Optical manipulation and fusion of aqueous droplets containing inorganic and organic solutes in air using the dual-beam laser trapping technique.

The comparative evaluation of two aerosol droplets of different chemical compositions using the dual-beam laser trapping technique can be employed for highly sensitive and accurate measurements of the water activities of such droplets. However, it is technically difficult to load droplets of different chemical compositions into adjacent optical traps that are only a few tens of micrometers apart. To overcome this challenge, a chamber with an overhanging roof was created. This roof prevented the initially trapped droplets from being contaminated by aerosol droplets that were subsequently introduced into the chamber. Herein, we report the simultaneous laser trapping of an aqueous ammonium sulfate (AS) droplet and an aqueous succinic acid (SA) droplet in air using the dual-beam laser trapping technique. Two droplets were successfully fused through optical manipulation to form a mixed inorganic/organic droplet in air. This experimental approach is advantageous because it forms mixed inorganic/organic droplets under constant relative humidity (RH) conditions. However, in previous studies, it was necessary to compensate for changes in RH prior to and after droplet fusion. To assess the validity of theoretical predictions of the water activity of droplets containing AS and SA, the equilibrium radii of the droplet were compared with those calculated using certain theoretical models.

In situ Raman and X-ray scattering of a single supersaturated aqueous Mg(NO3)2 droplet ultrasonically levitated.

A single liquid droplet in the air generated by ultrasonic levitation provides such analytical advantages as a small sample volume (~ µL) for expensive proteins, container-free condition for deeply supercooling and supersaturation, time-dependent observation, and homogeneous rapid mixing. The investigation of the properties and structure of a droplet at a molecular level is highly needed for understanding the physicochemical behaviors of a droplet and an underlying mechanism of processes in the droplet. We develop in situ Raman and synchrotron X-ray scattering methods of a single liquid droplet of ~ 1 mm size ultrasonically levitated. The composition of a supersaturated Mg(NO3)2 droplet and speciation in the droplet are determined by analyzing the nitrate N-O and the water O-H stretching vibrational Raman bands. The X-ray interference function of an supersaturated Mg(NO3)2 droplet is subjected to an empirical potential structure refinement modeling to reveal the ion solvation, association, and solvent water structure. Furthermore, crystallization of Mg(NO3)2⋅nH2O from a saturated droplet is observed and identified.

Tuning the Ground- and Excited-State Redox Potentials of Octahedral Hexanuclear Rhenium(III) Complexes by the Combination of Terminal Halide and N-Heteroaromatic Ligands.

