Construction of high-throughput magnetic circular dichroism measurement system and its application to research on magnetic and optical properties of phthalocyanine complexes.

Magnetic circular dichroism (MCD) spectroscopy is a powerful method for evaluating the electronic structure and magnetic and optical properties of molecules. In particular, MCD measurements have been performed on phthalocyanines and porphyrins with various central metal ions, axial ligands, and substituents to elucidate their properties. It is essential to develop a robust high-throughput technique to perform these measurements comprehensively and efficiently. However, MCD spectroscopy requires very high optical quality for each component of the instrument, and even slight cell distortions can impair the baseline flatness. Consequently, when versatility and data quality are important, an optical system designed for a microplate reader is not suitable for the MCD spectrometer. Therefore, in this study, we develop a new magnetic flow-through cell and combine it with an existing CD spectrometer and autosampler to construct a high-throughput system. The effectiveness and performance of this new system are then evaluated. In addition, based on the MCD and absorption spectra of various phthalocyanine complexes, the effects of substituents and solvents on their magnetic and optical properties and the causes of these effects are discussed. The results demonstrate that this system is effective for the evaluation of the physicochemical properties of various phthalocyanine complexes.

Electronic structure analysis of phthalocyanine complexes using magnetic circular dichroism and magnetic circularly polarized luminescence spectroscopy.

In the study of phthalocyanine complexes using magnetic circular dichroism (MCD) spectroscopy, the electronic structure of excited states is generally discussed based on the rigid-shift approximation, in which the band profiles for left-handed circularly polarized (lcp) and right-handed circularly polarized (rcp) light are assumed to be the same. This assumption may not necessarily be valid for cases where there are multiple initial states having different geometries. Magnetic circularly polarized luminescence (MCPL) from phthalocyanine complexes can be regarded as an example of such cases, since the two degenerate emission states are split in a magnetic field and can undergo a structural deformation. Here, we investigated an alternative approach, where the lcp and rcp components are independently determined. This method, which we refer to as the direct-separation approach, allows direct determination of the distribution of the two emission states as well as the orbital angular momentum L z $$ \left|{L}_z\right| $$ . Using this approach, L z $$ \left|{L}_z\right| $$ and the distribution were determined from MCD and MCPL spectra of a series of phthalocyanine complexes. Comparison of the two methods shows that the rigid-shift and the direct-separation approaches give practically equivalent results for the systems under study, but the latter is advantageous for systems where the former is not applicable.

Attenuated Total Reflection Infrared and Far-Infrared, and Raman Spectroscopy Studies of Minerals, Rocks, and Biogenic Minerals.

Attenuated total reflection infrared (ATR-IR, 4000-400 cm-1), ATR-far-IR (ATR-FIR, 400-50 cm-1), and Raman spectra (4000-10 cm-1) were measured for calcium carbonate, three kinds of minerals (calcite, aragonite, and quartz), two kinds of rocks (obsidian and pumice), and four kinds of biogenic minerals, i.e., coral (aragonite), Ruditapes philippinarum (aragonite), Meretrix lusoria (aragonite), and Corbicula japonica (aragonite), to investigate the polymorphism of minerals and biogenic minerals, differences in the crystal structure among aragonite and aragonite biogenic minerals, water in the minerals and biogenic minerals, Boson peaks of obsidian and pumice, very small amounts of carotenoids in the three kinds of shells, and so on. In this study, we put some emphasis on the low-frequency region of IR (FIR) and Raman spectra. ATR-FIR spectra were measured down to 50 cm-1 and Raman spectra were obtained down to 10 cm-1. Second derivative spectra were calculated for the FIR spectra. It has been found from the present study that the FIR spectra are the most powerful for exploring polymorphism and differences in the crystal structure among aragonite and aragonite biogenic minerals. A Boson peak, which is a characteristic low-frequency Raman band for amorphous materials, was observed at around 40 cm-1 in the Raman spectra of obsidian and pumice. The Boson peak of pumice is located at a lower frequency by 12 cm-1 than that of obsidian, indicating that the mean atomic volume of pumice is larger than that of obsidian. The present study has revealed that IR spectra are useful to investigate the amounts and structure of fluid and bound water. Moreover, it has also been found that Raman spectra can detect a very tiny amount of carotenoids in the shells due to the resonance Raman effect.

Characterization of Carbohydrates, Amino Acids, Viscosity, and Antioxidant Capacity in Rice Wines Made in Saitama, Japan, with Different Sake Rice.

We investigated the physicochemical properties of Japanese rice wines, including their functional properties and carbohydrate and amino acid content in solution and solid state. Three samples were tested. The glucose, allose, and raffinose contents in samples (A, B, C) in g/100 g were (3.47, 3.45, 7.05), (1.60, 1.63, 1.61), and (2.14, 2.75, 1.49), respectively. The total amino acid in µmol/mL was (3.1, 3.5, 4.4). Glutamic acid, alanine, and arginine varied in content across the samples. The viscosity (10 °C) and activation energy (ΔE) calculated using the Andrade equation were (2.81 ± 0.03, 2.74 ± 0.06, 2.69 ± 0.03) mPa-s and (22.3 ± 1.1, 22.0 ± 0.2, 21.3 ± 0.5) kJ/mol, respectively. Principal component analysis using FT-IR spectra confirmed the separation of the samples into principal components 2 and 3. The IC50 values from the DPPH radical scavenging test were (2364.7 ± 185.3, 3041.9 ± 355.1, 3842.7 ± 228.1) µg/mL. Thus, the three rice wines had different carbohydrate and amino acid contents, viscosities, and antioxidant capacities.

