Fast Heavy-Ion-Induced Anion-Molecule Reactions on the Methanol Droplet Surface.

To gain insight into complex ion-molecule reactions induced by MeV-energy heavy ion irradiation of condensed matter, we performed a mass spectrometric study of secondary ions emitted from methanol microdroplet surfaces by 2.0 MeV C2+. We observed positive and negative secondary ions, including fragments, clusters, and reaction products. We found that a wider variety of negative ions than positive ions (such as C2H-, C2HO-, C2H5O-, and C2H3O2-) were formed. We performed measurements for deuterated methanol (CH3OD) droplets to identify the hydrogen elimination site of the intermediates involved in the reactions and to reveal the mechanism that generates various negative reaction product ions. Comparing the results of CH3OD with CH3OH droplets, we propose that the primary formation mechanism is association reactions of anion and neutral fragments, such as CH3O- + CO → C2H3O2-. Quantum chemical calculations confirmed that the reactions can proceed with no barrier. This study provides new insights into the importance of rapid anion-molecule reactions among fragments as the mechanism that generates complex molecular species in fast heavy-ion-induced reactions.

Revealing ultrafast vibronic dynamics of tetracene molecules with sub-8 fs UV impulsive Raman spectroscopy.

Ultrafast dynamics of tetracene molecules in THF solution were investigated using sub-8 fs ultraviolet pulse lasers and ab initio calculations. The time trace of absorbance changes exhibited ultrafast decay with a time constant of 165 ± 10 fs because of the relaxation from a vibronically hot excited state to the potential minimum in the S1 state. From the signals of absorbance changes in the negative time region, we obtained the electronic dephasing time of 31.27 ± 1.63 fs. Inverse Fourier transform of stationary absorption spectra exhibited rapid decay with 2.1 ± 0.08 fs. From these data, we estimated the ratio of total dephasing time to homogenous and inhomogeneous broadening as 6.7% and 93.3%, respectively. Impulsive Raman spectra reflect the wave packet dynamics of vibrational modes. Although inhomogeneous broadening blurred the phase jump across the resonance peak in the spectral range, 1156 and 1680 cm-1 vibrational modes exhibited a phase jump from -π to ∼π and -0.5π to ∼0.5π, respectively. The amplitude profiles of these vibrational modes agree with simulated vibronic progressions of combination bands. Time-frequency analysis revealed coupling dynamics between low- and high-frequency modes, where high-frequency modes are in-plane motions and low-frequency modes are out-of-plane motions. Therefore, these coupling dynamics induce symmetry-breaking of the molecular framework, which fastens the singlet fission process.

Ultrafast Excited State Dynamics of Forward and Reverse trans-cis Photoisomerization of Red-Light-Absorbing Indigo Derivatives.

Femtosecond time-resolved transient absorption (TRTA) spectroscopy was carried out to investigate the ultrafast excited state dynamics of both trans → cis and trans ← cis photoisomerization of red-light-absorbing indigo derivatives. For N,N'-bis(tert-butyloxycarbonylmethyl)indigo (tBOMI), the excited state lifetime of the trans-form was measured to be 41 ps while that of the cis-form was as short as 730 fs in acetonitrile (Acn). The excited state lifetime of trans-N,N'-dimethylindigo (DMI) in Acn was also measured to be as short as 10 ps. These values are much shorter than those of the blue-light-absorbing trans-forms of indigo derivatives such as N,N'-diacetylindigo (DAI) and thioindigo (ThI). The chromophore of indigo is composed of two pairs of electron donor and acceptor substituents conjugated in the shape of a letter "H" (so-called "H-chromophore"), although DFT and TDDFT calculations suggest that the charge transfer (CT) character is not very significant. Nevertheless, when a weak CT within the H-chromophore is promoted, the absorption band shifts to longer wavelengths and the excited state lifetime shortens. For the photoisomerization of DAI and ThI, a relatively long excited state lifetime is required for the photoisomerization, while for tBOMI and DMI, a vibrationally hot ground state that overcomes the energy barrier in the ground state is produced by rapid nonradiative decay through conical intersection. In the case of cis-tBOMI, the repulsion between the two adjacent negatively charged carbonyl groups and the weakening of the central C═C double bond in the S1 state twist the molecule, shorten the excited state lifetime, and increase the quantum yield of the trans ← cis photoisomerization.

Multi-modal 3D imaging of radionuclides using multiple hybrid Compton cameras.

