Optimization of SIMS analytical parameters for water content measurement of olivine

Secondary ion mass spectrometry (SIMS) has a wide range of applications in Earth Science research, thanks to its high precision and sensitivity, and its capacity in direct insitu micromeasurement. The technique is operated in ultra-high vacuum (UHV) conditions, especially for the measurement of volatiles such as hydrogen, or the water content in nominally anhydrous minerals (NAMs). To minimize the water background and obtain accurate and precise water contents in NAMs (eg, olivine) critical parameters such as presputtering time, field aperture (FA), dynamic transfer on/off, and primary beam current intensity were investigated for a CAMECA IMS 1280-HR system. When the chamber vacuum reaches approximately 2 × 10⁻⁹ mbar, we set the DTOS OFF, raster size to 50 μm and primary beam current to 5 nA, and used 2000 μm FA and 170-second presputtering time. Consequently, an approximately 1.2 ppmw water background and 3.6 ppmw limit of detection (LOD) were yielded, from analyzing the San Carlos olivine. Meanwhile, the water content and homogeneity of a range of olivine minerals were characterized for potential use as reference materials for SIMS water content measurement. Olivine water content calibration curve was also established by comparing the Fourier transform infrared (FTIR) results with the SIMS-measured ¹⁶O¹H⁻/¹⁶O⁻ ratios. Accuracy and precision of water content measurement were estimated to be better than approximately 10% in this study.     

Analysis of A-DLTS spectra of MOS structures with thin NAOS SiO2 layers

A set of MOS structures with thin SiO₂ layers prepared by nitric acid oxidation (NAOS) method was investigated using acoustic deep level transient spectroscopy (A-DLTS) to explain the role of annealing treatment (post-oxidation annealing (POA) and post-metallization annealing (PMA)) at different conditions on the distribution of interface states. The activation energies of interface states and the corresponding capture cross-section were calculated both from Arrhenius plots constructed for individual peaks of the A-DLTS spectra and applying the method of modeling of measured acoustic spectra. The energy distribution of the interface states was determined also from the dependence of acoustoelectric response signal (ARS) on the external bias voltage (U _ac - V _G curves). By comparing the A-DLTS spectra, U _ac - V _G characteristics and some electrical measurements (G-V, I-V curves) of investigated MOS structures with no treatment with those treated with POA and/or PMA, the role of individual treatments was observed. The definite decrease of the interface states in the structures with the PMA treatment in comparison with the POA treatment was confirmed too.     

Analysis of the pure-rotational spectrum in the ν28 = 1 excited torsional state and torsional couplings of trans-ethyl methyl ether

The trans-ethyl methyl ether molecule has three low-lying torsional modes, that is, two inequivalent methyl internal rotations and an asymmetric skeletal torsion. The internal rotations of the CCH₃ and OCH₃ methyl rotors and the skeletal torsion correspond to the vibrational modes, ν₂₈, ν₂₉ and ν₃₀ respectively. In this study, the microwave absorption spectrum in the ν₂₈ = 1 CCH₃ torsional state was analyzed for the first time. Nine hundred fifty seven lines up to J = 48 and K = 4 were assigned, and the rotational, centrifugal distortion and internal rotational tunneling parameters were determined with the use of a tunneling matrix formalism. By combining the present results on the ν₂₈ = 1 torsional state with those for the ν₃₀ = 1 skeletal torsional state and the ν₂₉ = 1 OCH₃ torsional state, torsional couplings are estimated in order to understand quantitatively the inverted A/E sequence patterns observed for those three excited torsional states.     

Special functions associated with a certain fourth-order differential equation

We develop a theory of “special functions” associated with a certain fourth-order differential operator D_m,n\mathcal{D}_{\mu,\nu} on ℝ depending on two parameters μ,ν. For integers μ,ν≥−1 with μ+ν∈2ℕ₀, this operator extends to a self-adjoint operator on L ²(ℝ₊,x ^μ+ν+1 dx) with discrete spectrum. We find a closed formula for the generating functions of the eigenfunctions, from which we derive basic properties of the eigenfunctions such as orthogonality, completeness, L ²-norms, integral representations, and various recurrence relations.     

Optical pulsation mechanism based on optical near-field interactions

We theoretically demonstrate optical pulsation based on optical near-field interactions between quantum nanostructures. It is composed of two quantum dot systems, each of which consists of a combination of smaller and larger quantum dots, so that optical excitation transfer occurs. With an architecture in which the two systems take the role of a timing delay and frequency up-conversion, we observe pulsation in populations pumped by continuous-wave light irradiation. The pulsation is induced with suitable setting of parameters associated with the optical near-field interactions. This will provide critical insights toward the design and implementation of experimental nanophotonic pulse generating devices.     