Mogamulizumab for post-transplant relapse of adult T-cell leukemia/lymphoma: a case study.

Mogamulizumab (MOG), a humanized monoclonal anti-CCR4 antibody, exerts strong antibody-dependent cellular cytotoxic effects on CCR4-positive adult T-cell leukemia/lymphoma (ATLL) cells. As CCR4 is highly expressed on regulatory T cells as well as ATLL cells, pre-transplant MOG induces severe graft-versus-host disease (GvHD). However, limited data are available on post-transplant use of MOG for relapsed ATLL. Here we describe the case of a patient with ATLL who experienced post-transplant relapse with involvement of peripheral blood, skin, lungs, and lymph nodes. Neither tacrolimus dose reduction nor cytotoxic chemotherapy was effective, but a single dose of MOG (1 mg/kg) induced complete remission. After treatment with MOG, leukemic cells in the peripheral blood rapidly disappeared, and the skin, lymph node, and lung lesions gradually regressed. Most notably, the long-term remission was accompanied by recurrence of moderate acute GvHD (grade II, skin stage 2, gut stage 1, liver stage 0). Our findings indicate that MOG can augment allogeneic immune-mediated anti-tumor reactions through graft-versus-ATLL (GvATLL) even during post-transplant relapse involving the lymph nodes and lungs, along with inducing GvHD.

Performance Comparison of Spectral Distance Calculation Methods.

Circular dichroism (CD) spectroscopy is a widely used technique for assessing the higher-order structure (HOS) of biopharmaceuticals, including antibody drugs. Since the International Council for Harmonisation of Technical Requirements for Pharmaceuticals for Human Use established quality control guidelines, objective evaluation of spectral similarity has been required in order to assess structural comparability. Several spectral distance quantification methods and weighting functions to increase sensitivity have been proposed, but not many reports have compared their performance for CD spectra. We constructed comparison sets that combine actual spectra and simulated noise and performed a comprehensive performance evaluation of each spectral distance calculation method and weighting function under conditions that consider spectral noise and fluctuations from pipetting errors. The results showed that using the Euclidean distance or Manhattan distance with Savitzky-Golay noise reduction is effective for spectral distance assessment. For the weighting function, it is preferable to combine the spectral intensity weighting function and the noise weighting function. In addition, the introduction of the external stimulus weighting function should be considered to improve the sensitivity. It is crucial to select the weighting function based on the balance between spectral changes and noise distributions for robust, sensitive antibody HOS similarity assessment.

Post-transplant food anaphylaxis in an adult cord blood transplant recipient (Ms. No. IJHM-D-20-01037R1).

Transplant acquired food allergy (TAFA) is a well-known complication following pediatric liver transplantation, but post-cord blood transplantation (post-CBT) TAFA has rarely been reported. Here, we describe a case of new-onset food anaphylaxis after CBT in an adult patient that demonstrates that post-CBT allergen-challenge is not a risk for long-term allergic sensitization even in adult recipients. The patient was a 39-year-old Japanese man with aggressive NK cell leukemia. He had no previous history of allergies. After receiving CBT, the patient had an unbalanced diet with high preference for bread, bananas, miso-soup, cow's milk, cheese, egg, sesame and buckwheat soba noodles, and experienced repeated diarrhea. Six months later, he developed symptoms such as vomiting, epigastric pain, diarrhea, high fever and hypotension. The condition was initially diagnosed as enterocolitis, but symptoms recurred after consumption of buckwheat. Anaphylaxis induced by buckwheat was confirmed with serum radioallergosorbent tests (RAST), showing allergen-specific IgE for buckwheat (greater than 100 U/mL, Class 6) and egg ovomucoid (Class 4). Nineteen months after a buckwheat and egg-free diet, serum RAST for buckwheat and egg significantly improved. As a result, the patient acquired a tolerance and was able to consume buckwheat and egg without allergic symptoms.

Vitrification is essential for anhydrobiosis in an African chironomid, Polypedilum vanderplanki.

