Magnetotransport properties and magnetocaloric effect in La0.67Ca0.33Mn1−xTMxO3 (TM=Cu,Zn) perovskite manganites

The magnetic and transport properties of the perovskites La_0.67Ca_0.33Mn_1-xTM_xO₃ were found to be sufficiently changed with the substitution of Mn-sites by other 3d transition-metal cations (TM=Cu,Zn; x=0.15). The values of T_C, T_M−I, and T_CMR were surveyed when Mn was replaced by Cu and Zn. The magnetic field induced resistivity and magnetic entropy change of these samples showed abrupt changes near T_C (194.2 and 201.5 K for Cu and Zn-doped case respectively) and attained the highest values among the doped cases (up to 20% Cu). The maximum values (obtained at H=4 kOe) of magnetoresistance ratio (CMR) were 27.8%, and 24.5% and of magnetic entropy change (−ΔS_M) were 3.9 and 3.2 J/kg K for Cu and Zn-doped, respectively.     

Luminescence enhancement by the reduction–oxidation synthesis in monoclinic RE2O3 (RE=Eu,Gd) phosphors containing Eu3+ activator

A novel synthesis was developed for enhanced luminescence in sesquioxide phosphors containing Eu³⁺ activator. It consisted of two annealing steps: reduction under vacuum with gaseous H₂ at 10 Torr and 1300 °C and re-oxidation at 300–1500 °C in air. The integrated luminescence intensity of the monoclinic Eu₂O₃ phosphor was enhanced ca. 21 times by this method compared with conventional processing. The photoluminescence (PL) intensity was maximized at re-oxidation temperatures of 500–1100 °C. The PL characteristics of monoclinic Eu₂O₃ and Gd₂O₃:0.06Eu samples were compared with a commercial cubic Y₂O₃:Eu phosphor. The evolution of physical characteristics during the two-step annealing was studied by Raman spectroscopy, XPS, XRD, PL decay analysis, and SEM. PL decay lifetime increased proportionally to the PL intensity over the range 0.5–100 μs. Additional vibrational modes appeared at 490, 497, and 512 cm^?1 after the two-step annealing. The increase in PL intensity was ascribed to the formation of excess oxygen vacancies and their redistribution during annealing. Resonance crossovers between the charge transfer state and the emitting ⁵D_J states are discussed in relation to reported luminescence saturation mechanisms for oxysulfides Ln₂O₂S:Eu³⁺ (Ln=Y, La).     

Chiral orbital-angular momentum in the surface states of Bi2Se3

We performed angle-resolved photoemission (ARPES) experiments with circularly polarized light and first-principles density functional calculation with spin-orbit coupling to study surface states of a topological insulator Bi2Se3. We observed circular dichroism (CD) as large as 30% in the ARPES data with upper and lower Dirac cones showing opposite signs in CD. The observed CD is attributed to the existence of local orbital-angular momentum (OAM). First-principles calculation shows that OAM in the surface states is significant and is locked to the electron momentum in the opposite direction to the spin, forming chiral OAM states. Our finding opens a new possibility for strong light-induced spin-polarized current in surface states. We also provide a proof for local OAM origin of the CD in ARPES.     

Self-assembled, pH-sensitive retinoate nanostructures ionically complexed with PEG-grafted cationic polyelectrolytes

All-trans-retinoic acids (ATRA) are ionically complexed with cationic polyelectrolytes containing tertiary amines and self-assembled into nanoscale colloidal structures. Poly(2-(dimethylamino)ethyl methacrylate) grafted with polyethylene glycol, poly(DMAEMA-g-PEG), is used as a double hydrophilic, cationic polyelectrolyte. The polyion/ATRA complexes are formed by adding ATRA in dimethyl sulfoxide into aqueous solution of poly(DMAEMA-g-PEG). This complexation effectively suppresses the formation of undesirable drug crystallites and produces stable colloidal nanostructures having a hydrodynamic diameter of about 15?nm at a neutral pH. However, as the pH decreases below about 6, they undergo dramatic structural change into large aggregates of about 250?nm in diameter presumably due to the dissociation of ATRA from the polyelectrolyte. We expect that this pH-sensitive response of the polyion/ATRA complexes is useful for intracellular translocation at a neutral pH followed by the endosomal escape of ATRA in an acidic condition.     

Multiple color reflection in a single unit cell using double-layer electrochromic reaction

Multiple color states have been realized in single unit cell using double electrochromic (EC) reaction. The precise control of bistability in EC compounds which can maintain several colors on the two separated electrodes allows this new type of pixel to be realized. The specific electrical driving gives a way to maintain both sides in the reduced EC states and this colors overlapping in the vertical view direction can achieve the black state. The four color states (G, B, W, BK) in one cell/pixel can make a valuable progress to achieve a high quality color devices such like electronic paper, outdoor billboard, smart window and flexible display using external light source.     