For radiological diagnosis and radionuclide therapy, X-ray and gamma-ray imaging technologies are essential. Single-photon emission tomography (SPECT) and positron emission tomography (PET) play essential roles in radiological diagnosis, such as the early detection of tumors. Radionuclide therapy is also rapidly developing with the use of these modalities. Nevertheless, a limited number of radioactive tracers are imaged owing to the limitations of the imaging devices. In a previous study, we developed a hybrid Compton camera that conducts simultaneous Compton and pinhole imaging within a single system. In this study, we developed a system that simultaneously realizes three modalities: Compton, pinhole, and PET imaging in 3D space using multiple hybrid Compton cameras. We achieved the simultaneous imaging of Cs-137 (Compton mode targeting 662 keV), Na-22 (PET mode targeting 511 keV), and Am-241 (pinhole mode targeting 60 keV) within the same field of view. In addition, the imaging of Ga-67 and In-111, which are used in various diagnostic scenarios, was conducted. We also verified that the 3D distribution of the At-211 tracer inside a mouse could be imaged using the pinhole mode.

Neopentyl Glycol as a Scaffold to Provide Radiohalogenated Theranostic Pairs of High In Vivo Stability.

The high in vivo stability of 2,2-dihydroxymethyl-3-[18F]fluoropropyl-2-nitroimidazole ([18F]DiFA) prompted us to evaluate neopentyl as a scaffold to prepare a radiotheranostic system with radioiodine and astatine. Three DiFA analogues with one, two, or without a hydroxyl group were synthesized. While all 125I-labeled compounds remained stable against nucleophilic substitution, only a 125I-labeled neopentyl glycol was stable against cytochrome P450 (CYP)-mediated metabolism and showed high stability against in vivo deiodination. 211At-labeled neopentyl glycol also remained stable against both nucleophilic substitution and CYP-mediated metabolism. 211At-labeled neopentyl glycol showed the biodistribution profiles similar to those of its radioiodinated counterpart in contrast to the 125I/211At-labeled benzoate pair. The urine analyses confirmed that 211At-labeled neopentyl glycol was excreted in the urine as a glucuronide conjugate with the absence of free [211At]At-. These findings indicate that neopentyl glycol would constitute a promising scaffold to prepare a radiotheranostic system with radioiodine and 211At.

Ultrafast Dynamics of a Solvatochromic Dye, Phenol Blue: Tautomerization and Coherent Wavepacket Oscillations.

Femtosecond time-resolved transient absorption spectroscopy was performed for a nonfluorescent solvatochromic dye, phenol blue, N-(4-dimethylaminophenyl)-1,4-benzoquinoneimine, which exhibits ultrafast nonradiative decay due to its flexible molecular structure. By exciting the molecule in ethanol (EtOH) solution with two excitation wavelengths located at shorter- and longer-wavelength sides of the visible absorption band, we observed ultrafast nonradiative decay from the excited state, followed by spectral evolution in the ground state. The nonradiative decay in the subpicosecond range creates a vibrationally hot ground state with the lifetime in the picosecond range. Subsequently, a tautomer that absorbs at shorter wavelengths is produced from the hot state, which causes a red shift of the ground-state bleach (GSB). The tautomerization presumably involves twisting of the benzoquinoneimine moiety induced by the breaking of the hydrogen bond (H-bond) between the solute and the solvent molecules. The recombination of the H-bond occurs with a time constant of ∼30 ps, and the system returns to its original state. We also observed low-frequency coherent wavepacket oscillations that modulate the GSB with dephasing times similar to the excited-state lifetime.

Synthesis of [211At]4-astato-L-phenylalanine by dihydroxyboryl-astatine substitution reaction in aqueous solution.

Astatine-211 (211At)-labeled phenylalanine is expected to be a promising agent for targeted alpha-particle therapy for the treatment of patients with glioma. The existing reactions to prepare the labeled compound usually require organic solvents and metals that are toxic and hazardous to the environment. In this study, we developed a novel method wherein astatination was realized via the substitution of 211At for a dihydroxyboryl group coupled to phenylalanine. [211At]4-astato-L-phenylalanine was obtained as the carrier-free product in aqueous medium in high radiochemical yields (98.1 ± 1.9%, n = 5). The crude reaction mixture was purified by solid-phase extraction, and the radiochemical purity of the product was 99.3 ± 0.7% (n = 5). The high yield and purity were attributed to the formation of [211At]AtI and AtI2- as the reactive intermediates in the astatination reaction. The reaction did not require any organic solvents or toxic reagents, suggesting that this method is suitable for clinical applications.

Synthesis, structural characterization, and optical properties of benzo[f]naphtho[2,3-b]phosphoindoles.

