An absorption spectrophotometer compatible paper-based thin-layer cuvette with an integrated pneumatic pump.

This study presents a paper-based thin-layer optical cuvette for absorption spectroscopy with a pneumatically driven pump for the introduction of an aqueous sample. The three major components, a sample reservoir, an open-channel as an optical path and a pneumatic pump, are patterned in polypropylene paper using an electronic cutting machine. When sealed with transparent tape, the patterned paper serves as the side walls of the paper-based cuvette with an integrated pneumatic pump. Due to the reduced pressure inside the open-channel caused by the depression of the pump with a finger, aqueous samples spotted onto the reservoir are introduced into the open-channel of the paper-based cuvette. We demonstrated that the paper-based cuvettes are compatible with conventional spectrophotometers for absorption spectroscopic measurements and capable of quantifying the concentrations of various colored dyes in aqueous samples.

Recent Progress in Ionic Liquid Extraction for the Separation of Rare Earth Elements.

This review summarizes recent progress in solvent extraction of rare earth elements (REEs) using an ionic liquid (IL) as the extraction solvent. These IL extraction systems are advantageous owing to the affinity of ILs for both charged and neutral hydrophobic species, in contrast to conventional organic solvent extraction systems. Herein, REE extraction studies using ILs are detailed and classified based on the type of extraction system, namely extraction using anionic ligands, extraction using neutral ligands, synergistic extraction, extraction without extractants, and a specific system using task-specific ionic liquids (TSILs). In IL extraction systems, the extracted complexes are often different from those in organic solvent systems, and the REE extraction and separation efficiencies are often significantly enhanced. Synergistic IL extraction is an effective approach to improving the extractability and separability of REEs. The development of novel TSILs suitable for IL extraction systems is also effective for REE separation.

Mutual Separation of Fe(II) and Fe(III) Using Cyclohexane/Water/Ionic-liquid Triphasic Extraction System with 2,2'-Bipyridine and Tri-n-octylphosphine Oxide.

The triphasic extraction system with two extract phases can be used to separate two materials simultaneously into each phase. In this article, a possible mutual separation of Fe(II) and Fe(III) was studied using the cyclohexane/water/ionic liquid (IL) triphasic extraction system for Fe speciation. For Fe(II) and Fe(III) extraction, 2,2'-bipyridine (bpy) and tri-n-octylphosphine oxide (TOPO) were selected as extractants, respectively. It was suggested that [FeII(bpy)3]2+ and FeIII(TOPO)43+·3Tf2N- were extracted into the IL (1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, C4mimTf2N) phase and the cyclohexane phase, respectively, and both of the extractants also acted as masking agents. On simultaneous separation using the triphasic system, Fe(II) and Fe(III) were quantitatively extracted into the IL phase and the cyclohexane phase, respectively, and their mutual separation was achieved.

Capillary Electrophoretic Characterization of Water-soluble Carbon Nanodots Formed from Glutamic Acid and Boric Acid under Microwave Irradiation.

Water-soluble carbon nanodots (CND) were synthesized under microwave irradiation from glutamic acid or glutamic acid-boric acid mixture. The CNDs were collected in an aqueous solution through size fractionation by centrifugal filtration. The CNDs thus prepared were subjected to characterization by capillary electrophoresis (CE). A peak signal of anionic substance was detected in the electropherogram, and it was found to be a major component of the CNDs. The effective electrophoretic mobility of the major component was almost identical over the pH range between 6.7 and 11.6, suggesting that the functional group of amine or boric acid moiety was not included in the CNDs. The effective electrophoretic mobility decreased at an acidic pH of less than 5, and it was suggested that carboxylate moiety was included in the CNDs. A signal of less-charged CNDs was also detected in the electropherogram, and the CNDs were characterized by a CE format of micellar electrokinetic chromatography. Two or four peaks were detected just after the electroosmotic flow; the less-charged CNDs were thus hydrophilic. The affinity interaction was also examined between the major anionic CNDs and a hydrophobic pairing cation. The peak signal of the major anionic CNDs broadened, and its theoretical number of plates decreased in the presence of tetrabutylammonium ion in the separation buffer. A small portion of the anionic CNDs were a little hydrophobic at different degrees, and their effective electrophoretic mobility decreased by the hydrophobic interaction, resulting in peak broadening of the anionic CNDs.

Solar-Driven Photoelectrochemical Water Oxidation over an n-Type Lead-Titanium Oxyfluoride Anode.

