Reaction Rates of OH Radicals with CH3OCF2CHFCF3 and CHF2CF2OCH2CF2CHF2: Measurements and Estimation Using Neural Network Method.

The reaction rates of OH radicals with CH3OCF2CHFCF3 (k1) and CHF2CF2OCH2CF2CHF2 (k2) were measured over a temperature range of 250-430 K. Kinetic measurements were performed using the flash and laser photolysis methods combined with a laser-induced fluorescence technique. The Arrhenius rate parameters were determined as k1 = (2.52 ± 0.25) × 10-12·exp[-(1390 ± 30)/T], k2 = (1.83 ± 0.20) × 10-12·exp[-(1420 ± 35)/T] cm3 molecule-1 s-1. The infrared absorption spectra of the two hydrofluoroethers were measured at approximately 298 K in 760 Torr of N2. The atmospheric lifetimes of CH3OCF2CHFCF3 and CHF2CF2OCH2CF2CHF2 have been estimated as 2.5 and 3.8 years, respectively, and their global warming potentials were determined as 245 and 405, respectively. Additionally, a method, using a three-layered feed-forward neural network, for estimating the rates of the reaction of the OH radicals with alkanes, ethers, and alcohols was investigated. The ratios of the calculated reaction rates to the observed ones agreed within a factor of 2. The ability of the neural network method to predict reaction rates was examined by using a leave-one-out test.

A quantum chemical study on the effects of varying the central metal in extended photosynthetic pigments.

In a certain period of Earth's history, chlorophylls with Mg as their central metal would have been selected as the major photosynthetic pigments, reflecting the radiation in habitats. Assuming evolution in different light and material environments, different photosynthetic pigments would occur. This study is the first attempt to evaluate the physical and chemical properties of model photosynthetic pigments and their potential to function in a variety of light environments using quantum chemistry calculations. Specifically, bacteriochlorophyll b (Bchl b), phthalocyanine (Pht) and meso-dibenzoporphycene (mDBPc) were selected as template molecules, while Be, Mg, Ca, Ni, Zn, Sr, Pd, Cd, Ba, Pt, Hg, Pb and H2 were examined as the central metals in each molecule in various solvents. The results showed that the light absorption by each of these compounds varied over a range of 100 nm depending on the central metal and the surrounding solvent, and Pb produced the largest red shift in the absorption bands of all three photosynthetic pigments. The Pht molecules showed similar redox properties to the chlorophylls, suggesting that these derivatives could be substituted for the special pairs in reaction centers, while the mDBPc molecules appear to be more suitable as accessory pigments due to their extraordinarily broad absorption ranges of approximately 500 nm depending on the conditions.

Rate Constants for the Reactions of OH Radicals with the ( E)/( Z) Isomers of CFCl=CFCl and ( E)-CHF=CHF.

The rate constants for the OH radical reactions with halogenated ethenes were investigated experimentally and computationally. The rate constants for the reactions of OH radicals with ( E)-CFCl=CFCl ( k1), ( Z)-CFCl=CFCl ( k2), and ( E)-CHF=CHF ( k3) were measured using flash and laser photolysis methods. The temporal profile of the OH radical was monitored by a laser-induced fluorescence technique. Kinetic measurements were carried out over the temperature range of 250-430 K. Arrhenius rate constants were determined to be k1 = (1.67 ± 0.06) × 10-12·exp[(140 ± 10) K/ T], k2 = (1.75 ± 0.04) × 10-12·exp[(140 ± 10) K/ T], and k3 = (3.99 ± 0.15) × 10-12·exp[(260 ± 10) K/ T] cm3 molecule-1 s-1. The quoted uncertainties are 95% confidence levels and do not include systematic errors. Infrared absorption spectra were measured at room temperature. The atmospheric lifetimes and the global warming potentials of ( E)-CFCl=CFCl, ( Z)-CFCl=CFCl, and ( E)-CHF=CHF were estimated to be 4.3, 4.2, and 1.2 days and 0.035, 0.036, and 0.0056, respectively. The ozone depletion potentials of ( E)-CFCl=CFCl and ( Z)-CFCl=CFCl were determined to be 0.00011 and 0.00010, respectively. The photochemical ozone creation potentials of the halogenated ethenes were less than 1/4 that of ethene. In addition, the ( E)/( Z) differences in the energy and IR spectra of the CFCl=CFCl and CHF=CHF molecules were computationally examined. The reactivities of these halogenated ethenes toward OH radicals were investigated through the combination of DFT and ab initio computations. The rate constants calculated for the OH radical reactions of these halogenated ethenes showed reasonable agreement with the experimentally determined values. Our computational results for the CFCl=CFCl and CHF=CHF ( E)/( Z) isomeric pairs indicated that the rate constants toward OH radicals are larger for the higher-energy geometrical isomers than for the lower-energy counterparts.

