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Among various polycyclic aromatic hydrocarbons, C 6 -C 5 -C 6 -C 7 -C 6 fused pentacyclic aromatic hydrocarbons have the unique potential to adopt quinonoid, zwitterion, singlet, or triplet biradical electronic configurations. Two such hybrid structures between pentacene and azulene were synthesized and their ground state electronic configuration was deduced from the reactivity patterns they exhibit respectively. Compound 6, where the radicaloid carbons are linked through a para-phenylene, forms a head-to-head dimer like a singlet biradical. In contrast, isomer 7 , where the para-linkage was switched to meta, reacts readily with oxygen which resembles the reactivity of a triplet state. The oxidized intermediate(s) then undergoes rearrangement to furnish the C 6 -C 5 -C 6 -C 6 -C 6 ring contraction product 13 . Cation 14 , the protonated form of 7 , was synthesized, which implies 7 also reacts like a zwitterion. It was revealed the oxidative rearrangement takes place even with mesityl dibenzotropylium cation despite its perceived aromaticity. DFT calculations confirm the most stable forms of 6 and 7 are singlet and triplet diradical, which is consistent with the observed reactivity of respective molecules.

The central dogma in constructing organic electron acceptors is to attach electron-withdrawing groups to polycyclic aromatic hydrocarbons. Yet, the full potentials of many organic acceptors were never realized due to synthetic obstacles. By combining the Wittig-Knoevenagel benzannulation, the Pd(0)-catalyzed cyanation, and nucleophilic addition/oxidation cyanation, six polynitrile Z-shaped perylene diimide were synthesized. These stable and soluble electron acceptors possess LUMO energy levels comparable with those of benchmark compounds. Electrochemical investigation reveals that each additional nitrile group reduces the LUMO energy by 0.2 eV.

Attaching electron-withdrawing nitrile groups to π-conjugated systems is an effective approach toward electron acceptors. By combining various cyanation methodologies, perylene and anthracene polynitriles with up to eight nitrile substituents on one aromatic scaffold were synthesized. This strategy produces stable electron acceptors with lowest unoccupied molecular orbital (LUMO) levels comparable to benchmark acceptors. A very stable octanitrile anion was also produced serendipitously. Reactivity patterns of these acceptors were rationalized by density functional theory (DFT) calculation.

Dicyclopenta[ghi,pqr]perylene (DCPP) is a substructural fragment on the surface of C70 yet not on C60. Unlike its intensely investigated buckybowl cousins, corannulene and sumanene, DCPP is largely...

2,3,9,10-Substituted pentacene tetraesters and pentacene diester-dinitriles were synthesized. These pentacene derivatives underwent an unusual solid state [4 + 4] thermal dimerization with good efficiency and complete stereoselectivity. This observation indicates this series of pentacene derivatives adopt π-π stacking geometry with large mutual overlap in solid state. This notion was confirmed by molecualr dynamic simulation.

Pentacene is one of the most versatile organic semiconductors. New synthetic strategies to construct the pentacene skeleton are imperative to produce pentacene derivatives with appropriate solubility, stability, and optoelectronic properties for various applications. This paper describes a template-directed approach to pentacene derivatives. In the retrosynthesis, the acene skeleton is viewed as a laddered double strand polyene instead of the more intuitive linearly fused hexagons. Based on this vision, the template strand of polyene is constructed with Wittig olefination, whereas the second strand is accomplished with Knoevenagel condensation to produce pentacene and tetracene derivatives. The synthetic scheme is flexible enough to generate an array of acene derivatives with substitution patterns that were hitherto difficult to access. Amphiphilic pentacene and tetracene derivatives were also synthesized by the template strategy. One pentacene based amphiphilic rod-coil molecule undergoes self-assembly to form helical wire structures that were visualized with TEM.

