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A novel dinitrogen-dichromium complex, [{Cr(LBn)}2(µ-N2)] (1), has been prepared from reaction of CrCl3 with a lithiated triamidoamine ligand (Li3LBn) under dinitrogen. The X-ray crystal structure analysis of 1 revealed that it is composed of two independent dimeric Cr complexes bridged by N2 in the unit cell. The bridged N-N bond lengths (1.188(4) and 1.185(7) Å) were longer than the free dinitrogen molecule. The elongations of N-N bonds in 1 were also supported by the fact that the ν(N-N) stretching vibration at 1772 cm-1 observed in toluene is smaller than the free N2. Complex 1 was identified to be a 5-coordinated high spin Cr(IV) complex by Cr K-edge XANES measurement. The 1H NMR spectrum and temperature dependent magnetic susceptibility of 1 indicated that complex 1 is in the S = 1 ground state, in which two Cr(IV) ions and unpaired electron spins of the bridging N22- ligand are strongly antiferromagnetically coupled. Reaction of complex 1 with 2.3 equiv of Na or K gave chromium complexes with N2 between the Cr ion and the respective alkali metal ion, [{CrNa(LBn)(N2)(Et2O)}2] (2) and [{CrK(LBn)(N2)}4(Et2O)2] (3), respectively. Furthermore, the complexes 2 and 3 reacted with 15-crown-5 and 18-crown-6 to form the respective crown-ether adducts, [CrNa(LBn)(N2)(15-crown-5)] (4) and [CrK(LBn)(N2)(18-crown-6)] (5). The XANES measurements of complexes 2, 3, 4, and 5 revealed that they are high spin Cr(IV) complexes like complex 1. All complexes reacted with a reducing agent and a proton source to form NH3 and/or N2H4. The yields of these products in the presence of K+ were higher than those in the presence of Na+. The electronic structures and binding properties of 1, 2, 3, 4, and 5 were evaluated and discussed based on their DFT calculations.
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Cu-containing nitrite reductases (NiRs) are 110 kDa enzymes that play central roles in denitrification. Although the NiRs have been well studied, with over 100 Protein Data Bank entries, such issues as crystal packing, photoreduction, and lack of high pH cases have impeded structural analysis of their catalytic mechanisms. Here we show the cryogenic electron microscopy (cryo-EM) structures of Achromobacter cycloclastes NiR (AcNiR) at pH 6.2 and 8.1. The optimization of 3D-reconstruction parameters achieved 2.99 and 2.85 Å resolution. Comprehensive comparisons with cryo-EM and 56 AcNiR crystal structures suggested crystallographic artifacts in residues 185-215 and His255' due to packing and photoreduction, respectively. We used a newly developed map comparison method to detect structural change around the type 2 Cu site. While the theoretical estimation of coordinate errors of cryo-EM structures remains difficult, combined analysis using X-ray and cryo-EM structures will allow deeper insight into the local structural changes of proteins.
Assuntos
Cobre , Nitrito Redutases , Achromobacter cycloclastes/metabolismo , Catálise , Cobre/química , Microscopia Crioeletrônica/métodos , Nitrito Redutases/química , Nitrito Redutases/metabolismoRESUMO
One-electron-oxidized Ni(III)-phenoxide complexes with salen-type ligands, [Ni(salen)py2](2+) ([1(en)-py](2+)) and [Ni(1,2-salcn)py2](2+) ([1(cn)-py](2+)), with a five-membered chelate dinitrogen backbone and [Ni(salpn)py2](2+) ([2(pn)-py](2+)), with a six-membered chelate backbone, have been characterized with a combination of experimental and theoretical methods. The five-membered chelate complexes [1(en)-py](2+) and [1(cn)-py](2+) were assigned as Ni(III)-phenoxyl radical species, while the six-membered chelate complex [2(pn)-py](2+) was concluded to be a Ni(II)-bis(phenoxyl radical) species with metal-centered reduction in the course of the one-electron oxidation of the Ni(III)-phenoxide complex [2(pn)-py](+). Thus, the oxidation state of the one-electron-oxidized Ni(III) salen-type complexes depends on the chelate ring size of the dinitrogen backbone.
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Níquel/química , Compostos Organometálicos/química , Óxidos/química , Elétrons , Ligantes , Estrutura Molecular , Compostos Organometálicos/síntese química , OxirreduçãoRESUMO
The rational structural and computational studies of a blue copper protein, pseudoazurin (PAz), and its Met16X (X = Phe, Leu, Val, Ile) variants gave clear functional meanings of the noncovalent interaction (NCI) through the second coordination sphere. The high-resolution X-ray crystal structures of Met16X PAz demonstrated that the active site geometry is significantly affected by the substitution of Met16, which is located within the NCI distance from the His81 imidazole ring at the copper active site. The computational chemistry calculations based on the crystal structure analyses confirmed that the NCI of S-π/CH-π (wild-type), π-π (Met16Phe), double CH-π (Met16Leu), and single CH-π (Met16Val and Met16Ile). The estimated interaction energies for the NCI demonstrated that the fine-tuning of the protein stability and Cu site properties form the second coordination sphere of PAz.