Rate Constants for the Reactions of OH Radicals with Fluorinated Ethenes: Kinetic Measurements and Correlation between Structure and Reactivity.

The rate constants for the reaction of OH radicals with four fluorinated ethenes (CF2═CHF, ( E)-CHF═CHF, CF2═CH2, and CHF═CH2) have been measured over the temperature range of 250-430 K. Kinetic measurements have been carried out using flash photolysis and laser photolysis methods combined with a laser-induced fluorescence technique. The Arrhenius expressions for the rate constant have been determined as k(CF2═CHF) = (3.12 ± 0.11) × 10-12 exp[(270 ± 10)/ T], k(( E)-CHF═CHF) = (3.75 ± 0.08) × 10-12 exp[(230 ± 10)/ T], k(CF2═CH2) = (1.15 ± 0.07) × 10-12 exp[(230 ± 20)/ T], and k(CHF═CH2) = (1.16 ± 0.09) × 10-12 exp[(390 ± 20)/ T] cm3 molecule-1 s-1. Infrared absorption spectra of the fluorinated ethenes have been measured at room temperature. The atmospheric lifetimes and global warming potentials of the fluorinated ethenes have been estimated. The correlation between the reactivity and the structure of the halogenated ethenes has been investigated by considering the structure containing the atoms attached to the carbons on both sides of the double bond. The calculated rate constants of 14 halogenated ethenes showed agreement with the measured rate constants within a factor of 2, except for that of one compound.

Rate Constants for the Reactions of OH Radical with the ( E)/( Z) Isomers of CF3CF═CHCl and CHF2CF═CHCl.

The rate constants for the reactions of OH radical with ( E)- and ( Z)-isomers of CF3CF═CHCl and CHF2CF═CHCl have been measured over the temperature range of 250-430 K. Kinetic measurements have been performed using flash and laser photolysis methods combined with laser-induced fluorescence. Arrhenius rate constants have been determined as k(( E)-CF3CF═CHCl) = (1.09 ± 0.03) × 10-12 · exp[(50 ± 10)K/ T], k(( Z)-CF3CF═CHCl) = (8.02 ± 0.19) × 10-13 · exp[-(100 ± 10)K/ T], k(( E)-CHF2CF═CHCl) = (1.50 ± 0.03) × 10-12 · exp[(160 ± 10)K/ T], and k(( Z)-CHF2CF═CHCl) = (1.36 ± 0.03) × 10-12 · exp[(360 ± 10)K/ T] cm3 molecule-1 s-1. Infrared absorption spectra have also been measured at room temperature. The atmospheric lifetimes of ( E)-CF3CF═CHCl, ( Z)-CF3CF═CHCl, ( E)-CHF2CF═CHCl, and ( Z)-CHF2CF═CHCl have been estimated as 8.9, 20, 4.6, and 2.6 days, respectively, and their global warming potentials and ozone depletion potentials were determined as 0.23, 0.88, 0.060, and 0.016 and 0.00010, 0.00023, 0.000057, and 0.000030, respectively. Additionally, the rate constants for OH radical addition and IR spectra of these compounds were determined computationally. Consistent with experiment, our calculations indicate that the reactivity toward OH radical addition is reduced as ( Z)-CHF2CF═CHCl > ( E)-CHF2CF═CHCl > ( E)-CF3CF═CHCl > ( Z)-CF3CF═CHCl, where the ( E)/( Z) reactivity is reversed for CF3CF═CHCl and CHF2CF═CHCl. The calculations reproduced the observed temperature dependencies of the rate constants for the OH radical reactions, which is slightly positive for ( Z)-CF3CF═CHCl but negative for the other compounds.

Chloroplast remodeling during state transitions in Chlamydomonas reinhardtii as revealed by noninvasive techniques in vivo.