Zeta potentials of several polar protic (water, ethylene glycol, formamide) as well as polar aprotic (dimethyl sulfoxide) liquids were measured in contact with three non-polar surfaces using closed-cell electro-osmosis. The test surfaces were chemisorbed monolayers of alkyl siloxanes, fluoroalkyl siloxanes and polydimethylsiloxanes (PDMS) grafted on glass slides. All these liquids exhibited substantial electrokinetics in contact with the non-polar surfaces with these observations: the electrokinetic effect on the fluorocarbon-coated surface is the strongest; and on a PDMS grafted surface, the effect is the weakest. Even though these hygroscopic liquids contain small amounts of water, the current models of charging based on the adsorption of hydroxide ions at the interface or the dissociation of preexisting functionalities (e.g., silanol groups) appear to be insufficient to account for the various facets of the experimental observations. The results illustrate how ubiquitous the phenomenon of electro-kinetics is with polar liquids contacting such apparently passive non-polar surfaces. We hope that these results will inspire further experimental and theoretical studies in this important area of research that has potential practical implications.

Z-shape (1,2,7,8-tetrasubstituted) perylene derivatives are novel chromophores with great potential in various applications. Yet, the synthetic entry into this class of molecules is hitherto quite limited. In this communication, the synthesis of a series of Z-shape perylene derivatives via a double Wittig-Knoevenagel benzannulation protocol is reported. Preliminary photophysical and electrochemical studies indicate that the frontier orbital energy levels of these new perylene systems are modulated by electronic, regiochemical, and conformational effects.

Background Anti-Mullerian hormone (AMH), which is secreted by preantral and small antral follicles, has been found to be a valuable marker of ovarian reserve. The purpose of this study was to determine age-related changes in AMH levels that occur in Taiwanese women and to determine whether measuring AMH is a highly sensitive and specific tool for diagnosing polycystic ovarian syndrome (PCOS) in Taiwanese women. Methods A group of 59 healthy, fertile, regularly cycling women, a second group of seven patients with premature ovarian failure or menopause, and a third group of 45 PCOS patients were enrolled. Serum AMH concentrations were measured using an enzyme-linked immunosorbent assay. Results AMH levels in healthy fertile women with regular menstrual cycles demonstrated an age-related decline, with a rapid drop between 30–40 years of age that was followed by a slow decrease after 40 years old. All patients with premature ovarian failure and menopause had undetectable AMH levels. AMH levels in PCOS patients were found to be significantly higher than those measured in healthy fertile controls. The sensitivity and specificity of AMH for detecting PCOS in patients aged 29–38 years were calculated to be 74% and 79%, respectively, using an AMH cut-off value of 3.5 ng/mL. Conclusion Here, we provide data on Taiwanese women that demonstrate age-related decline in AMH levels and establish an AMH-based method for detecting PCOS, which may be used as reference data for future AMH studies on Taiwanese women.

We have previously shown that helioxanthin can suppress human hepatitis B virus gene expression. A series of helioxanthin analogues were synthesized and evaluated for their anti-hepatitis B virus activity. Modifications at the lactone rings and methylenedioxy unit of helioxanthin can modulate the antiviral activity. Among them, compound 32 is the most effective anti-HBV agent. Compound 32 can suppress the secretion of viral surface antigen and e antigen in HepA2 cells with EC(50) values of 0.06 and 0.14 microM, respectively. Compound 32 not only inhibited HBV DNA with wild-type and lamivudine-resistant strain but also suppressed HBV mRNA, core protein and viral promoters. In this study, a full account of the preparation, structure-activity relationships of helioxanthin analogues, and the possible mechanism of anti-HBV activity of this class of compounds are presented. This type of compounds possesses unique mode of action differing from existing therapeutic drugs. They are potentially new anti-HBV agents.