Mixed-anion compounds (e.g., oxynitrides and oxysulfides) are potential candidates as photoanodes for visible-light water oxidation, but most of them suffer from oxidative degradation by photogenerated holes, leading to low stability. Here we show an exceptional example of a stable, mixed-anion water-oxidation photoanode that consists of an oxyfluoride, Pb2Ti2O5.4F1.2, having a band gap of ca. 2.4 eV. Pb2Ti2O5.4F1.2 particles, which were coated on a transparent conductive glass (FTO) support and were subject to postdeposition of a TiO2 overlayer, generated an anodic photocurrent upon band gap photoexcitation of Pb2Ti2O5.4F1.2 (λ <520 nm) with a rather negative photocurrent onset potential of ca. -0.6 V vs NHE, which was independent of the pH of the electrolyte solution. Stable photoanodic current was observed even without loading a water oxidation promoter such as CoOx. Nevertheless, loading CoOx onto the TiO2/Pb2Ti2O5.4F1.2/FTO electrode further improved the anodic photoresponse by a factor of 2-3. Under AM1.5G simulated sunlight (100 mW cm-2), stable water oxidation to form O2 was achieved using the optimized Pb2Ti2O5.4F1.2 photoanode in the presence of an applied potential smaller than 1.23 V, giving a Faradaic efficiency of 93% and almost no sign of deactivation during 4 h of operation. This study presents the first example of photoelectrochemical water splitting driven by visible-light excitation of an oxyfluoride that stably works, even without a water oxidation promoter, which is distinct from ordinary mixed-anion photoanodes that usually require a water oxidation promoter.

Ionic Liquid Chelate Extraction Behavior of Trivalent Group 13 Metals into 1-Alkyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imides Using 8-Quinolinol as Chelating Extractant.

Ionic liquid (IL) chelate extraction behavior of trivalent Group 13 metals including aluminum(III), gallium(III) and indium(III) with 8-quinolinol (HQ) was investigated using three 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (CnmimTf2N, n = 2, 4 and 8) ILs. Although the three extraction systems showed similar extraction selectivity among the metals, the extractability order for the metals among the extraction systems was C8mimTf2N > C4mimTf2N > C2mimTf2N, which was the same as the order of hydrophobicity in the IL cation. Only the neutral 1:3 complex species was extracted in use of more-hydrophobic C8mimTf2N, whereas use of less-hydrophobic C4mimTf2N and C2mimTf2N resulted in competitive extraction of neutral 1:3 and cationic 1:2 complexes. For each of the metals, in addition, similar extraction constants were obtained in these three extraction systems.

Formation of Minimal Third Phase in Ionic Liquid Extraction System with Trioctylphosphine Oxide and Its Possible Application to Extraction Concentration.

The third-phase formation behavior in ionic liquid (IL) extraction system using trioctylphosphine oxide (TOPO) was investigated. In the use of a relatively less-lipophilic IL, such as 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C4mimTf2N), the third phase was formed between the aqueous phase and the IL phase. The third phase seems to have a relatively high lipophilicity compared to the IL phase. The main components of the third phase were suggested as being (H3O)TOPO+, IL anion (Tf2N-), IL cation (C4mim+) and free TOPO. In addition, the third phase showed an extraction concentration ability for the Fe(III)-thiocyanato complex.

Distribution Equilibria of Amphoteric 8-Quinolinol between 1-Alkyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide and Aqueous Phases and Their Effect on Ionic Liquid Chelate Extraction Behavior of Iron(III).

The distribution behavior of amphoteric 8-quinolinol (HQ) between ionic liquid (IL) phase and aqueous phase and ionic liquid chelate extraction behavior of iron(III) with HQ were investigated using four 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (CnmimTf2N, n = 2, 4, 6 and 8) ILs. Not only neutral HQ but also cationic H2Q+ were distributed into the IL phase, and the latter distribution based on cation-exchange with Cnmim+ was pronounced in the use of IL having a less-hydrophobic cation, such as C2mim+. In the IL chelate extraction of iron(III), the extractability increased with the increase in the hydrophobicity of IL as the extraction phase. Nevertheless, the determined equilibrium constants for the extraction as the neutral complex FeQ3 were similar to one another. The difference in the extractability among the ILs was due to the difference in the distribution of H2Q+ into the extraction phase. In addition, the cationic coordinatively-unsaturated complex FeQ2+ was also extracted in use of less-hydrophobic C2mimTf2N.