Plants respond to changes in light quality by regulating the absorption capacity of their photosystems. These short-term adaptations use redox-controlled, reversible phosphorylation of the light-harvesting complexes (LHCIIs) to regulate the relative absorption cross-section of the two photosystems (PSs), commonly referred to as state transitions. It is acknowledged that state transitions induce substantial reorganizations of the PSs. However, their consequences on the chloroplast structure are more controversial. Here, we investigate how state transitions affect the chloroplast structure and function using complementary approaches for the living cells of Chlamydomonas reinhardtii. Using small-angle neutron scattering, we found a strong periodicity of the thylakoids in state 1, with characteristic repeat distances of ∼ 200 Å, which was almost completely lost in state 2. As revealed by circular dichroism, changes in the thylakoid periodicity were paralleled by modifications in the long-range order arrangement of the photosynthetic complexes, which was reduced by ∼ 20% in state 2 compared with state 1, but was not abolished. Furthermore, absorption spectroscopy reveals that the enhancement of PSI antenna size during state 1 to state 2 transition (∼ 20%) is not commensurate to the decrease in PSII antenna size (∼ 70%), leading to the possibility that a large part of the phosphorylated LHCIIs do not bind to PSI, but instead form energetically quenched complexes, which were shown to be either associated with PSII supercomplexes or in a free form. Altogether these noninvasive in vivo approaches allow us to present a more likely scenario for state transitions that explains their molecular mechanism and physiological consequences.

Isolation of the elusive supercomplex that drives cyclic electron flow in photosynthesis.

Photosynthetic light reactions establish electron flow in the chloroplast's thylakoid membranes, leading to the production of the ATP and NADPH that participate in carbon fixation. Two modes of electron flow exist-linear electron flow (LEF) from water to NADP(+) via photosystem (PS) II and PSI in series and cyclic electron flow (CEF) around PSI (ref. 2). Although CEF is essential for satisfying the varying demand for ATP, the exact molecule(s) and operational site are as yet unclear. In the green alga Chlamydomonas reinhardtii, the electron flow shifts from LEF to CEF on preferential excitation of PSII (ref. 3), which is brought about by an energy balancing mechanism between PSII and PSI (state transitions). Here, we isolated a protein supercomplex composed of PSI with its own light-harvesting complex (LHCI), the PSII light-harvesting complex (LHCII), the cytochrome b(6)f complex (Cyt bf), ferredoxin (Fd)-NADPH oxidoreductase (FNR), and the integral membrane protein PGRL1 (ref. 5) from C. reinhardtii cells under PSII-favouring conditions. Spectroscopic analyses indicated that on illumination, reducing equivalents from downstream of PSI were transferred to Cyt bf, whereas oxidised PSI was re-reduced by reducing equivalents from Cyt bf, indicating that this supercomplex is engaged in CEF (Supplementary Fig. 1). Thus, formation and dissociation of the PSI-LHCI-LHCII-FNR-Cyt bf-PGRL1 supercomplex not only controlled the energy balance of the two photosystems, but also switched the mode of photosynthetic electron flow.

How much heat does non-photochemical quenching produce?

Non-photochemical quenching (NPQ) is a protective mechanism used by plants to safely dissipate excess absorbed light energy as heat, minimizing photo-oxidative damage. Although the importance of NPQ as a safety valve for photosynthesis is well-known, the physiological and environmental effects of the heat produced remain unclear because the amount of heat produced by NPQ is considered negligible, and its physiological effects have not been directly observed. Here, we calculated the heat produced by NPQ and evaluated its impact on the leaf and global warming based on simplified models. Our evaluation showed that the heat produced by NPQ in a given leaf area is 63.9 W m-2 under direct sunlight. Under the standard condition, NPQ warms up the leaf at less than 0.1°C, but it could be 1°C under particular conditions with low thermal conductance. We also estimated the thermal radiation of vegetation's NPQ to be 2.2 W m-2 par global averaged surface area. It is only 0.55% of the thermal radiation by the Earth's surface, but still significant in the current climate change response. We further discuss the possible function of NPQ to plant physiology besides the safety valve and provide strategies with artificial modification of the NPQ mechanism to increase food production and mitigate global warming.

A case of retained placenta increta successfully treated via uterine arterial embolization using N-butyl 2-cyanoacrylate.

A 29-year-old woman with placenta increta with hemorrhage underwent uterine artery embolization using 12.5% NBCA (N-butyl 2-cyanoacrylate) diluted with iodized oil (Lipiodol). Complete resolution of placenta increta without performing curettage was obtained. The uterus returned to its normal shape, with restored endometrium, junctional zone, and myometrium. Menstruation resumed after 3 months. In cases of retained placenta due to placenta accreta, and even those with placenta increta, uterine artery embolization using NBCA is a useful treatment.