Phosphole-fused π-conjugated acenes have been attracting interest because of the attractive features of the phosphole moiety, such as fluorescence and chemically modifiable properties. Herein, 6-phenyl-6H-benzo[f]naphtho[2,3-b]phosphoindole was prepared by reacting dichlorophenylphosphine with a dilithium intermediate derived from 3,3'-dibromo-2,2'-binaphthyl. Various derivatives, such as a phospholium salt and a borane-phosphole complex with functional groups on the phosphorus atom were synthesized using the obtained phosphole as a common starting material. Single-crystal X-ray analysis of the parent benzo[f]naphtho[2,3-b]phosphoindole revealed that the pentacyclic ring is almost planar. Fluorescence spectroscopy data showed that the phosphole derivatives, such as phosphine oxide and the phospholium salt and borane complex exhibited photoluminescence in chloroform.

Intensity-dependent self-induced dual-color laser phase modulation and its effect on terahertz generation.

Powerful, broadband terahertz (THz) pulses and its application attract an exponential growth of interests. Dual-color laser filamentation in gases is one of the promising THz sources because of the scalability of the THz energy and wavelength with input parameters. But the additional phase induced by the nonlinearities associated with high intensities cannot be neglected because it may result in modulation of the THz waves. We investigate the influences of the infrared pump energy and air dispersion on the terahertz generation in dual-color laser filament. We observe that optimum dual-color laser relative phase of the THz generation undergoes a linear shift with increasing pump energy due to the intensity-induced refractive index change. This phase shift is verified by the spectral broadening of a two-color laser affected by the same mechanism. The result improves our understanding of the theoretical framework for a higher power THz source.

Development of high-resolution YAP(Ce) x-ray camera for the imaging of astatine-211(At-211) in small animals.

PURPOSE: Astatine-211 (At-211) is a promising alpha emitter for radionuclide therapy. High-resolution in vivo imaging of At-211 in small animals is needed for the development of At-211 radiopharmaceuticals. For this purpose, we developed a low-energy x-ray camera using a thin YAlO3 :Ce (YAP(Ce)) plate to image the low-energy x rays (73-87 keV) from the daughter radionuclide of At-211 (Po-211). METHOD: We optically coupled a 38 × 38 × 1-mm YAP (Ce) plate to a position-sensitive photomultiplier (PSPMT) to develop an imaging detector. A pinhole or a parallel hole collimator was attached to the imaging detector, and the performance was measured for 60-keV gamma photons. With the developed x-ray camera, we carried out imaging of a mouse that had been administered At-211-NaAt. RESULTS: The intrinsic spatial resolution of the YAP (Ce) x-ray camera was approximately 1.2 mm FWHM, and the energy resolution was 22% FWHM. With a 5-mm-thick parallel hole collimator, the spatial resolution was 3.8 mm FWHM with a sensitivity of 8 × 10-4 at 10 mm, which is a typical distance from the surface of the collimator to a subject in mouse imaging. Using a 1-mm diameter pinhole collimator, the spatial resolution was 1.8 mm FWHM with a sensitivity of 3.5 × 10-4 at 10 mm from the collimator. In the mouse images measured by the developed x-ray camera, we could clearly observe that the At-211 accumulated in the thyroid gland and the stomach of the mouse. CONCLUSION: We concluded that the YAP (Ce) x-ray camera is useful for in vivo imaging of At-211.

Evidence of Direct Dissolution of CO2 into the Ionic Liquid [C4min] [NTf2] during Their Initial Interaction.

Ionic liquids (ILs) are known for their high ability to capture CO2. However, the mechanism of CO2 solubility into ILs during their initial interaction remains controversial. In this study, we analyzed the initial dissolution of CO2 into an IL 1-butyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide ([C4min] [NTf2]) by measuring its solubility using a combination of a molecular beam and a flowing liquid jet sheet beam (FJSB) and the King and Wells method (KW method). The temperature dependence of the initial dissolution probability indicates that the solubility of CO2 in the IL [C4min] [NTf2] increases with increasing temperature. This result is not consistent with what has been reported in an equilibrium state. The initial dissolution probability was well-fitted by the Vogel-Fulcher-Tammann (VFT) equation, which describes the dynamical cage structure in IL systems. We also find that the initial dissolution probability was correlated to the cage lifetime and correlation length. The simple model of CO2 dissolution into an IL with the cage model was implemented to explain the experimental results in this study. Our results indicate that the initial dissolution of CO2 into the IL corresponds to a direct solution and not an uptake process.

Performance demonstration of a hybrid Compton camera with an active pinhole for wide-band X-ray and gamma-ray imaging.