Effect of the Elemental Composition of Precursors from Amino Acids and Their Binary Mixtures on the Photoluminescent Intensity of Carbon Nanodots.

We report on the photoluminescent (PL) properties of carbon nanodots (CNDs) doped with nitrogen and sulfur obtained by the pyrolytic carbonization of amino acids as precursors. Prepared CNDs exhibit stable PL emission under a wide variety of aqueous conditions. The results also provided the way to tune a PL intensity of CNDs by varying the amount of heteroatoms in precursors with a binary mixture of amino acids. The PL quantum yields of the obtained CNDs were determined to be from 0.079 to 0.571.

Electrocatalytic Reduction of Free Chlorine at an N,N-Diethylaniline-grafted Carbon Electrode for Improved Sensitivity in Amperometric Detection.

The electrocatalytic activity of an N,N-diethylaniline-grafted carbon (DEA/PFC) electrode was utilized to improve the sensitivity in the cathodic detection of free chlorine. Voltammetric curves showed a well-defined cathodic peak of free chlorine on DEA/PFC, lowering the overlap with that of dissolved oxygen. Amperometric measurements were applied for the determination of free chlorine for a concentration range of 4 orders of magnitude. The results showed that measurements of the amperometric response with DEA/PFC can be used as the basis for a simple, accurate, and rapid method to determine free chlorine.

Synergistic Ion-pair Extraction of Strontium Ion with Tri-n-octylphosphine Oxide and Dicyclohexano-18-crown-6.

The co-use of two neutral ligands, tri-n-octylphosphine oxide (TOPO) and dicyclohexano-18-crown-6 (DC18C6), for ion-pair extraction of divalent strontium (Sr2+) with bis(trifluoromethanesulfonyl)imide anion (Tf2N-) showed unique synergistic effect. The extracted species in use of a single ligand is Sr(TOPO)32+·2Tf2N- or Sr(DC18C6)2+·2Tf2N-, whereas the co-use resulted in extraction enhancement based on additional formation of Sr(DC18C6)(TOPO)2+·2Tf2N- and Sr(DC18C6)(TOPO)22+·2Tf2N-.

A specific synergistic effect in ionic liquid chelate extraction based on neutral ternary chloro-complex formation.

In the chelate extraction of zinc(II) into an ionic liquid (IL), 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C4mimTf2N), with 8-(p-toluenesulfonamido)quinoline (Htsq), the co-existence of a certain amount of chloride anion in the aqueous phase resulted in an enhancement of the extractability. This enhancement did not occur at all in that into chloroform, a conventional organic extraction solvent. The specific synergistic effect was based on the dominant extraction of a neutral ternary complex, Zn(tsq)Cl, which is unstable in molecular organic solvents.

Mechanical gate control for atom-by-atom cluster assembly with scanning probe microscopy.

Nanoclusters supported on substrates are of great importance in physics and chemistry as well as in technical applications, such as single-electron transistors and nanocatalysts. The properties of nanoclusters differ significantly from those of either the constituent atoms or the bulk solid, and are highly sensitive to size and chemical composition. Here we propose a novel atom gating technique to assemble various atom clusters composed of a defined number of atoms at room temperature. The present gating operation is based on the transfer of single diffusing atoms among nanospaces governed by gates, which can be opened in response to the chemical interaction force with a scanning probe microscope tip. This method provides an alternative way to create pre-designed atom clusters with different chemical compositions and to evaluate their chemical stabilities, thus enabling investigation into the influence that a single dopant atom incorporated into the host clusters has on a given cluster stability.

50-Gb/s ring-resonator-based silicon modulator.

We achieved 50-Gb/s operation of a ring-resonator-based silicon modulator for the first time. The pin-diode phase shifter, which consists of a side-wall-grating waveguide, was loaded into the ring resonator. The forward-biased operation mode was applied, which exhibited a V(π)L as small as 0.28 V · cm at 25 GHz. The driving voltage and optical insertion loss at 50-Gb/s were 1.96 V(pp) and 5.2 dB, respectively.

Valence discriminative detection of metal cations by a chromotropic acid-grafted glassy carbon electrode.

