Enhanced Photoluminescence of Crystalline Alq3 Micro-Rods Hybridized with Silver Nanowires.

An enhancement of the local electric field at the metal/dielectric interface of hybrid materials due to the localized surface plasmon resonance (LSPR) phenomenon plays a particularly important role in versatile research fields resulting in a distinct modification of the electrical, as well as optical, properties of the hybrid material. In this paper, we succeeded in visually confirming the LSPR phenomenon in the crystalline tris(8-hydroxyquinoline) aluminum (Alq3) micro-rod (MR) hybridized with silver (Ag) nanowire (NW) in the form of photoluminescence (PL) characteristics. Crystalline Alq3 MRs were prepared by a self-assembly method under the mixed solution of protic and aprotic polar solvents, which could be easily applied to fabricate hybrid Alq3/Ag structures. The hybridization between the crystalline Alq3 MRs and Ag NWs was confirmed by the component analysis of the selected area electronic diffraction attached to high-resolution transmission electron microscope. Nanoscale and solid state PL experiments on the hybrid Alq3/Ag structures using a lab-made laser confocal microscope exhibited a distinct enhancement of the PL intensity (approximately 26-fold), which also supported the LSPR effects between crystalline Alq3 MRs and Ag NWs.

Direct Visualization of UV-Light on Polymer Composite Films Consisting of Light Emitting Organic Micro Rods and Polydimethylsiloxane.

We experimentally demonstrate the direct visualization of ultraviolet (UV) light using flexible polymer composite films consisting of crystalline organic tris-(8-hydroxyquinoline) aluminum (Alq3) micro-rods and polydimethylsiloxane (PDMS). The representative organic mono-molecule Alq3, which is a core material of organic light-emitting diodes, was used to detect light in the invisible UV region and visualize photoluminescence (PL). Alq3 shows absorption in the UV region and light-emitting characteristics in the green region, making it an optimal material for UV visualization because of its large Stokes transition. Crystalline Alq3 micro-rods were fabricated in a deionized water solution through a sequential process of reprecipitation and self-assembly. Highly bright photoluminescence was observed on the highly crystalline Alq3 micro-rods under UV light excitation, indicating that the crystalline structures of Alq3 molecules affect the visible emission decay of excitons. The Alq3 micro-rods were manufactured as flexible polymer composite films using a PDMS solution to observe UV photodetector characteristics according to UV intensity, and it was confirmed that the intensity of the fine UV light reaching the earth's surface can be visualized by making use of this UV photodetector.

Interactions of Cinnamycin-Immobilized Gold Nanorods with Biomimetic Membranes.

The behavior of the cinnamycin immobilized on the gold nanorod(AuNR) was investigated using surface plasmon resonance(SPR). For the comparison of the immobilized cinnamycin, the study for the free cinnamycin was also conducted. The bilayer was fabricated by tethering 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanols on a gold surface to form a monolayer and then using liposomes to adsorb an outer layer on the tethered-monolayer. The liposomes were prepared with a desired ratio of 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine to 1,2-dioleoyl-sn-glycero-3-phosphocholine (0:100, 5:95, 10:90, 20:80, and 30:70). After the cinnamycin was injected on the bilayers, the specific binding between the cinnamycin and the bilayer was monitored with SPR. The inclusion of DOPE in the outer layer clearly led to the specific binding of the cinnamycin on the membranes. Specifically, the binding behavior of the immobilized was different from that of the free. For the free cinnamycin, the binding amount of cinnamycin at 10% was two times more than that at 5%. For the immobilized cinnamycin, the amounts were identical for both compositions. However, the rate was much faster for the immobilized cinnamycin at 10% than 5%, compared to that for the free at both compositions. This difference was attributed to the mean-molecular areas of the cinnamycin and DOPE, and the steric effect of the AuNR. For the effects of the heat and storage, the immobilized enzyme showed less decrease in the relative binding amount than the free one.

Photoluminescence Enhancement of Poly(3-methylthiophene) Nanowires upon Length Variable DNA Hybridization.