Anhydrobiosis is an extremely dehydrated state in which organisms show no detectable metabolism but retain the ability to revive after rehydration. Thus far, two hypotheses have been proposed to explain how cells are protected during dehydration: (i) water replacement by compatible solutes and (ii) vitrification. The present study provides direct physiological and physicochemical evidence for these hypotheses in an African chironomid, Polypedilum vanderplanki, which is the largest multicellular animal capable of anhydrobiosis. Differential scanning calorimetry measurements and Fourier-transform infrared (FTIR) analyses indicated that the anhydrobiotic larvae were in a glassy state up to as high as 65 degrees C. Changing from the glassy to the rubbery state by either heating or allowing slight moisture uptake greatly decreased the survival rate of dehydrated larvae. In addition, FTIR spectra showed that sugars formed hydrogen bonds with phospholipids and that membranes remained in the liquid-crystalline state in the anhydrobiotic larvae. These results indicate that larvae of P. vanderplanki survive extreme dehydration by replacing the normal intracellular medium with a biological glass. When entering anhydrobiosis, P. vanderplanki accumulated nonreducing disaccharide trehalose that was uniformly distributed throughout the dehydrated body by FTIR microscopic mapping image. Therefore, we assume that trehalose plays important roles in water replacement and intracellular glass formation, although other compounds are surely involved in these phenomena.

Time-resolved step-scan infrared imaging system utilizing a linear array detector.

A time-resolved infrared (IR) imaging system combined with a multichannel IR microscope, which utilizes a 16 channel linear array (LA) detector, and step-scan Fourier transform infrared (FT-IR) microscope was developed. The LA detector integrates a readout circuit on each detector element, so the detected signals can be read simultaneously. Thus, this system can perform high speed imaging using the step-scan method, similar to a single channel detector. To verify the capabilities of this system, a reflective sample was examined whose position was altered using a piezo actuator activated by an alternating voltage. In addition, the localization of relaxation dynamics for the liquid crystal (LC) molecules in an LC cell under oscillating electric field conditions was detected by this system.

Absolute stereochemistry of citrinadins a and B from marine-derived fungus.

[Structure: see text]. Citrinadin A (2) is a pentacyclic indolinone alkaloid isolated from the cultured broth of a fungus, Penicillium citrinum, which was separated from a marine red alga. The absolute stereochemistry of the pentacyclic core in 2 and its new congener, citrinadin B (1), was elucidated by analysis of the ROESY spectrum for the chlorohydrin derivative (3) of 1 as well as comparison of the electronic circular dichroism (ECD) spectra for 1 and 2 with those of known spirooxiindole alkaloids. On the other hand, the absolute configuration at C-21 bearing an epoxide ring was assigned as S by comparison of the vibrational circular dichroism (VCD) spectra of 1 with those of model compounds 2S- and 2R-2,3-epoxy-3,3-dimethyl-1-phenylpropan-1-one (4a and 4b, respectively).

Supercritical CO(2) fluid extraction of crystal water from trehalose dihydrate. Efficient production of form II (T(alpha)) phase.

Form II is a kind of metastable crystalline form of trehalose anhydrate, and it is easily converted to the dihydrate crystal by absorbing water in moist atmosphere at room temperature (Akao et al., Carbohydr. Res. 2001, 334, 233-241). It can be utilized as an edible and nontoxic desiccant, and thus its efficient production from the dihydrate is significant from a viewpoint of industrial applications. In this study, we attempt to extract crystal water from the dihydrate using supercritical CO(2). We examine the dependence of extraction efficiency on the extraction time, the temperature and pressure of the fluid. Then, FTIR measurements are carried out to detect the extracted water and to identify the polymorphic phase of the sugar sample after the extraction treatment. In particular, the so-called first derivative euclidean distance analysis for IR spectra is shown to be quite useful for the structural identification. Consequently, we demonstrate that form II is produced from the dihydrate through supercritical CO(2) fluid extraction if appropriate temperature and pressure conditions (around 80 degrees C and 20 MPa) are maintained.

Observation of molecular changes of a necrotic tissue from a murine carcinoma by Fourier-transform infrared microspectroscopy.

PURPOSE: Our purpose is to develop infrared (IR) microspectroscopy as a new optical diagnostic tool to support conventional lightscopic techniques in investigating the viability of carcinoma tissues and to develop its use in the evaluation of the early effects of anticancer therapy by monitoring the IR spectra in the necrotic area. EXPERIMENTAL DESIGN: We evaluated the tissue which amassed for 4 weeks after the isotransplantation of mouse squamous cell carcinoma into the thigh of mice. The borders of the necrotic area of frozen tissue specimens were investigated by Fourier-transform IR microspectroscopy and conventional histological staining. RESULTS: A significantly higher accumulation of cholesterol was observed in the necrotic tissue of a carcinoma. The mechanism of this phenomenon is hitherto unrecognized. We proposed that the accumulated cholesterol may lie extracellularly as a result of the ruptured plasma and internal membranes after the swelling of the necrotic cells brought on by hypoxia. The analysis of the secondary structure of protein revealed that the amounts of beta-sheet increased significantly in striking contrast to the decreasing amounts of alpha-helix in a necrotic area of a carcinoma. It is plausible that this structural conversion of protein was because of lipid-autooxidation products, such as cholesterol oxide but not cholesterol itself, which possesses cell toxicity and could be generated in a necrotic area. CONCLUSIONS: We conclude that it will be possible to evaluate the efficacy of the clinical treatment of carcinoma by monitoring subtle biological changes of cholesterol absorbance in the early stage of necrosis because of anticancer treatment.