Covalent grafting of chromotropic acid (CA) moiety to a glassy carbon electrode was performed by electrochemical reduction of the corresponding diazonium cation generated in situ. Grafted electrodes were subjected to the electrochemical detection of multivalent cations using Fe(CN)(6)(3-/4-) as an electrochemical probe molecule. In the absence of metal cations, redox reaction of the anionic probe was depressed by electrostatic repulsion between the probe and negatively charged CA moieties on the electrode surface. Binding of tetravalent cations such as Zr(IV) and Hf(IV) and trivalent cations such as Al(III) and lanthanide(III) to the CA moiety on the electrode surface resulted in an increase in the current intensity of the probe due to a decrease in electrostatic repulsion. Highly selective detection of the tetravalent cations was achieved in the micromolar concentration range at pH 1.0.

Demonstration of 12.5-Gbps optical interconnects integrated with lasers, optical splitters, optical modulators and photodetectors on a single silicon substrate.

One of the most serious issues in information industries is the bandwidth bottleneck in inter-chip interconnects. We propose a photonics-electronics convergence system to solve this issue. We fabricated a high density optical interposer to demonstrate the feasibility of the system by using silicon photonics integrated with an arrayed laser diode, an optical splitter, silicon optical modulators, germanium photodetectors, and silicon optical waveguides on a single silicon substrate. Error-free data transmission at 12.5 Gbps and a transmission density of 6.6 Tbps/cm2 were achieved with the optical interposer. We believe this technology will solve the bandwidth bottleneck problem in the future.

Specific cooperative effect of a macrocyclic receptor for metal ion transfer into an ionic liquid.

An intramolecular cooperative extraction system for the removal of strontium cations (Sr(2+)) from water by use of a novel macrocyclic receptor (H(2)ßDA18C6) composed of diaza-18-crown-6 and two ß-diketone fragments in ionic liquid (IL) is reported, together with X-ray spectroscopic characterization of the resulting extracted complexes in the IL and chloroform phases. The covalent attachment of two ß-diketone fragments to a diazacrown ether resulted in a cooperative interaction within the receptor for Sr(2+) transfer, which remarkably enhanced the efficiency of Sr(2+) transfer relative to a mixed ß-diketone and diazacrown system. The intramolecular cooperative effect was observed only in the IL extraction system, providing a 500-fold increase in extraction performance for Sr(2+) over chloroform. Slope analysis and potentiometric titration confirmed that identical extraction mechanisms operated in both the IL and chloroform systems. Extended X-ray absorption fine structure spectroscopy revealed that the average distance between Sr(2+) and O atoms in the Sr(2+) complex was shorter in IL than in chloroform. Consequently, Sr(2+) was held by H(2)ßDA18C6 more rigidly in IL than in chloroform, representing an important factor dominating the magnitude of the intramolecular cooperative effect of H(2)ßDA18C6 for Sr(2+). Furthermore, competitive extraction studies with alkaline earth metal ions revealed that the magnitude of the intramolecular cooperative effect depended on the suitability between metal ion size and the cavity size of H(2)ßDA18C6. Sr(2+) was successfully recovered from IL by controlling the pH in the receiving phase, and the extraction performance of H(2)ßDA18C6 in IL was maintained after five repeated uses.

Evaluation of a hydrophilic ionic liquid as a salting-out phase separation agent to a water-tetrahydrofuran homogeneous system for aqueous biphasic extraction separation.

The use of a hydrophilic ionic liquid (IL), 1-butyl-3-methylimidazolium chloride (C(4)mimCl), as a salting-out phase separation agent to a water-tetrahydrofuran homogeneous system was studied for possible applications to novel aqueous biphasic extraction separation. The IL showed a salting-out phase-separation ability. Also, differences in the polarity between the formed two phases were smaller than that when using NaCl as a salting-out agent. This result suggested that C(4)mimCl remaining in water-rich phase acts not only as a salting-out agent, but also a component of a mixed-solvent. Possible uses of C(4)mimCl/NaCl mixed salting-out agent system were also discussed.

12.5-Gb/s operation with 0.29-V·cm V(π)L using silicon Mach-Zehnder modulator based-on forward-biased pin diode.

We present high-speed operation of pin-diode-based silicon Mach-Zehnder modulators that have side-wall gratings on both sides of the waveguide core. The use of pre-emphasis signals generated with a finite impulse response digital filter was examined in the frequency domain to show how the filter works for different filter parameter sets. In large signal modulation experiments, V(π)L as low as 0.29 V·cm was obtained at 12.5 Gb/s using a fabricated modulator and the pre-emphasis technique. Operation of up to 25-Gb/s is possible using basically the same driving configurations.