The present study reports that the ground- and excited-state Re6(23e)/Re6(24e) redox potentials of an octahedral hexanuclear rhenium(III) complex can be controlled by systematically changing the number and type of the N-heteroaromatic ligand (L) and the number of chloride ions at the six terminal positions. Photoirradiation of [Re6(µ3-S)8Cl6]4- with an excess amount of L afforded a mono-L-substituted hexanuclear rhenium(III) complex, [Re6(µ3-S)8Cl5(L)]3- (L = 4-dimethylaminopyridine (dmap), 3,5-lutidine (lut), 4-methylpyridine (mpy), pyridine (py), 4,4'-bipyridine (bpy), 4-cyanopyridine (cpy), and pyrazine (pz)). The bis- and tris-lut-substituted complexes, trans- and cis-[Re6(µ3-S)8Cl4(lut)2]2- and mer-[Re6(µ3-S)8Cl3(lut)3]-, were synthesized by the reaction of [Re6(µ3-S)8Cl6]3- with an excess amount of lut in refluxed N,N-dimethylformamide. The mono-L-substituted complexes showed one-electron redox processes assignable to E 1/2[Re6(23e)/Re6(24e)] = 0.49-0.58 V versus Ag/AgCl. The ground-state oxidation potentials were linearly correlated with the pK a of the N-heteroaromatic ligand [pK a(L)], the 1H NMR chemical shift of the ortho proton on the coordinating ligand, and the Hammett constant (σ) of the pyridyl-ligand substituent. The series of [Re6(µ3-S)8X6-n (L) n ] n-4 complexes (n = 0, X = Cl, Br, I, or NCS; n = 1-3, X = Cl) showed a linear correlation with the sum of the Lever electrochemical parameters at the six terminal ligands (ΣE L). The cyclic voltammograms of the mono-L-substituted complexes (L = bpy, cpy, and pz) showed one-electron redox waves assignable to E 1/2(L0/L-) = -1.28 to -1.48 V versus Ag/AgCl. Two types of photoluminescences were observed for the complexes, originating from the cluster core-centered excited triplet state (3CC) for L = dmap, lut, mpy, and py and from the metal-to-ligand charge-transfer excited triplet state (3MLCT) for L = bpy, cpy, and pz. The complexes with the 3CC character exhibited emission features and photophysical properties similar to those of ordinary hexanuclear rhenium complexes. The emission maximum wavelength of the complexes with 3MLCT shifted to the longer wavelength in the order L = 4-phenylpyridine (ppy), bpy, pz, and cpy, which agreed with the difference between E 1/2[Re6(23e)/Re6(24e)] and E 1/2(L0/L-). The calculated oxidation potential of the excited hexanuclear rhenium complex with the 3CC character was linearly correlated with pK a(L), σ, and ΣE L. The ground- and excited-state oxidation potentials were finely tuned by the combination of halide and L ligands at the terminal positions.

Liquid-Liquid Phase Separation of Single Optically Levitated Water-Ionic Liquid Droplets in Air.

In this study, to investigate the equilibrium morphology of liquid-liquid phase-separated droplets in air, a temperature-responsive ionic liquid (IL) showing lower critical solution temperature behavior was employed. ILs have negligible vapor pressure and do not evaporate from aerosol droplets during dehumidifying processes. We demonstrated that the liquid-liquid phase separation of single optically levitated aqueous droplets containing the temperature-responsive IL can be induced by controlling the air relative humidity. The formation of liquid-liquid phase-separated droplets of partially engulfed morphology was successfully observed under an optical microscope, and their configurations were compared with those calculated by a thermodynamic model based on interfacial tensions and relative volume ratios of two immiscible phases.

Fabrication of Paper-based Microfluidic Devices Using a Laser Beam Scanning Technique.

This paper describes a novel method for fabricating paper-based microfluidic devices using a laser beam scanning technique. Cellulose chromatography papers were treated with octadecyltrichlorosilane (OTS) to make them entirely hydrophobic. A photoacid generator (CPI-410S) was soaked into the paper, and irradiated with a 405-nm laser beam to induce acid generating reactions. Since the silyl ether bond between cellulose and OTS was cleaved by the hydrolysis reaction, the photo-irradiated area changed to hydrophilic. By scanning the laser beam using a Galvo mirror system, arbitrary shaped hydrophilic patterns were successfully created on the paper in 50 µm resolution. To the best of our knowledge, this is the first report on the fabrication of hydrophilic channels on the OTS-treated paper using photo-induced acid generation processes coupled with the laser beam scanning technique. Quantification of nitrite was demonstrated with the paper device made by this method.

Control of Emissive Excited States of Silver(I) Halogenido Coordination Polymers by a Solid Solution Approach.

Luminescent silver(I) halogenido coordination polymers [Ag2X2(PPh3)2(bpy)] n (X = I, Br, Cl) have been prepared. The iodido and bromido complexes exhibit strong blue phosphorescence assignable to the 3π-π*-excited-state of bpy, whereas the chlorido complex shows luminescence thermochromism due to the π-π*-state of bpy and charge transfer from the {Ag2Cl2} core to the bpy π*-orbital. Taking advantage of their structural similarities, we prepared a series of mixed-halogenido silver(I) complexes [Ag2(X xX'(1- x))2(PPh3)2(bpy)] n (X, X' = I, Br, Cl) at varying molar fractions as solid solutions. The mixed-halogenido complexes are as strongly luminescent as their parent complexes. The detailed study of their structure and emissive properties revealed smooth energy migration between the luminescent units and modification of the luminescence properties based on the planarity of bpy.