X-ray and gamma-ray imaging are technologies with several applications in nuclear medicine, homeland security, and high-energy astrophysics. However, it is generally difficult to realize simultaneous wide-band imaging ranging from a few tens of keV to MeV because different interactions between photons and the detector material occur, depending on the photon energies. For instance, photoabsorption occurs below 100 keV, whereas Compton scattering dominates above a few hundreds of keV. Moreover, radioactive sources generally emit both X-ray and gamma-ray photons. In this study, we develop a "hybrid" Compton camera that can simultaneously achieve X-ray and gamma-ray imaging by combining features of "Compton" and "pinhole" cameras in a single detector system. Similar to conventional Compton cameras, the detector consists of two layers of scintillator arrays with the forward layer acting as a scatterer for high-energy photons (> 200 keV) and an active pinhole for low-energy photons (< 200 keV). The experimental results on the performance of the hybrid camera were consistent with those from the Geant4 simulation. We simultaneously imaged [Formula: see text]Am (60 keV) and [Formula: see text]Cs (662 keV) in the same field of view, achieving an angular resolution of 10[Formula: see text] (FWHM) for both sources. In addition, imaging of [Formula: see text]At was conducted for the application in future nuclear medicine, particularly radionuclide therapy. The initial demonstrative images of the [Formula: see text]At phantom were reconstructed using the pinhole mode (using 79 keV) and Compton mode (using 570 keV), exhibiting significant similarities in source-position localization. We also verified that a mouse injected with 1 MBq of [Formula: see text]At can be imaged via pinhole-mode measurement in an hour.

Rate Constants for Reactions of HCCO and HCCCO Radicals with O2 over the Temperature Range 243-423 K.

A pulsed laser photolysis-photoionization mass spectrometer system has been employed to measure the rate constants of HCCO + O2 and HCCCO + O2 over the temperature range 243-423 K in 1.2-8.4 Torr of He or N2. Radicals of HCCO and HCCCO were produced by 193 nm ArF laser photolysis of ethyl ethynyl ether and methyl propiolate, respectively. HCCO was photoionized by a Kr resonance lamp with a CaF2 window (10.03 eV), and HCCCO was ionized by a Xe lamp with a sapphire window (8.44 eV). Both ions were detected as parent ions in a quadrupole mass spectrometer. From analysis of the time profiles of the ion signals for various O2 concentrations, the overall rate constants at 298 K are represented by the values k2 = (6.3 ± 1.0) × 10-13 for HCCO + O2 and k5 = (5.7 ± 0.6) × 10-12 for HCCCO + O2 in the units cm3 molecule-1 s-1. The rate coefficients for the two reactions can be described by k2(T) = (1.5-0.7+1.5) × 10-12 exp[-(225 ± 220)/T] and k5(T) = (1.8-0.9+1.9) × 10-12 exp[(343 ± 228)/T] in the units cm3 molecule-1 s-1 over the temperature range 243-423 K.

Targeted alpha therapy using astatine (211At)-labeled phenylalanine: A preclinical study in glioma bearing mice.

Phenylalanine derivatives, which target tumors especially through L-type amino acid transporter-1 (LAT1), have elicited considerable attention. In this study, we evaluated the treatment effect of phenylalanine labeled with the alpha emitter astatine (211At-PA) in tumor bearing mice. The C6 glioma, U-87MG, and GL261 cell lines were subjected to a cellular 211At-PA uptake analysis that included an evaluation of the uptake inhibition by the system L amino acid transporter inhibitor 2-aminobicyclo-(2,2,1)-heptane-2-carboxylic acid (BCH). BCH significantly inhibited para-211At-PA uptake in C6 glioma (12.2 ± 0.8%), U-87MG (27.6 ± 1.1%), and GL261 (12.6 ± 2.0%) cells compared to baseline, suggesting an uptake contribution by system L amino acid transporters. Subsequently, xenograft and allograft models were prepared by subcutaneously injecting C6 glioma (n = 12) or GL-261 cells (n = 12), respectively. C6 glioma mice received three 211At-PA doses (0.1, 0.5, or 1 MBq, n = 3/dose), while GL261 mice received one high dose (1 MBq, n = 7). 211At-PA exhibited a tumor growth suppression effect in C6 glioma models in a dose-dependent manner as well as in GL-261 models. This phenylalanine derivative labeled with astatine may be applicable as an alpha therapy that specifically targets system L amino acid transporters.

Soft X-Ray Imaging of Cellular Carbon and Nitrogen Distributions in Heterocystous Cyanobacteria.

