Spectroscopy and reactivity of a photogenerated tryptophan radical in a structurally defined protein environment

Near-UV irradiation of structurally characterized [Re(I)(CO)3(1,10-phenanthroline)(Q107H)](W48F/Y72F/H83Q/Y108W)AzM(II) [Az = Pseudomonas aeruginosa azurin, M = Cu, Zn]/[Co(NH3)5Cl]Cl2 produces a tryptophan radical (W108*) with unprecedented kinetic stability. After rapid formation (k = 2.8 x 106 s-1), the radical persists for more than 5 h at room temperature in the folded ReAzM(II) structure. The absorption spectrum of ReAz(W108*)M(II) exhibits maxima at 512 and 536 nm. Oxidation of K4[Mo(CN)8] by ReAz(W108*)Zn(II) places the W108*/W108 reduction potential in the protein above 0.8 V vs NHE.     

Applicability of in situ detectors for radiological assessment of strontium-90 in rivers and lakes

Journal of Radioanalytical and Nuclear Chemistry - An in situ detector for radiological assessments of strontium-90 (90Sr) in river and lake water is developed, based on a CaF2(Eu) scintillator,...     

Structural and functional stabilities of artificially designed DNA ultra-thin films grown by silica Assistance

We report the structural and functional stabilities of artificially synthesized DNA ultra-thin films. Fully covered DNA ultra-thin films on a silica substrate were fabricated by the silica-assisted growth method and those samples were then incubated in various chemicals and physical conditions. The DNA ultra-thin films showed high maintainability under those harsh conditions and these results would aid to facilitate the use of artificial DNA ultra-thin films in advanced research areas such as biophotonics and bioelectronics.     

Liquid crystalline epoxy resin with improved thermal conductivity by intermolecular dipole–dipole interactions

To address tremendous needs for developing efficiently heat dissipating materials with lightweights, a series of liquid crystalline epoxy resins (LCEs) are designed and synthesized as thermally conductive matrix. All prepared LCEs possess epoxies at the molecular side positions and cyanobiphenyl mesogenic end groups. Based on several experimental results such as differential scanning calorimetry, polarized optical microscopy, and X‐ray diffraction, it is found that the LCEs exhibited liquid crystalline mesophases. When LCE is cured with a diamine crosslinker, the cured LCE maintains the oriented LC domain formed in the uncured state, ascribing to a presence of dipole–diploe and π–π interactions between cyanobiphenyl mesogenic end groups. Due to the anisotropic molecular orientation, the cured LCE exhibits a high thermal conductivity of 0.46 W m^?1 K^?1, which is higher than those of commercially available crystalline or amorphous epoxy resins. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 708–715     

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N-doped Carbon Catalysts

Ni,N-doped carbon catalysts have shown promising catalytic performance for CO₂ electroreduction (CO₂R) to CO; this activity has often been attributed to the presence of nitrogen-coordinated, single Ni atom active sites. However, experimentally confirming Ni−N bonding and correlating CO₂ reduction (CO₂R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile-derived Ni,N-doped carbon electrocatalysts (Ni-PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO₂R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X-ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square-planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.     

Understanding the Origin of Highly Selective CO2 Electroreduction to CO on Ni,N‐doped Carbon Catalysts

Ni,N‐doped carbon catalysts have shown promising catalytic performance for CO₂ electroreduction (CO₂R) to CO; this activity has often been attributed to the presence of nitrogen‐coordinated, single Ni atom active sites. However, experimentally confirming Ni?N bonding and correlating CO₂ reduction (CO₂R) activity to these species has remained a fundamental challenge. We synthesized polyacrylonitrile‐derived Ni,N‐doped carbon electrocatalysts (Ni‐PACN) with a range of pyrolysis temperatures and Ni loadings and correlated their electrochemical activity with extensive physiochemical characterization to rigorously address the origin of activity in these materials. We found that the CO₂R to CO partial current density increased with increased Ni content before plateauing at 2 wt % which suggests a dispersed Ni active site. These dispersed active sites were investigated by hard and soft X‐ray spectroscopy, which revealed that pyrrolic nitrogen ligands selectively bind Ni atoms in a distorted square‐planar geometry that strongly resembles the active sites of molecular metal–porphyrin catalysts.     

双参数变形量子代数SU（1，1）_（q，s）的Nodvik实现和Holstein—Primakoff实现

给出了双参数变形量子代数ＳＵ（１，１）ｑ，ｓ的Ｎｏｄｖｉｋ实现和Ｈｏｌｓｔｅｉｎ－Ｐｒｉｍａｋｏｆｆ实现，并给出了ＳＵ（１，１）ｑ，ｓ，和双参数变形振子的变形映射。     

Two new phenolic amides from the seeds of Pharbitis nil

Two new phenolic amides, pharnilatins A (1) and B (2), were isolated from the seeds of Pharbitis nil. These new compounds possess a p-coumaroyl unit with a structurally unique side chain, (2S,3S)-2,3-dihydroxyputrescine. The chemical structures and absolute stereochemistries of the new compounds were determined on the basis of spectroscopic analyses including 1D- and 2D-NMR experiments and chemical reactions. Compounds 1 and 2 exhibited cytotoxicity against A549, SK-OV-3, SK-MEL-2, and HCT-15 human tumor cells. However, none of the compounds inhibited nitric oxide (NO) production in lipopolysaccharide (LPS)-activated microglia cells.     

The enhanced expression of IL-17-secreting T cells during the early progression of atherosclerosis in ApoE-deficient mice fed on a western-type diet

Atherosclerosis is a chronic progressive inflammatory disorder and the leading cause of cardiovascular mortality. Here we assessed the dynamic changes of T-cell-derived cytokines, such as inteferon (IFN)-γ, interleukin (IL)-17 and IL-4, during the progression of atherosclerosis in apolipoprotein E-null (ApoE^−/−) mice, to understand the role of immune responses in different stages of atherosclerosis. Male ApoE^−/− mice were fed a high-fat, western-type diet (WD: 21% lipid, 1.5% cholesterol) after 5 weeks of age and were compared with C57BL/6 wild-type control mice fed a standard chow diet. Atherosclerotic lesions appeared in the aortic sinus of ApoE^−/− mice 4 weeks after WD and the lesions progressed and occupied >50% of the total sinus area 16 weeks after WD. Aortic IL-17 mRNA and protein expression started to increase in ApoE^−/− mice after 4 weeks on the WD and peaked at around 8–12 weeks on the WD. In terms of systemic expression of T-cell-derived cytokines, IL-17 production from splenocytes after anti-CD3/CD28 stimuli increased from 4 weeks on the WD, peaked at 12 weeks and returned to control levels at 16 weeks. The production of IFN-γ and IL-4 (Th1 and Th2 cytokines, respectively) from splenocytes was delayed compared with IL-17. Taken together, the present data indicate that Th17 cell response may be involved at an early stage in the development of atherosclerosis.