The use of low-dimensional inorganic or organic nanomaterials has advantages for DNA and protein recognition due to their sensitivity, accuracy, and physical size matching. In this research, poly(3-methylthiophene) (P3MT) nanowires (NWs) are electrochemically prepared with dopant followed by functionalization with probe DNA (pDNA) sequence through electrostatic interaction. Various lengths of pDNA sequences (10-, 20- and 30-mer) are conjugated to the P3MT NWs respectively followed with hybridization with their complementary target DNA (tDNA) sequences. The nanoscale photoluminescence (PL) properties of the P3MT NWs are studied throughout the whole process at solid state. In addition, the correlation between the PL enhancement and the double helix DNA with various lengths is demonstrated.

Huge Enhancement of Luminescence from a Coaxial-Like Heterostructure of Poly(3-methylthiophene) and Au.

Recently, the light-matter interaction at nanoscale has attracted great interest from physicists, chemists and material scientists, as it gives peculiar optical properties that couldn't be observed at the bulk scale. The synthesis and characterization of organic-inorganic heterostructures forming quantum dots, nanowires or nanotubes provide opportunities to understand their photophysical mechanism and to apply optoelecronic devices. Herein, we report a huge enhanced luminescence in a coaxial-like heterostructured poly (3-methylthiophene) (P3MT) with Au. We electrochemically synthesized P3MT nanowires (NWs) on a nanoporous template, and sequentially deposited Au on the surface of P3MT NWs. The diameter of heterostructured P3MT/Au NWs was about 200 nm, where the cladding-shape Au were about 10 nm. The visible range absorbance, with two new absorption peaks of P3MT/Au NWs, was significantly increased compared with that of P3MT NWs. Accordingly, the photoluminescence (PL) of a P3MT/Au NW was enormously increased; up to 170 times compared to that of P3MT NWs. More interestingly, an unexpected enhancement of PL was observed from cross-junction point of P3MT/Au NWs. The abnormal PL properties of P3MT/Au NWs were attributed to the charge transfer and the surface plasmon resonance between the cladding-shape Au and the core-shape P3MT, which resulted in the enhanced quantum yield. This incites us to reconsider the light-matter interaction in polymer-metal hybrid structures applicable for high-performance optoelectronic devices.

Clinical significance and predictive factors of early massive recurrence after radiofrequency ablation in patients with a single small hepatocellular carcinoma.

BACKGROUND/AIMS: Radiofrequency ablation (RFA) is one of the most frequently applied curative treatments in patients with a single small hepatocellular carcinoma (HCC). However, the clinical significance of and risk factors for early massive recurrence after RFA-a dreadful event limiting further curative treatment-have not been fully evaluated. METHODS: In total, 438 patients with a single HCC of size ≤3 cm who underwent percutaneous RFA as an initial treatment between 2006 and 2009 were included. Baseline patient characteristics, overall survival, predictive factors, and recurrence after RFA were evaluated. In addition, the incidence, impact on survival, and predictive factors of early massive recurrence, and initial recurrence beyond the Milan criteria within 2 years were also investigated. RESULTS: During the median follow-up of 68.4 months, recurrent HCC was confirmed in 302 (68.9%) patients, with early massive recurrence in 27 patients (6.2%). The 1-, 3-, and 5-year overall survival rates were 95.4%, 84.7%, and 81.8%, respectively, in patients with no recurrence, 99.6%, 86.4%, and 70.1% in patients with recurrence within the Milan criteria or late recurrence, and 92.6%, 46.5%, and 0.05% in patients with early massive recurrence. Multivariable analysis identified older age, Child-Pugh score B or C, and early massive recurrence as predictive of poor overall survival. A tumor size of ≥2 cm and tumor location adjacent to the colon were independent risk factors predictive of early massive recurrence. CONCLUSION: Early massive recurrence is independently predictive of poor overall survival after RFA in patients with a single small HCC. Tumors sized ≥2 cm and located adjacent to the colon appear to be independent risk factors for early massive recurrence.

Malignant melanoma of unknown primary origin presenting as cardiac metastasis.

Malignant melanoma has a very high propensity to metastasize to the heart. However, melanoma may sometimes present as a metastatic lesion in the absence of a primary lesion, which are called melanomas of unknown primary origin. We report a case in which a patient presented with a metastatic maligant melanoma in the right atrium with pericardial effusion and without a primary origin.