Soft x-ray microscopy (SXM) is a minimally invasive technique for single-cell high-resolution imaging as well as the visualization of intracellular distributions of light elements such as carbon, nitrogen, and oxygen. We used SXM to observe photosynthesis and nitrogen fixation in the filamentous cyanobacterium Anabaena sp. PCC 7120, which can form heterocysts during nitrogen starvation. Statistical and spectroscopic analyses from SXM images around the K-absorption edge of nitrogen revealed a significant difference in the carbon-to-nitrogen (C/N) ratio between vegetative cells and heterocysts. Application of this analysis to soft x-ray images of Anabaena sp. PCC 7120 revealed inhomogenous C/N ratios in the cells. Furthermore, soft x-ray tomography of Anabaena sp. PCC 7120 revealed differing cellular C/N ratios, indicating different carbon and nitrogen distributions between vegetative cells and heterocysts in three dimensions.

Structure determination of molecules in an alignment laser field by femtosecond photoelectron diffraction using an X-ray free-electron laser.

We have successfully determined the internuclear distance of I2 molecules in an alignment laser field by applying our molecular structure determination methodology to an I 2p X-ray photoelectron diffraction profile observed with femtosecond X-ray free electron laser pulses. Using this methodology, we have found that the internuclear distance of the sample I2 molecules in an alignment Nd:YAG laser field of 6 × 1011 W/cm2 is elongated by from 0.18 to 0.30 Å "in average" relatively to the equilibrium internuclear distance of 2.666 Å. Thus, the present experiment constitutes a critical step towards the goal of femtosecond imaging of chemical reactions and opens a new direction for the study of ultrafast chemical reaction in the gas phase.

Photoelectron diffraction from laser-aligned molecules with X-ray free-electron laser pulses.

We report on the measurement of deep inner-shell 2p X-ray photoelectron diffraction (XPD) patterns from laser-aligned I2 molecules using X-ray free-electron laser (XFEL) pulses. The XPD patterns of the I2 molecules, aligned parallel to the polarization vector of the XFEL, were well matched with our theoretical calculations. Further, we propose a criterion for applying our molecular-structure-determination methodology to the experimental XPD data. In turn, we have demonstrated that this approach is a significant step toward the time-resolved imaging of molecular structures.

Real-time vibrational dynamics in chlorophyll a studied with a few-cycle pulse laser.

We use a 6.8-fs laser as the light source for broad-band femtosecond pump-probe real-time vibrational spectroscopy to investigate both electronic relaxation and vibrational dynamics of the Q(y)-band of Chl-a at 293 K. More than 25 vibrational modes coupled to the Q(y) transition are observed. Eleven of them have been clarified predominantly due to the excited state, and six of them are concluded to be nearly exclusively resulting from the ground-state wave-packet motion. Moreover, thanks to the broad-band detection over 5000 cm⁻¹, the modulated signals due to the excited state vibrational coherence are observed on both sides of the 0-0 transition with equal separation. The corresponding nonlinear process has been studied using a three-level model, from which the probe wavelength dependence of the phase of the periodic modulation can be calculated. The probe wavelength dependence of the vibrational amplitude is interpreted in terms of the interaction between the "pump" or "laser," Stokes, and anti-Stokes field intermediated by the molecular vibrations. In addition, an excited state absorption peak at ~709 nm has been observed. To the best of our knowledge, this is the first study of broad-band real-time vibrational spectroscopy in Chl-a.

Clean sub-8-fs pulses at 400 nm generated by a hollow fiber compressor for ultraviolet ultrafast pump-probe spectroscopy.

Clean 7.5 fs pulses at 400 nm with less than 3% energy in tiny satellite pulses were obtained by spectral broadening in a hollow fiber and dispersive compensating using a prism pair together with a deformable mirror system. As an example, this stable and clean pulse was used to study the ultrafast pump-probe spectroscopy of photoactive yellow protein. Moreover, the self-diffraction signal shows a smoothed and broadened laser spectrum and is expected to have a further clean laser pulse, which makes it more useful in the ultrafast pump-probe spectroscopy in the future.

Multiple mode coupling in Cy3 molecules by impulsive coherent vibrational spectroscopy using a few-cycle laser pulse.

Multiple vibrational mode coupling that induces the missing mode effect and Duschinsky rotation on the potential energy surface of the S(1) state in the Cy3 molecule was clarified by real-time ultrafast spectroscopy with a few-cycle laser pulse. The contributions of homogeneous and inhomogeneous dephasing to the total dephasing time were found to be 55% and 45%, respectively.