Control of Chromophore Symmetry by Positional Isomerism of Peripheral Substituents

The first example of the control of porphyrinoid chromophore symmetry based on the positional isomerism of peripheral substituents has been achieved by preparing tetraazaporphyrins (TAPs) with C_4h, D_2h, C_2v, and C_s symmetry due to the relative arrangement of peripheral tert‐butylamino and cyano groups as push and pull substituents, respectively. The four structural isomers were successfully isolated and characterized by ¹H NMR spectroscopy and X‐ray crystallography. The band morphology in the Q‐band region varies depending on the molecular symmetry due to the significant perturbation introduced into the chromophore by the push and pull substituents. The C_4h and C_2v isomers exhibit a single Q band, whereas the Q bands of the D_2h and C_s isomers show a marked splitting. The magnetic circular dichroism spectra indicate that the push–pull TAPs retain the properties of the 16‐membered 18π‐electron perimeter generally observed for porphyrinoids. Theoretical calculations have demonstrated that the perturbation introduced by the substituents lowers the D_4h symmetry of the parent TAP π‐conjugated system, and this results in significant spectral changes. A novel approach to the fine‐tuning of the spectral properties of porphyrinoids based on changes in the chromophore symmetry is described.     

Synthesis of New Chlorin e6 Trimethyl and Protoporphyrin IX Dimethyl Ester Derivatives and Their Photophysical and Electrochemical Characterizations

In view of increasing demands for efficient photosensitizers for photodynamic therapy (PDT), we herein report the synthesis and photophysical characterizations of new chlorin e₆ trimethyl ester and protoporphyrin IX dimethyl ester dyads as free bases and Zn^II complexes. The synthesis of these molecules linked at the β‐pyrrolic positions to pyrano[3,2‐c]coumarin, pyrano[3,2‐c]quinolinone, and pyrano[3,2‐c]naphthoquinone moieties was performed by using the domino Knoevenagel hetero Diels–Alder reaction. The α‐methylenechromanes, α‐methylenequinoline, and ortho‐quinone methides were generated in situ from a Knoevenagel reaction of 4‐hydroxycoumarin, 4‐hydroxy‐6‐methylcoumarin, 4‐hydroxy‐N‐methylquinolinone, and 2‐hydroxy‐1,4‐naphthoquinone, respectively, with paraformaldehyde in dioxane. All the dyads as free bases and as Zn^II complexes were obtained in high yields. All new compounds were fully characterized by 1D and 2D NMR techniques, UV/Vis spectroscopy, and HRMS. Their photophysical properties were evaluated by measuring the fluorescence quantum yield, the singlet oxygen quantum yield by luminescence detection, and also the triplet lifetimes were correlated by flash photolysis and intersystem crossing (ISC) rates. The fluorescence lifetimes were measured by a time‐correlated single photon count (TCSPC) method, fluorescence decay associated spectra (FDAS), and anisotropy measurements. Magnetic circular dichroism (MCD) and circular dichroism (CD) spectra were recorded for one Zn^II complex in order to obtain information, respectively, on the electronic and conformational states, and interpretation of these spectra was enhanced by molecular orbital (MO) calculations. Electrochemical studies of the Zn^II complexes were also carried out to gain insights into their behavior for such applications.     

Efficient transformation of 7,14-dihydroxy-ent-kaurenes to novel ent-abietanes having cis-fused α-methylene γ-lactones under Mitsunobu reaction conditions and their cytotoxicities

Transformation of plant-origin 7,14-dihydroxy-ent-kaurenes to ent-abietanes having a cis-fused α-methylene γ-lactones was accomplished efficiently under the Mitsunobu reaction conditions. The yields of the desired products were apparently influenced by the steric hindrance at C-1. The cytotoxic activity on P388 murine leukemia cells of the ent-abietanes having cis-fused α-methylene γ-lactones produced were assayed.     

Hyrtimomines,indole alkaloids from Okinawan marine sponges Hyrtios spp.

Six new indole alkaloids, hyrtimomines F–K (1–6), were isolated from Okinawan marine sponges Hyrtios spp. The structures of 1–6 were elucidated on the basis of spectroscopic analysis. Hyrtimomine F (1) is a structurally unique bisindole alkaloid possessing an α-keto-?-caprolactam ring, while hyrtimomine G (2) is a symmetrical bisindole alkaloid. Hyrtimomines H–K (3–6) are indole alkaloids possessing β-carboline skeleton with an imidazolium unit. Antimicrobial activities of hyrtimomines F–K (1–6) were evaluated.