Fluorescence switch in red-phase polydiacetylene films and vesicles upon thermal cycles.

The switch phenomena of thermochromism of red-phase polymerized PCDA (10,12-pentacosadiynoic acid) Langmuir-Schaefer (LS) films and vesicles were investigated in situ during repeated heating and cooling processes between 25 degrees C and 70 degrees C. During repeated thermal cycles, the solid-supported LS films exhibited switch phenomena in both the visible and fluorescent spectra, that is, the colorimetric response (CR) of the PCDA LS films was ca. 80% at 70 degrees C but is ca. 50-60% at 25 degrees C with an increase of fluorescent intensity in the cooling process and a decrease in the heating process. On the other hand, the PCDA vesicles exhibited such phenomenon only in the fluorescent spectra, that is, the CR of the PCDA vesicles was constant as ca. 100% after being stable red form with the same trend in the fluorescent intensity. The changes in molecular configuration revealed by in situ Fourier transform infrared (FTIR) were in good agreement with the trend of fluorescence emission upon repeated thermal stimuli rather than that of visible absorption.

Fluorescence signal enhancement of polydiacetylene vesicle stacks.

Polydiacetylenes provide a good biological/chemical label-free detection system owing to their blue to red color change and fluorescence change from non-fluorescence to red fluorescence. One of the important factors to consider before applying polydiacetylenes to various sensors is to enhance the sensitivity against specific molecules. This paper reports two methods for stacking polydiacetylene vesicles for fluorescence signal enhancement of polydiacetylene on solid substrates. This focuses on how to achieve a highly sensitive sensor chip by introducing two strategies to immobilize the vesicles effectively on substrates. One method is layer-by-layer deposition through reactions of vesicles and avidins alternately on an avidin treated substrate. The other is to prepare a clustered vesicles solution by mixing the appropriate amount of a biotinylated vesicle solution and avidin solution, and then immobilize the clustered vesicles on the substrates. The former allows easy control of the layer thickness, whereas the latter can shorten the process time. These strategies can be applied to a range of biological/chemical sensors for fluorescence signal enhancement.

Effect of phospholipid insertion on arrayed polydiacetylene biosensors.

Micro-arrayed polydiacetylene (PDA) vesicles mixed with phospholipids on glass slides were prepared for label-free detection of Escherichia coli. When E. coli bound to its antibodies chemically attached to polydiacetylene, the fluorescence of the vesicles was dramatically increased. The insertion of dimyristoyl phosphatidylcholine (DMPC) in the vesicles drastically reduced the response time for the fluorescence changes. Vesicles with 20-30% DMPC provided optimal results for bacterial detection. Fourier transform infrared (FTIR) spectra analysis suggested that DMPC insertion decreased the strength of hydrogen bonding among the amide and carboxylic acid groups of the polydiacetylene vesicles. Reduced bonding strength resulted in less rigid structure of the polydiacetylene polymer, allowing more rapid detection upon molecular recognition.

A polydiacetylene-based fluorescent sensor chip.

Self-assembled diacetylene vesicles were spotted and immobilized on aldehyde-modified glass substrates using conventional microarray technology. Irradiation of the immobilized diacetylenes allowed generation of nonfluorescent "blue-phase" polydiacetylene (PDA) arrays. Specific interaction of the PDA vesicle arrays with carbohydrates or poly(acrylic acid) solutions afforded fluorescent profiles.

Colorimetric reversibility of polydiacetylene supramolecules having enhanced hydrogen-bonding under thermal and pH stimuli.

To investigate the role of hydrogen-bonding on colorimetric transition of polydiacetylene supramolecules, novel diacetylene derivatives allowing various hydrogen-bonding states were synthesized by coupling carboxy-substituted (ortho-, meta-, and para-) anilide groups with a typical single-chain diacetylene lipid. One with a terminal carboxyl group at the meta position provided the resulting supramolecular Langmuir-Schaefer films with enhanced hydrogen-bonding, and hence resulted in unprecedented colorimetric reversibility under both thermal and pH stimuli.