An elevated level of macrophage inflammatory protein-1beta (MIP-1beta) induced by IL-1beta has been correlated with chronic hepatic inflammatory disease. However, molecular mechanism of IL-1beta-induced MIP-1beta expression in hepatic cells is obscure. Previously, we reported the mechanism of the anti-hepatitis B virus (HBV) activity of helioxanthin (HE-145). Here, we demonstrated that HE-145 inhibited IL-1beta-induced MIP-1beta expression in a dose-dependent manner in Huh7 cells. To understand the mode of action of HE-145, we first examined how IL-1beta induced MIP-1beta expression at the molecular level. Using selective inhibitors, we found that JNK and p38 pathways participated in IL-1beta-induced MIP-1beta expression. HE-145 specifically suppressed IL-1beta-induced c-jun mRNA and protein expression and prevented c-jun-mediated AP-1 DNA-binding activity, whereas it had no effect on IL-1beta-induced activation of JNK, p38 and ATF2. Further studies indicated that HE-145 may downregulate c-jun mRNA expression directly at transcriptional level without requirement of de novo protein synthesis. Mutational analysis and supershift assays indicated that IL-1beta stimulated c-jun and CREB1 binding to the essential AP-1/CRE site of the MIP-1beta promoter. The inhibitory effect of HE-145 on IL-1beta-induced MIP-1beta promoter activity was completely reversed by overexpressing c-jun. Electrophoretic mobility shift assay (EMSA) and chromatin immunoprecipitation (ChIP) assay consistently revealed that HE-145 reduced c-jun binding to the AP-1/CRE site in vitro and in vivo. Our results established a major role for c-jun in IL-1beta-induced MIP-1beta expression in hepatic cells. The reduction in IL-1beta-induced c-jun expression and subsequent binding of the c-jun/CREB1 complex to AP-1/CRE site mainly contributed to the inhibitory action of HE-145 on IL-1beta-induced MIP-1beta production.

Ladder-type oligophenylene derivatives are important compounds for light-emitting devices. However, the closely related ladder-type oligonaphthalene derivatives have received little attention due to the lack of synthetic accessibility. We hereby report the syntheses of these novel conjugated systems by means of an intramolecular cationic cyclization protocol. Utilizing a one-pot-multiple-component reaction, the acyclic precursors to these ladder-type oligomers up to pentamer can be synthesized from small fragments in just two or three steps. Photophysical and electrochemical studies revealed that the electron delocalization in these compounds is considerably enhanced relative to that found in the regular unplanarized oligonaphthalene derivatives. However, such an effect is much weaker than that found in fully planar rylene derivatives.

A non-nucleosidic compound, Helioxanthin (HE-145), was found to suppress HBV gene expression and replication in HCC cells. To understand the molecular mode of action of HE-145 on HBV gene expression, the effects of HE-145 on four viral promoter activities using luciferase as a reporter were examined. It was found that HE-145 selectively suppresses surface antigen promoter II (SPII) and core promoter (CP) but has no effect on surface antigen promoter I (SPI) or promoter for X gene (Xp). The suppressive effects of HE-145 on either SPII or CP activity is liver-specific, since no suppressive activity of HE-145 was observed when CP or SPII promoter activity was assayed in non-liver cells such as HeLa or 293T. To examine the mode of action of HE-145, EMSA analysis revealed that HE-145 decreased the DNA-binding activity of nuclear extract of HepA2 cells to specific cis element of HBV promoter for core antigen, including peroxisome proliferator-activated receptors (PPARs), PPARs binding site (PPRE), alpha-fetoprotein transcription factor (FTF), and Sp1. Ectopic expression of PPAR gamma or HNF4 alpha partially reversed the HE-145-mediated suppression of HBV RNA. Therefore, HE-145 may represent a novel class of anti-HBV agents which selectively modulate transcriptional machinery of human liver cells to suppress HBV gene expression and replication.

A facile synthesis of tetracene sulfoxides and sulfones based on o-diallene annulation initiated cascade cyclization was developed. The photophysical behavior of these tetracene derivatives can be generally rationalized by the presence of electron-withdrawing sulfoxides and sulfones at the 5-position.