Photochemical generation of the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical from caged nitroxides by near-infrared two-photon irradiation and its cytocidal effect on lung cancer cells.

Novel caged nitroxides (nitroxide donors) with near-infrared two-photon (TP) responsive character, 2,2,6,6-tetramethyl-1-(1-(2-(4-nitrophenyl)benzofuran-6-yl)ethoxy)piperidine (2a) and its regioisomer 2b, were designed and synthesized. The one-photon (OP) (365 ± 10 nm) and TP (710-760 nm) triggered release (i.e., uncaging) of the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical under air atmosphere were discovered. The quantum yields for the release of the TEMPO radical were 2.5% (2a) and 0.8% (2b) in benzene at ≈1% conversion of 2, and 13.1% (2a) and 12.8% (2b) in DMSO at ≈1% conversion of 2. The TP uncaging efficiencies were determined to be 1.1 GM at 740 nm for 2a and 0.22 GM at 730 nm for 2b in benzene. The cytocidal effect of compound 2a on lung cancer cells under photolysis conditions was also assessed to test the efficacy as anticancer agents. In a medium containing 100 µg mL-1 of 2a exposed to light, the number of living cells decreased significantly compared to the unexposed counterparts (65.8% vs 85.5%).

Raman Spectroscopy of Single Light-Absorbing Carbonaceous Particles Levitated in Air Using an Annular Laser Beam.

A laser trapping technique is a powerful means to investigate the physical and chemical properties of single aerosol particles in a noncontact manner. However, optical trapping of strongly light-absorbing particles such as black carbon or soot is quite difficult because the repulsive force caused by heat is orders of magnitude larger than the attractive force of radiation pressure. In this study, a laser trapping and Raman microspectroscopy system using an annular laser beam was constructed to achieve noncontact levitation of single light-absorbing particles in air. Single acetylene carbon black or candle soot particles were arbitrarily selected with a glass capillary connected to a three-axis oil hydraulic micromanipulator and introduced into a minute space surrounded by a repulsive force at the focal point of an objective lens. Using the developed system, we achieved optical levitation of micrometer-sized carbonaceous particles and observation of their Raman spectra in air. Furthermore, we demonstrated in situ observations of changes in the morphology and chemical composition of optically trapped carbonaceous particles in air, which were induced by heterogeneous oxidation reactions with ozone and hydroxyl radicals.

Near-infrared Laser-induced Temperature Elevation in Optically-trapped Aqueous Droplets in Air.

Near-infrared laser-induced temperature elevation in single aqueous ammonium sulfate droplets levitated in air were evaluated by means of laser trapping and Raman spectroscopy. Since the vapor pressure in an aqueous solution droplet should be thermodynamically in equilibrium with that of water in air, the equilibrium size of the droplet varies sensitively through evaporation/condensation of water in accordance with the temperature change of the droplet. In this study, we demonstrated that the changes in the size of an optically levitated aqueous ammonium sulfate droplet were induced by irradiation of a 1064-nm laser beam as a heat source under an optical microscope. Temperature elevation in the droplet was evaluated successfully by means of Raman spectroscopy, and the values determined were shown to be in good agreement with those by the theoretical calculations based on the absorption coefficient of water at 1064-nm and the thermal conductivity of air. To the best of our knowledge, this is the first experimental demonstration showing that the absorption coefficient evaluated from changes in the size of optically-trapped aqueous droplets is consistent with that of pure water.

