Synthesis of large ring 3,4-alkylenedioxythiophenes (ADOT) derivatives via Mitsunobu reaction

Poly(3,4-ethylenedioxythiophene) (PEDOT) stands out for its optimized conductivity, stability, and high degree of transparency which has led to its successful commercialization. These excellent properties of PEDOT are mostly ascribed to the alkylenedioxy bridge across the 3- and 4-positions, and thus much effort has been dedicated to synthesizing 3,4-ethylenedioxythiophene (EDOT) analogs. However, only few homologous compounds were successfully synthesized, such as 3,4-propylenedioxythiophene (PrDOT) or 3,4-(1,4-butylenedioxy)thiophene (BuDOT). In this Letter, we use Mitsunobu reaction to synthesize a series of 3,4-alkylenedioxythiophenes (ADOTs) derivatives with 8- to 16-membered rings. The eight-membered compounds were obtained in high or excellent yield. We also found that the 9- to 16-membered EDOT analogs were obtained in relatively low yield because of the competitive reaction to make dimers. Our method provides an easy way to modify ethylenedioxythiophenes (EDOTs), and these obtained ADOTs compounds are promising building blocks for the synthesis of functional π-conjugated systems used in material chemistry.     

Broadband enhancement of spontaneous emission in a photonic-plasmonic structure

We demonstrate that a broadband enhancement of spontaneous emission can be achieved within a photonic-plasmonic structure. The structure can strongly modify the spontaneous emission by exciting plasmonic modes. Because of the excited plasmonic modes, an enhancement up to 30 times is observed, leading to a 4 times broader emission spectrum. The reflectance measurement and the finite-difference time-domain simulation are carried out to support these results.     

Charge dynamics in solar cells with a blend of π-conjugated polymer-fullerene studied by transient photo-generated voltage

The biphasic feature of transient photo-generated voltage (TPV) is investigated in organic solar cells (OSCs) with a blend active layer of poly(3-hexylthiophene) (P3HT) and phenyl C61 butyric acid methyl ester (PCBM). The positive and negative components in biphasic TPV are explained through PCBM only and P3HT only devices. The negative and positive components are ascribed to the dipole formation at the buried interface of P3HT/indium tin oxide (ITO) and PCBM/ITO respectively. Based on these findings, two fundamental phenomena are revealed as follows: (1) interfacial modification on the buried interface inverts the negative component in biphasic TPV to a positive component, which prevents the leakage current channel in the conventional OSC structure; and (2) the solvent chosen transforms the positive component in biphasic TPV into a negative signal, which blocks the leakage current channel in the inverted OSC structure. Consequently, the study of TPV polarity provides the justification of the interaction at the buried interface. Besides, the decay of TPV is found to be bi-exponential, which can be used as a tool to estimate the degree of charge balance in OSCs.     

Evidence of two-dimensional superconductivity in the single crystalline nanohybrid of organic-bismuth cuprate

A coordination compound of HgI(2)(pyridine)(2) can be successfully intercalated into a single crystalline Bi(2)Sr(2)CaCu(2)O(y) high-T(c) superconductor through an interlayer complexation reaction between pyridine molecules and bismuth cuprate pre-intercalated with mercuric iodide. X-ray diffraction and X-ray absorption spectroscopic results clearly demonstrate that the single crystalline nature of the pristine bismuth cuprate remains unchanged even after the intercalation of organic complex as well as those of iodine and mercuric iodide. According to the angle-dependent dc magnetization measurements, the intercalation of bulky organic molecules completely blocks superconductive currents along the c-axis, whereas a superconducting transition along the in-plane direction still occurs in the organic intercalate. In the case of the iodine or mercuric iodide intercalates with smaller lattice expansions, an out-of-plane diamagnetic transition is not wholly quenched but significantly depressed by the intercalation, confirming the reduction of interlayer interaction. The present finding can provide straightforward evidence of the two-dimensionality of high temperature superconductivity in the present cuprate-based nanohybrid material.     

Biodegradable Inorganic Nanovector: Passive versus Active Tumor Targeting in siRNA Transportation

The biodegradable inorganic nanovector based on a layered double hydroxide (LDH) holds great promise for gene and drug delivery systems. However, in vivo targeted delivery of genes through LDH still remains a key challenge in the development of RNA interference therapeutics. Here, we describe in vivo and in vitro delivery system for Survivin siRNA (siSurvivin) assembled with passive LDH with a particle size of 100 nm or active LDH conjugated with a cancer overexpressing receptor targeting ligand, folic acid (LDHFA), conferring them an ability to target the tumor by either EPR‐based clathrin‐mediated or folate receptor‐mediated endocytosis. When not only transfected into KB cells but also injected into xenograft mice, LDHFA/siSurvivin induced potent gene silencing at mRNA and protein levels in vitro, and consequently achieved a 3.0‐fold higher suppression of tumor volume than LDH/siSurvivin in vivo. This anti‐tumor effect was attributed to a selectively 1.2‐fold higher accumulation of siSurvivin in tumor tissue compared with other organs. Targeting to the tumor with inorganic nanovector can guide and accelerate an evolution of next‐generation theranosis system.     