Assuntos
Azurina , Cobre , Cobre/química , Modelos Moleculares , Azurina/química , Azurina/metabolismo , Domínio Catalítico , Cristalografia por Raios XRESUMO
OBJECTIVES: One primary concern about receiving care at home is that survival might be shortened because the quality and quantity of treatment provided at home will be inferior to that given in the hospital. Although our previous study demonstrated a longer survival of those with home-based palliative care (PC), it lacked adjustment for some potential confounders including symptoms and treatments during the stay. We aimed to compare the survival times among advanced cancer patients receiving home-based and hospital-based PC with adjusting for symptoms and treatments. METHOD: We compared survival time of participants who enrolled two multicenter, prospective cohort studies of advanced cancer patients at 45-home-based PC services between July 2017 and December 2017, and at 23-hospital-based PC services between January 2017 and December 2017. We analyzed with stratification by the estimated survival of Days, Weeks, and Months, which were defined by modified Prognosis in Palliative care Study predictor models-A. We conducted a Cox regression analysis with adjusting for potential confounders including symptoms and treatments during the stay. RESULTS: A total of 2,998 patients were enrolled in both studies and 2,878 patients were analyzed; 988 patients receiving home-based PC and 1,890 receiving hospital-based PC. The survival time of patients receiving home-based PC was significantly longer than that of patients receiving hospital-based PC for the Days Prognosis (estimated median survival time: 10 days [95% CI 8.1-11.8] vs. 9 days [95% CI 8.3-10.4], p = 0.157), the Weeks prognosis (32 days [95% CI 28.9-35.4] vs. 22 days [95% CI 20.3-22.9], p < 0.001), and the Months Prognosis, (65 days [95% CI 58.2-73.2] vs. 32 days [95% CI 28.9-35.4], p < 0.001). CONCLUSION: In this cohort of advanced cancer patients with a Weeks or Months prognosis, those receiving home-based PC survived longer than those receiving hospital-based PC after adjusting for symptoms and treatments.
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Neoplasias , Cuidados Paliativos , Humanos , Estudos Prospectivos , Neoplasias/terapia , Hospitais , Prognóstico , Estudos RetrospectivosRESUMO
We synthesized superconducting fullerene nanowhiskers (C(60)NWs) by potassium (K) intercalation. They showed large superconducting volume fractions, as high as 80%. The superconducting transition temperature at 17 K was independent of the K content (x) in the range between 1.6 and 6.0 in K-doped C(60) nanowhiskers (K(x)C(60)NWs), while the superconducting volume fractions changed with x. The highest shielding fraction of a full shielding volume was observed in the material of K(3.3)C(60)NW by heating at 200 °C. On the other hand, that of a K-doped fullerene (K-C(60)) crystal was less than 1%. We report the superconducting behaviors of our newly synthesized K(x)C(60)NWs in comparison to those of K(x)C(60) crystals, which show superconductivity at 19 K in K(3)C(60). The lattice structures are also discussed, based on the x-ray diffraction (XRD) analyses.
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Fulerenos/química , Nanoestruturas/química , Cristalização , Cristalografia por Raios X , Condutividade Elétrica , Microscopia Eletrônica de Varredura , Nanoestruturas/ultraestrutura , Potássio/química , TemperaturaRESUMO
BACKGROUND: In Japan, because of an increase in the elderly population, End-Of-Life care is of increasingconcern. In the future, the demand for home healthcare is expected to increase further. However, it is difficult to prepare numerous reports and to share accurate information rapidly because of the small-scale support for home medical care from clinics and visiting nursingstations, pharmacies, and various other establishments. METHOD: We used an information technology tool called the "Ohisama-system" to start our own information sharing system between doctors in different groups. Herein, we report and discuss the future issues for community medicine cooperation when usinginformation technology. RESULTS: Electronic medical records written by doctors only are not suitable for viewingand sharingwith multiple groups workingin the filed of home healthcare. A variety of detailed information that has not been described in the medical records, such as the floor plan of the home, the wishes of the family, and use of other services is important for the home healthcare team. CONCLUSIONS: The Ohisama-system is very useful for sharingpatient information to enable community medicine cooperation. However, it is also more important to maintain face-to-face communication.
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Medicina Comunitária/métodos , Redes Comunitárias , Internet/instrumentação , Equipe de Assistência ao PacienteRESUMO
The dynamic structure changes, including the unfolding, dimerization, and transition from the compact to the open-bundle unfolding intermediate structure of Cyt c', were detected by a small-angle neutron scattering experiment (SANS). The structure of Cyt c' was changed into an unstructured random coil at pD = 1.7 (Rg = 25 Å for the Cyt c' monomer). The four-α-helix bundle structure of Cyt c' at neutral pH was transitioned to an open-bundle structure (at pD ~13), which is given by a numerical partial scattering function analysis as a joint-clubs model consisting of four clubs (α-helices) connected by short loops. The compactly folded structure of Cyt c' (radius of gyration, Rg = 18 Å for the Cyt c' dimer) at neutral or mildly alkaline pD transited to a remarkably larger open-bundle structure at pD ~13 (Rg = 25 Å for the Cyt c' monomer). The open-bundle structure was also supported by ab initio modeling.