A Flow Method for Chemiluminescence Determination of Antimony(III) and Antimony(V) Using a Rhodamine B-Cetyltrimethylammonium Chloride Reversed Micelle System Following On-Line Extraction.

A rapid and sensitive flow method, based on the combination of on-line solvent extraction with reversed micellar mediated chemiluminescence (CL) detection using rhodamine B (RB), was developed for the determination of antimony(III) and antimony(V) in aqueous samples. The on-line extraction procedure involved ion-pair formation of the antimony(V) chloro-complex anion with the protonated RBH(+) ion and its extraction from an aqueous hydrochloric acid solution into toluene, followed by phase separation using a microporous membrane. When in a flow cell of a detector, the ion-pair in the extract driven was mixed with the reversed micellar solution of cetyltrimethylammonium chloride in 1-hexanol-cyclohexane/water (0.60 mol dm(-3) H2SO4) containing cerium(IV), its uptake by the reversed micelles and the subsequent CL oxidation of RB with Ce(IV) occurred easily, then the produced CL signal was measured. Using the proposed flow method under the optimized experimental conditions, a detection limit (DL) of 0.35 µmol dm(-3) and a linear calibration graph with a dynamic range from DL to 16 µmol dm(-3) were obtained for Sb(V) with a precision of 1.4% relative standard deviation (n = 5) at the Sb(V) concentration of 8.2 µmol dm(-3). The present method was successfully applied to the determination of Sb(V) in water samples and to the differential determination of Sb(III) and Sb(V) in copper electrolyte industrial samples, where total antimony Sb(III) + Sb(V) was determined after oxidation of Sb(III) to Sb(V) with Ce(IV) and Sb(III) was calculated by difference, for which the DL was almost the same as that for Sb(V).

Directional Energy Transfer in Mixed-Metallic Copper(I)-Silver(I) Coordination Polymers with Strong Luminescence.

Strongly luminescent mixed-metallic copper(I)-silver(I) coordination polymers with various Cu/Ag ratio were prepared by utilizing the isomorphous relationship of the luminescent parent homometallic coordination polymers (Φ(em) = 0.65 and 0.72 for the solid Cu and Ag polymers, respectively, at room temperature). The mixed-metallic polymer with the mole fraction of copper even as low as 0.005 exhibits a strong emission (Φ(em) = 0.75) from only the copper sites as the result of the efficient energy migration from the silver to the copper sites. The migration rates between the two sites were evaluated from the dependence of emission decays upon the mole fraction of copper.

Reversible control of the equilibrium size of a single aerosol droplet by change in relative humidity.

Noncontact levitation of single micrometer-sized water droplets in air can be achieved by a laser trapping technique. The equilibrium size of a water droplet is quite sensitive to relative humidity in the surrounding gas phase. In order to investigate the physical and chemical properties of single water droplets in air as a function of the droplet size or solute concentration, laser trapping experiments were conducted under controlled humidity conditions. In this study, we developed a trapping chamber equipped with a relative humidity controller and demonstrated the reversible control of the equilibrium size of a single droplet levitated in air through a change in relative humidity. Furthermore, relative humidity was successfully evaluated by means of cavity enhanced Raman spectroscopy of a trapped water droplet.

In situ quantification of ammonium sulfate in single aerosol droplets by means of laser trapping and Raman spectroscopy.

Noncontact levitation in air of single micrometer-sized water droplets containing ammonium sulfate was successful by a laser trapping technique. The trapping laser beam was also used simultaneously as an excitation light source for the Raman spectroscopy of trapped droplets. Raman scattering of the symmetric stretching vibration of the SO4(2-) anion and the OH stretching vibrations of H2O were observed at 980 and 3420 cm(-1), respectively. The intensity ratio of these two Raman peaks was linearly proportional to the ammonium sulfate concentration in water. Therefore, the in situ quantification of ammonium sulfate in single aerosol droplets was achieved by means of laser trapping and Raman spectroscopy. To the best of our knowledge, this study is the first experimental observation of the independence of ammonium sulfate concentrations of aerosol water droplets to those of the mother solutions under constant relative humidity conditions.