Study of 1-3 PZT fibre/epoxy composite force sensor

Lead zirconate titanate (PZT) fibres were prepared by a powder-based extrusion method. Pre-sintered PZT powder mixed with poly(acrylic acid) was spun in a spinnerette to produce fibres. The fibre of ∼400 μm diameter was used to fabricate 1-3 PZT fibre/epoxy composite discs with different volume fractions (ϕ) of PZT. Since the ceramic fibres are rather brittle, their elastic properties cannot be measured directly. In order to determine the properties of the ceramic fibres, effective properties of the fibres/epoxy 1-3 composite were measured. By using a modified series and parallel model, the properties of 1-3 composites can be calculated. Then, the elastic coefficient s_33,fibre^E, relative permittivity ε_33,fibre^T and piezoelectric strain coefficient d_33,fibre of the ceramic fibre could be found. Ring-shaped PZT fibre/epoxy materials composites with different ϕ were fabricated to be used as the sensing material in force sensor applications. The ring-shape composite with ϕ=0.5 was installed into a housing and the sensor was calibrated by different methods and its sensitivity was found to be 144 pC/N within the frequency range of 0.5–6.4 kHz which is much higher than that of a quartz force sensor with a similar structure. PACS 07.07.Df; 72.80.Tm; 77.84.Dy     

Transition metal oxides as hole-transporting materials in organic semiconductor and hybrid perovskite based solar cells

Organic polymer solar cells (OSCs) and organic-inorganic hybrid perovskite solar cells (PSCs) have achieved notable progress over the past several years. A central topic in these fields is exploring electronically efficient, stable and effective hole-transporting layer (HTL) materials. The goal is to enhance hole-collection ability, reduce charge recombination, increase built-in voltage, and hence improve the performance as well as the device stability. Transition metal oxides (TMOs) semiconductors such as NiO _x , CuO _x , CrO _x , MoO _x , WO₃, and V₂O₅, have been widely used as HTLs in OSCs. These TMOs are naturally adopted into PSC as HTLs and shows their importance. There are similarities, and also differences in applying TMOs in these two types of main solution processed solar cells. This concise review is on the recent developments of transition metal oxide HTL in OSCs and PSCs. The paper starts from the discussion of the cation valence and electronic structure of the transition metal oxide materials, followed by analyzing the structure-property relationships of these HTLs, which we attempt to give a systematic introduction about the influences of their cation valence, electronic structure, work function and film property on device performance.     

Stacking and separation of enantiomers by acetonitrile-salt mixtures in micellar electrokinetic chromatography

The feasibility of employing the "acetonitrile stacking" method in micellar electrokinetic chromatography (MEKC) for the on-line preconcentration and separation of enantiomers is demonstrated for the first time. The effects of various experimental parameters on the stacking and separation of three different pairs of optical isomers, i.e., two substituted naphthyl enantiomers and one dansylated-DL-amino acid, were examined. In particular, the effectiveness of the addition of acetonitrile and salt in the sample matrix to induce narrowing of the analyte bands was investigated in the presence of sodium cholate as the chiral surfactant micelle in the separation buffer. For example, it was found that the presence of both acetonitrile and 1% NaCl in the sample matrix (volume ratio = 2:1) led to a significant improvement of the peak height and resolution for the MEKC separation of a pair of R(-)/S(+)-1,1'-binaphthyl diyl hydrogen phosphate enantiomers when the injection sample size was relatively large (e.g., 12% capillary volume). Furthermore, the feasibility of combining salting-out solvent extraction (off-line) and acetonitrile stacking (on-line) as a novel approach for sample preconcentration in capillary electrophoresis was also demonstrated.     

Determination of catechins and catechin gallates in biological fluids by HPLC with coulometric array detection and solid phase extraction

Tea polyphenols are well known for their beneficial health effects that involve their anti-carcinogenic, anti-mutagenic, anti-pathogenic and anti-oxidative properties. The main polyphenols of green tea are favan-3-ols (catechins) and their corresponding gallate compounds, which constitute about one-third of the dry weight of tea leaves. Their main ingredients are (+)-catechin (C), (−)-epicatechin (EC), (−)-gallocatechin (GC), (−)-epigallocatechin (EGC), (−)-catechin gallate (CG), (−)-epicatechin gallate (ECG), (−)-gallocatechin gallate (GCG) and (−)-epigallocatechin gallate (EGCG). Each has slightly different biological properties. We have developed a method to simultaneously analyze all these compounds in plasma and urine. The samples were first incubated with β-d-glucuronidase and sulfatase to release the catechin residues from their corresponding conjugates for subsequent extraction by selective solid phase column, Waters Oasis HLB extraction cartridges. The extracted molecules were resolved by reversed phase HPLC and monitored by coulometric chemical detection on a CoulArray detector. All eight catechin compounds were analyzed in a single chromatogram within 25 min. For plasma and urine analyses, good linearity (>0.9950) was validated in the range 10-2000 and 10-5000 ng/ml, respectively. The coefficients of variance (CV) were less than 5%. Absolute recovery was greater than 85% and detection limit was 5 ng/ml. The chromatogram exhibited minimal interference as a result of the highly selective solid phase extraction and CoulArray detection.