Bilateral approach of redistributed subclavian arterial infusion chemotherapy for locally advanced breast cancer spreading to the contralateral chest wall.

A catheter port system technique called redistributed subclavian arterial infusion chemotherapy (RESAIC) for locally advanced breast cancer was reported and seemed to be effective for local control and as a palliative treatment. However, when the cancer spreads beyond the medial line to the contralateral chest wall, ipsilateral RESAIC would not achieve a favorable drug distribution. We report on two patients with advanced breast cancer spreading to the contralateral chest wall in whom bilateral RESAIC was attempted. In summary, when advanced breast cancer spreads to the contralateral chest wall, bilateral RESAIC may be useful for local control or palliation.

Characterization of photosystem I antenna proteins in the prasinophyte Ostreococcus tauri.

Prasinophyceae are a broad class of early-branching eukaryotic green algae. These picophytoplankton are found ubiquitously throughout the ocean and contribute considerably to global carbon-fixation. Ostreococcus tauri, as the first sequenced prasinophyte, is a model species for studying the functional evolution of light-harvesting systems in photosynthetic eukaryotes. In this study we isolated and characterized O. tauri pigment-protein complexes. Two photosystem I (PSI) fractions were obtained by sucrose density gradient centrifugation in addition to free light-harvesting complex (LHC) fraction and photosystem II (PSII) core fractions. The smaller PSI fraction contains the PSI core proteins, LHCI, which are conserved in all green plants, Lhcp1, a prasinophyte-specific LHC protein, and the minor, monomeric LHCII proteins CP26 and CP29. The larger PSI fraction contained the same antenna proteins as the smaller, with the addition of Lhca6 and Lhcp2, and a 30% larger absorption cross-section. When O. tauri was grown under high-light conditions, only the smaller PSI fraction was present. The two PSI preparations were also found to be devoid of the far-red chlorophyll fluorescence (715-730 nm), a signature of PSI in oxygenic phototrophs. These unique features of O. tauri PSI may reflect primitive light-harvesting systems in green plants and their adaptation to marine ecosystems. Possible implications for the evolution of the LHC-superfamily in photosynthetic eukaryotes are discussed.

Percutaneous vertebroplasty for vertebral compression fractures with intravertebral cleft: cement injection under vacuum aspiration.

PURPOSE: To evaluate the efficacy of cement injection under vacuum aspiration (CIVAS) of cleft contents in percutaneous vertebroplasty for osteoporotic vertebral compression fractures with an intravertebral cleft. MATERIALS AND METHODS: From April 2008 to October 2010, vertebroplasty for single-level osteoporotic vertebral compression fractures with clefts was performed in 34 patients (seven women, 27 men; mean age, 77 y) with CIVAS and in 41 patients (three women, 38 men; mean age, 77 y) by conventional injection (control group). In this retrospective study, the cement volume, cement ratio, visual analog scale (VAS) pain score, and incidences of leakage, new vertebral compression fracture, and nonhealing were compared between groups. Vertebral height changes in the CIVAS group were also evaluated. RESULTS: There were significant decreases in VAS scores in both groups (P < .001). There were no significant differences in complications between groups (cement leakage, P = .70; new vertebral compression fracture, P = .17; nonhealing, P = .086). Vertebral height was significantly decreased by vacuum aspiration and increased by cement injection (P < .001). The mean cement volume was significantly higher (P = .0057) in the CIVAS group (4.87 mL) than in the control group (3.58 mL). Cement filling was achieved more sufficiently in the CIVAS group (P = .014). CONCLUSIONS: The CIVAS method is feasible and appears to improve cleft filling in the treatment of single-level vertebral compression fractures with a cleft, compared with conventional cement injection.

[Oncology IVR--application to palliative medicine].

Oncology IVR is a minimum invasive and locoregional treatment by newly developed interventional techniques consisting of transarterial chemoembolization (TACE), radiofrequency ablation, cryoablation and percutaneous bone plasty (PBP), etc. These treatment methods are considered to be effective to rapid tumor reduction and palliation. The redistributed subclavian arterial infusion chemotherapy via an implanted catheter-port system which was newly developed by authors would be effective for local recurrence of breast cancer. The combination therapy of these interventional techniques can offer new treatment strategies for an improvement of patient's quality of life and more effective palliative medicine.