This brief addresses the design of a decision feedback equalizer (DFE) for gigabit throughput rate. It is well known that the feedback loop in a DFE limits an upper bound of the achievable speed. For a L-tap feedbackward filter (FBF) and M-pulse amplitude modulation, Parhi (1991) and Kasturia and Winters (1991) reformulated the FBF as a (M)L-to-1 multiplexer. Due to the reformulation, the overhead of extra adders and extra multiplexers are as large as (M)L. The required hardware overhead should be more severe when the DFE is implemented in parallel. In this brief, we propose two new approaches to implement the DFE when gigabit throughput rate is desired. The first approach is partial pre-computation scheme, which can trade-off between hardware complexity and computational speed. The second approach is two-stage pre-computation scheme, which can be applied to higher speed applications. In the later case, we can reduce the hardware overhead to about 2(M)(-L/2) times of [1], [2], and the iteration bound is (log2W+2)/(L/2+1)+(log2M) multiplexer-delays, where W is the wordlength of weight coefficient of a FBF. We demonstrate the proposed architectures by apply it to the 10 Gbase-LX4 optical communication systems

ROMP of 2 with Grubbs I catalyst in CH 2 Cl 2 furnished the corresponding polymer 5 which was characterized by spectroscopic means, particularly, MAS 13 NMR. The EXAFS of 5 results were compared with those of the monomeric starting material 2 and the X-ray data of 2 .

Photocrosslinkable polymers are clean and convenient materials for the biomedical uses. Chitosan, which owns excellent biocompatible and antimicrobial properties, is one of the choices while it is introduced with photosensitive functional groups. In this study, chitosan was N-phthaloylated to react with acryloyl chloride in the organic solvent homogeneously and the result has been verified by the solubility test. Fourier transformed infrared spectrometry and nuclear magnetic resonance spectrometer analysis indicated that the modification with the attachment of the photosensitive functional group, the acryloyl group, onto chitosan and poly(ethylene glycol) (PEG) was feasible. The differential scanning calorimetry analysis further indicated that the melting points of the N-phathaloylated chitosan were decreased as compared with the untreated chitosan control. Then photocrosslinkable chitosan derivative (CH-PAA) was photocopolymerized with PEG diacrylate (PEGA) under UV irradiation. The adhesion strength characterization and swelling capacity evaluation for this photocopolymer have shown obvious raises of the adhesiveness and water-adsorption abilities as compared with the photopolymer of CH-PAA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1794–1801, 2006

Endoscopic palliation for the obstructive jaundice caused by biliary or pancreatic malignant tumors is a commonly used medical treatment. However, plastic biliary stents are occluded by sludge deposition caused by bacterial adhesion in 3–5 months. Chitosan, which has both good biocompatibility and antimicrobial capability, was used to modify the inner surface of polyethylene (PE) tubing in this study. Chitosan was deposited onto the inner surface of oxidized PE tubing with the methanol precipitation technique. Attenuated total reflection/Fourier transform infrared and electron spectroscopy for chemical analysis indicated that the chitosan coating was feasible. Contact-angle measurements revealed that the surface hydrophilicity of the PE tubing increased with the chitosan coating. Morphological analysis with scanning electron microscopy showed that the PE surface became rougher and exhibited micropores after the chitosan coating. The adhesion of living Escherichia coli to chitosan-coated PE stents, characterized by the spreading plate method and scanning electron microscopy analysis, was more significant than that to unmodified stents after a 24-h phosphate-buffered saline or bile perfusion test. This finding may be attributed to the rougher and slightly positively charged surface of chitosan-coated PE tubing and to the CH3 hydrophobic functional groups in the chitosan structure. Because of its good biocompatibility, chitosan coated on the surface of PE can still be used for biliary stent applications with further chemical modification, such as sulfonation and quaternization, to increase its antimicrobial ability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 893–902, 2005

Under acidic condition, anthryl methyl ethers behave as anthryl cation synthons and undergo ipso-substitution to produce anthryl sulfides. These compounds are hard to access with currently available methodology and they have great potentials as organic electronic materials.