Mechanical stimulation and solid seeding trigger single-crystal-to-single-crystal molecular domino transformations.

Numerous studies have focused on the mechanical control of solid structures and phase changes in molecular crystals. However, the molecular-level understanding of how macroscopic forces affect the molecules in a solid remains incomplete. Here we report that a small mechanical stimulus or solid seeding can trigger a single-crystal-to-single-crystal transformation from a kinetically isolated polymorph of phenyl(phenyl isocyanide)gold(I) exhibiting blue photoluminescence to a thermodynamically stable polymorph exhibiting yellow emission without the need for heating or solvent. The phase transformation initiates at the location of the mechanical stimulation or seed crystal, extends to adjacent crystals, and can be readily monitored visually by the accompanying photoluminescent colour change from blue to yellow. The transformation was characterized using single crystal X-ray analysis. Our results suggest that the transformation proceeds through self-replication, causing the complex to behave as 'molecular dominoes'.

Flow chemiluminescence determination of antimony(III,V) using a rhodamine B-cetyltrimethylammonium chloride reversed micelle system following liquid-liquid extraction.

A flow chemiluminescence (CL) method combined with a liquid-liquid extraction technique is proposed for the indirect determination of antimony in aqueous samples using rhodamine B (RB). In the liquid-liquid extraction process, the antimony(V) chloro-complex anion, [SbCl(6)](-), was extracted from an aqueous acidic solution into toluene via ion-pair formation with the protonated RBH(+) ion. Upon mixing the extract with a reversed micellar reagent solution of cetyltrimethylammonium chloride (CTAC) in 1-hexanol-cyclohexane/water (0.60 mol dm(-3) H(2)SO(4)) containing cerium(IV), uptake of the ion-pair by CTAC reversed micelles occurred easily, followed by an oxidation reaction of RB with Ce(IV) in the CL process. The CL signal produced was then measured. Using a flow injection system, the detection limits (DL) of 0.25 µmol dm(-3) Sb(III) and 0.20 µmol dm(-3) Sb(V), and linear calibration graphs with dynamic ranges from the respective DLs to 16 µmol dm(-3) for Sb(III) and Sb(V) were obtained under optimized experimental conditions. The proposed method was successfully applied to a mixture of Sb(III) and Sb(V), where total antimony, Sb(III) + Sb(V), was measured using ceric sulfate as an oxidant to oxidize Sb(III) to Sb(V) prior to extraction, Sb(V) was determined directly without the use of an oxidant, and Sb(III) was calculated by difference.

Spectroscopic studies on the photochemical decarboxylation mechanisms of synthetic pyrethroids.

A novel radical trapping technique combined with a fluorescence spectroscopic analysis has been employed to investigate the radical intermediates produced by photodecarboxylation of four synthetic pyrethroids: fenvalerate (SMD), fenpropathrin (DTL), cyphenothrin (GKL), and cypermethrin (AGT). Under photoirradiation at >290 nm, all pyrethroids underwent direct photolysis via homolytic cleavage of the carbon-oxygen bonds in the ester groups. The consumed amount of a nitroxide free radical, as a trapping agent for the intermediate radical of a pyrethroid, was determined by ESR, which was the measure of the reaction yield of a photochemically generated α-cyano-3-phenoxybenzyl radical common to all pyrethroids. The reactivities of the pyrethroids studied was in the sequence of SMD >> DTL > GKL > AGT. Furthermore, nanosecond transient absorption spectroscopy demonstrated that geminate recombination of the radical pair within a solvent cage is the main deactivation route of the photochemically generated α-cyano-3-phenoxybenzyl radical common for all pyrethroids studied.