Structural basis of LhcbM5-mediated state transitions in green algae.

In green algae and plants, state transitions serve as a short-term light-acclimation process in the regulation of the light-harvesting capacity of photosystems I and II (PSI and PSII, respectively). During the process, a portion of light-harvesting complex II (LHCII) is phosphorylated, dissociated from PSII and binds with PSI to form the supercomplex PSI-LHCI-LHCII. Here, we report high-resolution structures of PSI-LHCI-LHCII from Chlamydomonas reinhardtii, revealing the mechanism of assembly between the PSI-LHCI complex and two phosphorylated LHCII trimers containing all four types of LhcbM protein. Two specific LhcbM isoforms, namely LhcbM1 and LhcbM5, directly interact with the PSI core through their phosphorylated amino terminal regions. Furthermore, biochemical and functional studies on mutant strains lacking either LhcbM1 or LhcbM5 indicate that only LhcbM5 is indispensable in supercomplex formation. The results unravel the specific interactions and potential excitation energy transfer routes between green algal PSI and two phosphorylated LHCIIs.

Risk factors for perioperative venous thromboembolism: A retrospective study in Japanese women with gynecologic diseases.

BACKGROUND: Patients with gynecologic cancer have a high risk of venous thromboembolism (VTE) like patients with other cancers. However, there is little information on risk factors for VTE during gynecologic surgery and no uniform preventive strategy. Our objectives were to identify risk factors for perioperative VTE in gynecologic patients and establish methods for prevention. METHODS: We analyzed 1,232 patients who underwent surgery at the Department of Obstetrics and Gynecology of St. Marianna University School of Medicine between January 2005 and June 2008. We investigated (1) risk factors for preoperative VTE, (2) use of an inferior vena cava (IVC) filter, and (3) risk factors for postoperative VTE. RESULTS: There were 39 confirmed cases of perioperative VTE (3.17%), including 25 patients with preoperative VTE and 14 with postoperative VTE. Thirty-two patients had cancer and seven patients had benign diseases. Twenty-two of the 32 cancer patients (68.7%) had preoperative VTE, while postoperative VTE occurred in 10 cancer patients. Multivariate analysis indicated that ovarian cancer, tumor diameter ≥10 cm, and previous of VTE were independent risk factors for preoperative VTE. Among ovarian cancer patients, multivariate analysis showed that an age ≥50 years, the presence of heart disease, clear cell adenocarcinoma, and tumor diameter ≥20 cm were independent risk factors for preoperative VTE. The factors significantly related to preoperative VTE in patients with benign disease included previous VTE, age ≥55 years, tumor diameter ≥20 cm, and a history of allergic-immunologic disease. Thirteen of the 25 patients (52%) with preoperative VTE had an IVC filter inserted preoperatively. Postoperative screening (interview and D-dimer measurement) revealed VTE in 14/1,232 patients (1.14%). Multivariate analysis indicated that cancer surgery, a history of allergic-immunologic disease, and blood transfusion ≥2,000 ml were independent risk factors for postoperative VTE. CONCLUSIONS: Perioperative VTE is often fatal and preventive measures should be taken in the gynecologic field, especially when patients have the risk factors identified in this study. Since VTE is often present before surgery, preoperative screening is important and use of an IVC filter should be considered.

Correction to: Rate constants for the reactions of OH radicals with CF3CX=CY2 (X=H, F, CF3, Y=H, F, Cl).

We make a correction to the original paper because there was a mistake in our preceding paper (Tokuhashi et al. 2018) that was cited in the original paper. In our preceding paper, we reported the measured rate constant of OH radicals with (E)-CHF=CHF.

[A case of lung adenocarcinoma of pancoast type successfully treated with concurrent chemoradiotherapy].

We reported a case of lung adenocarcinoma of Pancoast type that was successfully treated with chemoradiotherapy. A 66-year-old man was admitted to our hospital because of back pain. Chest computed tomography (CT) showed a Pancoast tumor on the left side. Using transbronchial needle aspiration, we diagnosed lung adenocarcinoma (cT3N0M0). The patient received chemoradiotherapy simultaneously(carboplatin AUC5 and irinotecan 60 mg/m2). There are no findings of tumor recurrence 8 years after chemoradiotherapy. This patient was successfully treated with concurrent chemoradiotherapy, which is suggested to be a useful therapy for Pancoast tumor.