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Citocromos c' , Citocromos c , Citocromos c/química , Dimerização , Espalhamento a Baixo ÂnguloRESUMO
Superconducting quantum interference devices (SQUIDs) are currently used as magnetic flux detectors with ultra-high sensitivity for various applications such as medical diagnostics and magnetic material microstructure analysis. Single-crystalline superconducting boron-doped diamond is an excellent candidate for fabricating high-performance SQUIDs because of its robustness and high transition temperature, critical current density, and critical field. Here, we propose a fabrication process for a single-crystalline boron-doped diamond Josephson junction with regrowth-induced step edge structure and demonstrate the first operation of a single-crystalline boron-doped diamond SQUID above 2 K. We demonstrate that the step angle is a significant parameter for forming the Josephson junction and that the step angle can be controlled by adjusting the microwave plasma-enhanced chemical vapour deposition conditions of the regrowth layer. The fabricated junction exhibits superconductor-weak superconductor-superconductor-type behaviour without hysteresis and a high critical current density of 5800 A/cm2.
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Noncovalent, weak interactions in the second coordination sphere of the copper active site of Pseudoazurin (PAz) from Achromobacter cycloclastes were examined using a series of Met16X variants. In this study, the differences in protein stability due to the changes in the nature of the 16th amino acid (Met, Phe, Val, Ile) were investigated by electrospray ionization mass spectrometry (ESI-MS) and far-UV circular dichroism (CD) as a result of acid denaturation. The percentage of native states (folded holo forms) of Met16Phe variants was estimated to be 75% at pH 2.9 although the wild-type (WT), Met16Val and Met16Ile PAz, became completely unfolded. The high stability under acidic conditions is correlated with the result of the active site being stabilized by the aromatic substitution of the Met16 residue. The π-π interaction in the second coordination sphere makes a significant contribution to the stability of active site and the protein matrix.
Assuntos
Azurina/química , Azurina/metabolismo , Azurina/genética , Proteínas de Bactérias/química , Proteínas de Bactérias/genética , Proteínas de Bactérias/metabolismo , Sítios de Ligação , Dicroísmo Circular , Cobre/química , Cobre/metabolismo , Modelos Moleculares , Estabilidade Proteica , Espectrometria de Massas por Ionização por ElectrosprayRESUMO
Superconductivity in alkali metal-doped fullerene nanowhiskers (C60NWs) was observed in K3.3C60NWs, Rb3.0C60NWs and Cs2.0Rb1.0C60NWs with transition temperatures at 17, 25 and 26 K, respectively. Almost full shielding volume fraction (~80%) was observed in K3.3C60NWs when subjected to thermal treatment at 200 °C for a duration of 24 h. In contrast, the shielding fraction of Rb3.0C60NWs and Cs2.0Rb1.0C60NWs were calculated to be 8% and 6%, respectively. Here we report on an extensive investigation of the superconducting properties of these AC60NWs (A = K3.3, Rb3.0 and Cs2.0Rb1.0). These properties are compared to the ones reported on the corresponding conventional (single-crystal or powder) K-doped fullerene. We also evaluated the critical current densities of these C60NWs using the Bean model under an applied magnetic field up to 50 kOe.
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A method is introduced to isolate and measure the electrical transport properties of individual single-walled carbon nanotubes (SWNTs) aligned on an ST-cut quartz, from room temperature down to 2 K. The diameter and chirality of the measured SWNTs are accurately defined from Raman spectroscopy and atomic force microscopy (AFM). A significant up-shift in the G-band of the resonance Raman spectra of the SWNTs is observed, which increases with increasing SWNTs diameter, and indicates a strong interaction with the quartz substrate. A semiconducting SWNT, with diameter 0.84 nm, shows Tomonaga-Luttinger liquid and Coulomb blockade behaviors at low temperatures. Another semiconducting SWNT, with a thinner diameter of 0.68 nm, exhibits a transition from the semiconducting state to an insulating state at low temperatures. These results elucidate some of the electrical properties of SWNTs in this unique configuration and help pave the way towards prospective device applications.
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We report on a high-frequency electron-paramagnetic-resonance study of the type 1 copper site of pseudoazurin. The spectra fully resolve the contribution of a nearly axial spectrum besides the rhombic spectrum, which unequivocally proves the existence of two conformations of the copper site. Pseudoazurins have been considered from Achromobacter cycloclastes including eight mutants and from Alcaligenes faecalis. The two conformations are virtually the same for all pseudoazurins, but the rhombic/axial population varies largely, between 91/9 and 33/67. These observations are discussed in relation to optical absorption spectra and X-ray diffraction structures. A similar observation for fern plastocyanin from Dryopteris crassirhizoma suggests that dual conformations of type 1 copper sites are more common.