Structural transformation and guest dynamics of methanol-loaded hydroquinone clathrate observed by temperature-dependent Raman spectroscopy

The structural transformations and guest dynamics of methanol-loaded β-form hydroquinone (HQ) clathrate were investigated using temperature-dependent Raman spectroscopy. Methanol-loaded β-form HQ clathrate was obtained by recrystallization and characterized by elemental analysis, synchrotron X-ray diffraction, solid-state (13)C NMR spectroscopy, and Raman spectroscopy. Temperature-dependent Raman spectra of methanol-loaded β-form HQ clathrate were measured in the temperature range 300-412 K at increments of 4 K. Although no significant changes were evident in the temperature range 300-376 K, abrupt changes in the relative intensity and shape of the Raman bands were observed between 380 and 412 K indicating the structural transition from methanol-loaded β-form HQ clathrate to pure α-form HQ. Methanol molecules were gradually released from the β-form HQ clathrate in the range 364-380 K. Upon returning to ambient conditions, the crystal structure of the HQ sample remained identical to that of pure α-form HQ. Therefore, the temperature-induced structural transition of methanol-loaded HQ clathrate is completely irreversible and α-form HQ is more stable at ambient conditions.     

Conversion of a murine monoclonal antibody A13 targeting epidermal growth factor receptor to a human monoclonal antibody by guided selection

Epidermal growth factor receptor (EGFR) is an attractive target for tumor therapy because it is overexpressed in the majority of solid tumors and the increase in receptor expression levels has been linked with a poor clinical prognosis. Also it is well established that blocking the interaction of EGFR and the growth factors could lead to the arrest of tumor growth and possibly result in tumor cell death. A13 is a murine monoclonal antibody (mAb) that specifically binds to various sets of EGFR-expressing tumor cells and inhibits EGF-induced EGFR phosphorylation. We isolated human immunoglobulin genes by guided selection based on the mAb A13. Four different human single chain Fvs (scFvs) were isolated from from hybrid scFv libraries containing a human VH repertoire with the VL of mAb A13 and a human VL repertoire with the VH of mAb A13. All the 4 scFvs bound to EGFR-expressing A431 cells. One scFv (SC414) with the highest affinity was converted to IgG1 (ER414). The ER414 exhibited ～17 fold lower affinity compared to the A13 mAb. In addition the ER414 inhibited an EGF-induced tyrosine phosphorylation of EGFR with much lower efficacy compared to the A13 mAb and Cetuximab (Merck KgaA, Germany). We identified that the epitope of A13 mAb is retained in ER414. This approach will provide an efficient way of converting a murine mAb to a human mAb.     

Role of vitamin D-binding protein in isocyanate-induced occupational asthma

The development of a serological marker for early diagnosis of isocyanate-induced occupational asthma (isocyanate-OA) may improve clinical outcome. Our previous proteomic study found that expression of vitamin D-binding protein (VDBP) was upregulated in the patients with isocyanate-OA. In the present study, we evaluated the clinical relevance of VDBP as a serological marker in screening for isocyanate-OA among exposed workers and its role in the pathogenesis of isocyanate-OA. Three study groups including 61 patients with isocyanate-OA (group I), 180 asymptomatic exposed controls (AECs, group II), 58 unexposed healthy controls (NCs, group III) were enrolled in this study. The baseline serum VDBP level was significantly higher in group I compared with groups II and III. The sensitivity and specificity for predicting the phenotype of isocyanate-OA with VDBP were 69% and 81%, respectively. The group I subjects with high VDBP (≥311 μg/ml) had significantly lower PC(20) methacholine levels than did subjects with low VDBP. The in vitro studies showed that TDI suppressed the uptake of VDBP into RLE-6TN cells, which was mediated by the downregulation of megalin, an endocytic receptor of the 25-hydroxycholecalciferol-VDBP complex. Furthermore, toluene diisocyanate (TDI) increased VEGF production and secretion from this epithelial cells by suppression of 1,25-dihydroxycholecalciferol [1,25(OH)(2)D(3)] production. The findings of this study suggest that the serum VDBP level may be used as a serological marker for the detection of isocyanate-OA among workers exposed to isocyanate. The TDI-induced VEGF production/ secretion was reversed by 1,25(OH)(2)D(3) treatment, which may provide a potential therapeutic strategy for patients with isocyanate-OA.     

A turn-on two-photon fluorescent probe for ATP and ADP

An acedan derivative containing Zn(II)-DPA has been developed as a two-photon probe for nucleoside phosphates, which shows enhanced fluorescence toward ATP and ADP at physiological pH 7.4 among other competing anions including AMP; the probe is permeable to cell membranes and thus can be directly used for two-photon imaging of ATP and ADP in live cells.     

Electrophosphorescent devices with solution processible emitter and hole transport layer stack

The light emitting behavior of the electrophosphorescent devices with solution-processible hole transport layer and light emitting layer was characterized. We have introduced the hole-transporting stacked layer composed of poly(3,4-ethylenedioxy thiophene): poly(4-styrenesulfonate) [PEDOT:PSS] and thin perfluorinated ionomer, aiming for the improvement of charge injection and transport with corresponding high efficiency behavior. In order to provide a suitable work function, composition and thickness of the ultra-thin perfluorinated ionomer was optimized for being an interfacial layer condition; 34 cd/A of green phosphorescent device was obtained while the control device without ionomer shows the luminous efficiency of 29 cd/A. Both for devices with vacuum-deposited and solution-processed electrophosphorescent emitters, change of the device efficiencies were analyzed in terms of the work function, surface chemical composition, and charge conduction behavior.