection). In addition, this electrochemical approach could employ simple and miniaturizable instrumentation compared to the bulky and expensive optics required in the fluorescence-based schemes. We have demonstrated a proof-of-concept experiment showing that the utilization of solid-phase extension of the electrode surface-immobilized capture probe with Fc-dUTP during PCR resulted in the accumulation of the redox marker on the transducer surface. This new technique can be applied to a microfabricated PCR electrochemical device for point-of-care diagnostics as well as on-site environmental monitoring and biowarfare agent detection.     

DNA-based bioanalytical microsystems for handheld device applications

This article reviews and highlights the current development of DNA-based bioanalytical microsystems for point-of-care diagnostics and on-site monitoring of food and water. Recent progresses in the miniaturization of various biological processing steps for the sample preparation, DNA amplification (polymerase chain reaction), and product detection are delineated in detail. Product detection approaches utilizing “portable” detection signals and electrochemistry-based methods are emphasized in this work. The strategies and challenges for the integration of individual processing module on the same chip are discussed.     

The geometric pattern of a pillared substrate influences the cell-process distribution and shapes of fibroblasts

Fibroblasts alter their shape, direction of movement, cytoskeleton arrangement, and focal contact when placed upon square array pillars. We prepared pillars of 1 μm diameter, separated by 3 μm, and having 1, 5, and 10 μm heights using substrates displaying identical surface chemistry. When cells seeded initially onto the tops of the pillars, fibroblasts subsequently were immobilized in situ by several pillars that visibly protruded through, but did not pierce, the cell bodies. The cytoplasma then migrated outward with long straight lamella along the interval of the pillars and formed several discrete attachment zones at their side walls – the value of their form index (FI) was as high as 35 – which altered the cellular shape entirely. Most of the cells interacted with the pillar substrate by spreading preferentially in a particular direction, but some of them had the ability to undergo coincident two-direction (x and y) migration; right-angle turn orientations led to the growth of dramatic cellular morphologies. Interestingly, this fibroblast's behavior variation was gradually in proportion to the pillar height of substrate. Our results confirm that cellular migration and cellular shape are both strongly affected by the geometry of the growth microenvironment.     

Synthesis and Characterization of Reversible Chemosensory Polymers: Modulation of Sensitivity through the Attachment of Novel Imidazole Pendants

Three novel electron donor–acceptor conjugated polymers ( P1 – P3 ) bearing various imidazole pendants have been synthesized. Their excellent photophysical and electrochemical properties make them suitable transduction materials for chemosensing applications. Indeed, polymers P1 – P3 have been found to show remarkable sensing capabilities towards H⁺ and Fe²⁺ in semi‐aqueous solutions. Upon titration with H⁺, polymers P1 and P2 showed hypsochromic shifts of their absorptions and photoluminescence (PL) maxima with enhanced fluorescence intensities. However, P3 showed diminished absorption and fluorescence intensities under similar conditions due to static quenching. The anomalous behavior of P3 compared with P1 and P2 has been clarified in terms of electronic distributions through computational analysis. Furthermore, P3 (K_SV=1.03×10⁷) showed a superior sensing ability towards Fe²⁺ compared with P1 (K_SV=2.01×10⁶) and P2 (K_SV=4.12×10⁶) due to its improved molecular wire effect. Correspondingly, the fluorescence lifetime of P3 was greatly decreased (almost 11‐fold) compared to those of polymers P1 (4.6‐fold) and P2 (6.2‐fold) in the presence of Fe²⁺. By means of a fluorescence on‐off‐on approach, chemosensing reversibilities in protonation–deprotonation and metallation–demetallation have been achieved by employing triethylamine (TEA) and the disodium salt of ethylenediaminetetraacetic acid (Na₂‐EDTA)/phenanthroline, respectively, as suitable counter ligands. ¹H NMR titrations have revealed the unique behavior of P3 compared with P1 and P2 . To the best of our knowledge, there have been no previous reports of Fe²⁺ sensors based on single imidazole receptors conjugated to a main‐chain polymer showing such a diverse sensitivity pattern depending on their attached substituents.     