Syntheses and luminescent properties of 3,5-diphenylpyrazolato-bridged heteropolynuclear platinum complexes. The influence of chloride ligands on the emission energy revealed by the systematic replacement of chloride ligands by 3,5-dimethylpyrazolate.

Heteropolynuclear Pt(II) complexes with 3,5-diphenylpyrazolate [Pt(2)Ag(4)(µ-Cl)(2)(µ-Ph(2)pz)(6)] (3), [Pt(2)Ag(2)Cl(2)(µ-Ph(2)pz)(4)(Ph(2)pzH)(2)] (4), [Pt(2)Cu(2)Cl(2)(µ-Ph(2)pz)(4)(Ph(2)pzH)(2)] (5), [Pt(2)Ag(4)(µ-Cl)(µ-Me(2)pz)(µ-Ph(2)pz)(6)] (7), and [Pt(2)Ag(4)(µ-Me(2)pz)(2)(µ-Ph(2)pz)(6)] (8) have been prepared and structurally characterized. These complexes are luminescent except for 5 in the solid state at an ambient temperature with emissions of red-orange (3), orange (4), yellow-orange (7), and green (8) light, respectively. Systematic red shift of the emission energies with the number of chloride ligands was observed for 3, 7, and 8. DFT calculations indicate that the highest occupied molecular orbital (HOMO) as well as HOMO-1 of the heterohexanuclear complexes, 3, 7, and 8, having Pt(2)Ag(4) core, mainly consist of dδ orbital of Pt(II) and π orbitals of Ph(2)pz ligands, while the lowest unoccupied molecular orbital (LUMO) of these complexes mainly consists of in-phase combination of 6p of two Pt(II) centers and 5p of four Ag(I) centers. It is likely that the emissions of 3, 7, and 8 are attributed to emissive states derived from the Pt(2)(d)/π → Pt(2)Ag(4) transitions, the emission energy of which depends on the ratio of chloride ligands to pyrazolate ligands.

Direct observation of a {Re6(µ3-S)8} core-to-ligand charge-transfer excited state in an octahedral hexarhenium complex.

A new complex, [Re(6)S(8)Cl(5)ppy](3-) (ppy = 4-phenylpyridine), was synthesized and characterized. The complex showed red emission at 296 K in both the crystalline phase and CH(3)CN. The transient absorption spectrum of [Re(6)S(8)Cl(5)ppy](3-) revealed that the emissive excited state involved the {Re(6)(µ(3)-S)(8)} core-to-ligand charge-transfer character.

Direct synthesis of fluorescent 1,3a,6a-triazapentalene derivatives via click-cyclization-aromatization cascade reaction.

An efficient and versatile method was established for the preparation of 1,3a,6a-triazapentalenes. The 1,3a,6a-triazapentalene skeleton without an additional fused ring system was discovered to be a compact and highly fluorescent chromophore, which exhibited various interesting fluorescent properties such as a noteworthy correlation of luminescent wavelength with the Hammett σ(p) value and a strongly positive solvatofluorochromism.

Laser trapping and picosecond time-resolved spectroscopy of water droplets in air: cavity-enhanced spontaneous emission of Ru(bpy)(3)Cl(2).

Whispering gallery mode (WGM) resonances were observed in the emission spectrum of Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) in a single laser-trapped water droplet levitated in air. The emission decay profiles of Ru(bpy)(3)(2+) in the water droplets comprised fast and slow decay components. The emission lifetime of the slow decay component was independent of the diameter of the droplet, and corresponded to the value in a bulk aqueous solution. On the other hand, the emission lifetime of the fast decay component decreased with decreasing the droplet diameter, which could be ascribed to the cavity-enhanced spontaneous emission. The decrease in the emission lifetime of the fast decay component as a function of the droplet diameter was explained on the basis of cavity quantum electrodynamic (QED) effects. It was shown that the mode characteristic of WGM resonances and the enhancement factor of the radiative rate of Ru(bpy)(3)(2+) were controlled by the size of the water droplet.