The technique of {orthogonal frequency division multiplexing (OFDM)} is famous for its robustness against frequency-selective fading channel. This technique has been widely used in many wired and wireless communication systems. In general, the {fast Fourier transform (FFT)} and {inverse FFT (IFFT)} operations are used as the modulation/demodulation kernel in the OFDM systems, and the sizes of FFT/IFFT operations are varied in different applications of OFDM systems. In this paper, we design and implement a variable-length prototype FFT/IFFT processor to cover different specifications of OFDM applications. The cached-memory FFT architecture is our suggested VLSI system architecture to design the prototype FFT/IFFT processor for the consideration of low-power consumption. We also implement the twiddle factor butterfly {processing element (PE)} based on the {{coordinate} rotation digital computer (CORDIC)} algorithm, which avoids the use of conventional multiplication-and-accumulation unit, but evaluates the trigonometric functions using only add-and-shift operations. Finally, we implement a variable-length prototype FFT/IFFT processor with TSMC 0.35 μm 1P4M CMOS technology. The simulations results show that the chip can perform (64-2048)-point FFT/IFFT operations up to 80 MHz operating frequency which can meet the speed requirement of most OFDM standards such as WLAN, ADSL, VDSL (256∼2K), DAB, and 2K-mode DVB.

The coordinate rotational digital computer (CORDIC) algorithm is a well-known iterative method for the computation of vector rotation. For applications that require forward rotation (or vector rotation) only, the angle recoding (AR) technique provides a relaxed approach to speed up the operation of the CORDIC algorithm. In this paper, we further apply the concept of AR technique to extend the elementary angle set in the microrotation phase. This technique is called the extended elementary-angle set (EEAS) scheme. The proposed EEAS scheme provides a more flexible way of decomposing the target rotation angle in CORDIC operation, and its quantization error performance is better than the AR technique. Meanwhile, to solve the optimization problem encountered in the EEAS scheme, we also proposed a novel search algorithm, called the trellis-based searching (TBS) algorithm. Compared with the greedy algorithm used in the conventional AR technique, the proposed TBS algorithm yields apparent signal-to-quantization-noise ratio (SQNR) improvement. Moreover, in the scaling phase of the EEAS-based CORDIC algorithm, we suggest a novel scaling operation, called Extended Type-II (ET-II) scaling operation. The ET-II scaling operation applies the same design concepts as the EEAS scheme. It results in much smaller quantization error than conventional Type-I scaling operation in the numerical approximation of scaling factor. By combining the aforementioned new schemes, the proposed EEAS-based CORDIC algorithm can improve the overall SQNR performance by up to 25 dB compared with previous works. Also, given the same target SQNR performance, we require only about 66% iteration number in the iterative CORDIC structure, or use 66% hardware complexity in the parallel CORDIC structure compared with conventional AR technique. Hence, high-performance/low-latency CORDIC very large-scale integration architectures can be achieved without degrading the SQNR performance.

The pi-stacking interaction between shape-persistent cyclophanes works cooperatively with multiple hydrogen bonding sites to form cyclophane dimers. These findings considerably broaden the applicability of pi-stacking interactions as a driving force in self-assembly chemistry. A gel formation effect was also noticed in one of the cyclophanes.

Helioxanthin and analogues have been demonstrated to suppress gene expression of human hepatitis B virus. In the continuous attempt to optimize antiviral activity, various structural motifs were grafted on the helioxanthin scaffold. Many such analogues were synthesized and evaluated for their anti-hepatitis B virus activity. Structure–activity relationships of these helioxanthin derivatives are also discussed. Among these new compounds, 15 exhibits the highest activity against HBV (EC50 = 0.06 μM). This compound can suppress viral surface antigen and DNA expression. Furthermore, viral RNA is also diminished while the core promoter is deactivated upon treatment by 15. A plausible working mechanism is postulated. Our results establish helioxanthin lignans as potent anti-HBV agents with unique mode of action. Since their antiviral mechanism is distinct from current nucleoside/nucleotide drugs, helioxanthin lignans constitute a potentially new class of anti-HBV agents for combination therapy.