Synthesis and electroluminescence properties of fluorene containing arylamine oligomer

We synthesized a blue fluorescent fluorene containing arylamine oligomer, bis(9,9,9′,9′‐tetra‐n‐octyl‐2,2′‐difluorenyl‐7‐yl)phenylamine (DFPA), and investigated its electroluminescence (EL) properties. Organic EL devices with a structure of glass/indium‐tin oxide/acid‐doped poly(thiophene) derivative/DFPA/aluminum complex (BAlq)/cesium‐doped macrocyclic compound/Al were fabricated. The device exhibited blue emission, peaking at 432 nm, from the DFPA layer. The maximum luminance of 1800 cd/m² and an external quantum efficiency of 1.5% were observed. Copyright © 2004 John Wiley & Sons, Ltd.     

An Efficient Method for the Preparation of Nitriles via the Dehydration of Aldoximes with Phthalic Anhydride

A new and highly efficient method for the conversion of aldoximes to nitriles was established. By fusing with phthalic anhydride, aldoximes were efficiently and smoothly converted into nitriles, in high yields (over 85%) and in a short time (within 5 minutes). The mixture of phthalic anhydride, a cyclic anhydride, and aldoximes in fusing state set up an ideal transition state for a selective [3.3]‐sigmatropic rearrangement of the acylated aldoximes to nitriles.     

Asymptotic behavior of the solutions of an integrodifferential system

Summary We consider the system(L): , t ⩾ p, y(t)=f(t), t⩽0, where y is an n-vector and each A_i, B(t) are n × n matrices. System(L) generates a semigroup by means of T_tf(s)=y (t+s, f), f(s) ∈ BC_l(− ∞, 0]. Under some hypotheses concerning the roots ofdet where is the Laplace transform of B(t), the asymptotic behavior of y(t) is discussed. Two typical results are: Theorem 3.1: suppose ∥B(t)∥ ɛ L₁[0, ∞), thendet forRe λ>0 iff for every ɛ>0 there is an M_ɛ>0 such that ∥T_tf∥_l ⩽ ⩽ M_ɛ exp [ɛt]∥f∥_l for t ⩾ 0. Corollary 3.1.1: suppose exp [at]B(t) ∈ ∈ L₁[0, ∞) for some a>0 anddet forRe λ>−a. Then the solution of(L) is exponentially asymptotically stable. Entrata in Redazione il 21 marzo 1975. The author is grateful to ProfessorC. Corduneanu for suggesting this problem and for many helpful discussions during the preparation of the paper.     

Tetrazine Assists Reduction of Water by Phosphines: Application in the Mitsunobu Reaction

Reaction of 3,6‐disubstituted‐1,2,4,5‐tetrazines with water and PEt₃ forms the corresponding 1,4‐dihydrotetrazine and OPEt₃. Thus PEt₃, as a stoichiometric reductant, reduces water, and the resulting two reducing equivalents serve to doubly hydrogenate the tetrazine. A variety of possible initial interactions between electron‐deficient tetrazine and electron‐rich PR₃, including a charge transfer complex, were evaluated by density functional calculations which revealed that the energy of all these make them spectroscopically undetectable at equilibrium, but one of these is nevertheless suggested as the intermediate in the observed redox reaction. The relationship of this to the Mitsunobu reaction, which absorbs the components of water evolved in the conversion of alcohol and carboxylic acid to ester, with desirable inversion at the alcohol carbon, is discussed. This enables a modified Mitsunobu reaction, with tetrazine replacing EtO₂CN=NCO₂Et (DEAD), which has the advantage that dihydrotetrazine can be recycled to tetrazine by oxidation with O₂, something impossible with the hydrogenated DEAD. For this tetrazine version, a betaine‐like intermediate is undetectable, but its protonated form is characterized, including by X‐ray structure and NMR spectroscopy.