Previously, we developed an iterative elongation methodology to synthesize acene esters, nitriles, and imides. The strategy uses the concept of bidirectional synthesis, and we can now make a series of electron deficient anthracene, tetracene, and pentacene derivatives via the bidirectional iterative elongation protocol. Central units, used to initiate the bidirectional elongation, were synthesized by employing a double anionic Fries rearrangement as the key step. The photophysical and electrochemical properties of these novel electron acceptors are investigated and interpreted based on the electron withdrawing power of the substitutions. An excited state charge transfer was proposed for one compound to account for its peculiar fluorescent behavior.

Starting from aromatic ortho-dialdehydes, we devised a homo-elongation protocol that combines a Wittig olefination and subsequent intramolecular Knoevenagel condensation to produce acene diesters and dinitriles.

A method is introduced for determining the zeta potential of planar surfaces by combining electroosmosis and capillarity. In this method, an electric field is applied across the channel, which is filled with aqueous solution seeded with fluorescent tracer particles. Some excess liquid is applied on both ends of the channel, which bulges out and modulates the capillary force across the channel by adjusting its curvature. While the velocity profile in the channel approaches steady state, a balance of the electroosmotic stress and Laplace pressure difference is achieved across the channel. However, as soon as the electric field is turned off, a Poiseuille flow develops in the channel due to the difference in the curvatures of the liquid bulges. We show that the measurement of the centerline velocity of the liquid inside the channel is enough to deduce the zeta potential of the surface. Utilizing this technique, the zeta potential of a hydrophobic glass surface (silanized by n-hexadecyltrichlorosilane, HC-16) has been measured to be -52.2 +/- 7.7 mV in distilled deionized water, which is in close agreement with the literature values. This technique has also been used to estimate the zeta potential of the HC-16 surface (zeta w(HC-16)), in the presence of the aqueous solutions of polyoxyethylene (23) lauryl ether (Brij 35). The zeta potential here at first becomes more negative than that in pure water, it stays flat for a while, and then it continues to become less negative as the concentration of the surfactant increases above the critical micelle concentration (CMC). This effect, where changes take place beyond the CMC but not below it, leads to a complementary Gibbs plot, where all the changes occur below the CMC but not above it. It is conjectured that the scavenging of hydroxyl ions by the Brij 35 micelles may be responsible for the observed effect.

This paper addresses the design of a DFE for Gbits throughput rate in each communication path of a 10G base LX4 Ethernet system. It is well-known that the feedback loop within a DFE limits an upper bound of the achievable speed. For an L-tap feed-backward filter (FBF) with word-length W and M-PAM signal, previous authors have reformulated the FBF as a (log/sub 2/M)/sup L/- to-1 multiplexer. However, the overhead of extra adders and extra multiplexers are as large as (log/sub 2/M)/sup L/. The required hardware overhead would be more severe when the DFE is designed in parallel. In this paper, we propose two new approaches to implement the DFE when Gbit speed is required. The first approach is partial pre-computation, which can trade-off between hardware complexity and computation speed. The second approach is two-stage pre-computation, which can be applied to higher speed applications. We can reduce the hardware overhead to about 2(log/sub 2/M)/sup (-L/2)/ times that of the previous authors, and the iteration bound is 2(log/sub 2/W+2)/L+(log/sub 2/M) multiplexer-delays.

Most cost-effective DFE implementations suffer from the phenomenon of error propagation, which degrades its bit error rate (BER) performance. To solve this problem, we proposes a soft-threshold-based multi-layer DFE (STM-DFE) technique to reduce the BER. It costs very low hardware overhead compared to the conventional DFE. The key idea is to define a reliable/unreliable region in the DFE algorithm. When the output of the equalizer is in the unreliable region, the STM-DFE does not make a decision on the current symbol, but outputs a log-likelihood ratio to the next symbol. This process continues until the decision becomes reliable, or reaches the maximum stage number. The optimal threshold value between the reliable and unreliable region is analyzed in close-form. Simulation results show that the proposed scheme can efficiently reduce the burst error length (BEL) as well as the BER.

Selective synthesis of anthracene ethers was achieved under mild conditions via an acid-catalyzed ether-ether exchange reaction and its scope and limitations, as well as its potential in synthesizing anthracene-based crown ethers, tested.