{[Gd(DMF)_3(DMSO)(H_2O)_3](μ-CN)[Fe(CN)_5]}·2H_2O的合成,结构表征和磁性(英文)

0IntroductionThefirstmolecule鄄basedmagnetswerereportedin1986[1].Duringthelasttwodecades,moreandmoreattentionhasbeenpaidtothesynthesisofmolecule鄄basedmagnets,especiallytoPrussianBlueanalogu鄄es[2].TheoldPrussianBlueanalogueshavebeenbroughtuptodateduetoth…     

Efficient transport of saccharides through a liquid membrane mediated by a cyclodextrin dimer

A new efficient system for transporting saccharides through a liquid membrane has been constructed. The transport rates of saccharides were accelerated greatly by the cyclodextrin dimer 2; by contrast, the corresponding cyclodextrin monomer 1 was not effective at mediating saccharide transport. The transport rate of D-ribose through a chloroform liquid membrane was 17 times faster when the cyclodextrin dimer 2 was used as the transporter than when the cyclodextrin monomer 1 was used. Similarly the transport rate of methyl D-galactopyranoside was 16 times faster by 2 than by 1.     

Onq-deformation of bi-local system

We study a way ofq-deformation of the bi-local system, the two-particle system bounded by a relativistic harmonic-oscillator type of potential, from both points of view of mass spectra and the behavior of scattering amplitudes. In our formulation, the deformation is done so thatP ², the square of center-of-mass momentum, enters into the deformation parameters of relative coordinates. As a result, the wave equation of the bi-local system becomes nonlinear with respect toP ²; then, the propagator of the bi-local system suffers significant change so as to get a convergent self energy to the second order. The study is also made on the covariantq-deformation in four-dimensional spacetime.     

Cobalt oxide supported gold nanoparticles as a stable and readily-prepared precursor for the in situ generation of cobalt carbonyl like species

A treatment of cobalt oxide supported gold nanoparticles (Au/Co₃O₄) under syngas atmosphere effectively generated a cobalt carbonyl-like active species in the reaction vessel. The preparation of Au/Co₃O₄ was quite simple and the in situ generated cobalt species could be used as a stable and easy handling alternative for dicobalt octacarbonyl without bothersome purification prior to use. The reactions, which are sensitive to the purity of the dicobalt octacarbonyl, such as the alkoxycarbonylation of epoxides and the Pauson-Khand reaction, smoothly progressed with Au/Co₃O₄.     

tert-Butylnitrite as a convenient and easy-removable oxidant for the conversion of benzylic alcohols to ketones and aldehydes

The oxidation of primary and secondary benzylic alcohols was achieved by using tert-butyl nitrite (t-BuONO) as a stoichiometric oxidant. Various substrates were effectively converted into the corresponding ketones or aldehydes in good to excellent yields. The reaction presumably proceeded by a nitrosyl exchange and a subsequent thermal decomposition of benzylic nitrites. This process would realize an oxidation of alcohols with oxygen in theory by combining with a reproduction of alkyl nitrites from NO and alcohols under an O₂ atmosphere. In addition, almost pure oxidized products were readily obtained by simple evaporation of the reaction mixtures since t-BuONO produced only volatile side products.     

{[Gd(DMF)3(DMSO)(H2O)3](μ-CN)[Fe(CN)5]}·2H2O的合成，结构表征和磁性

A new cyano-bridged Gadolinium^Ⅲ-Iron^Ⅲ complex {[Gd(DMF)₃(DMSO)(H₂O)₃](μ-CN)[Fe(CN)₅]}·2H₂O (DMF=N,N-dimethylformamide; DMSO=dimethylsulfoxide) was synthesized by the grinding reaction method. It crysta-llizes in the triclinic, space group P1 with cell parameters: a=0.90363(2) nm, b=1.250 78(3) nm, c=1.41303(1) nm, α=93.174(1)°, β=94.406(1)°, γ=91.817(2)°, and V=1.588 87(5) nm³, D_c=1.582 g·cm^-3, Z=2, M_r=756.72, F(000)=760, μ=2.645 mm^-1. The slightly distorted square-antiprism eightfold-coordinated Gd(Ⅲ) and the approxi-mately oriented octahedrally sixfold-coordinated Fe(Ⅲ) are linked by a cyano-bridge group to construct a dinuclear compound. The {[Gd(DMF)₃(DMSO)(H₂O)₃](μ-CN)[Fe(CN)₅]} species are held together via hydrogen bonds to form a three-dimensional framework. The Gd(Ⅲ)-Fe(Ⅲ) interaction is antiferromagnetic. CCDC: 223430.     

The Progress of the Gait Impairment and Brain Activation in a Patient with Post-stroke Hemidystonia

Objective: We explore the effects of body weight-supported (BWS) treadmill training, including the change of cortical activation, on a patient with post-stroke hemidystonia. Patient: The patient was a 71-year-old man with left thalamus hemorrhage. His motor symptoms indicated slight impairment. There was no overactive muscle contraction in the supine, sitting, or standing positions. During his gait, the right initial contact was the forefoot, and his right knee showed an extension thrust pattern. These symptoms suggested that he had post-stroke hemidystonia. Methods: The patient performed BWS treadmill training 14 times over 3 weeks. The effects of the BWS training were assessed by a step-length analysis, electromyography and functional magnetic resonance imaging (fMRI). Results: The patient''s nonparetic step length was extended significantly in the Inter-BWS (p<0.001) and Post-BWS (p=0.025) periods compared to the Pre-BWS session. The excessive muscle activity of the right gastrocnemius medialis in the swing phase was decreased at the Inter-BWS, Post-BWS, and follow-up compared to the Pre-BWS session. The peak timing difference of the bilateral tibialis anterior muscle became significant (p<0.05) on the first day of the intervention. The fMRI revealed that the cortical areas activated by the motor task converged through the intervention (p<0.05, family-wise error corrected). Conclusion: These results suggest that there was improvement of the patient''s symptoms of post-stroke hemidystonia due to changes in the brain activity during voluntary movement after BWS intervention. Body weight-supported treadmill training may thus be an effective treatment for patients with poststroke hemidystonia.     

High benzene selectivity of mesoporous silicate for BTX gas sensing microfluidic devices

The gas selectivities of highly ordered mesoporous silicates and commercially-obtained porous silicates with respect to benzene, toluene and xylene were studied. After studying the porosities, pore uniformities, and surface silanol structures of the silicates and their relationships to gas selectivity in detail, we found that we could achieve high benzene selectivity by controlling the micropore size (less than 1 nm). Concluding that mesoporous silicate has a suitable micropore size and structure for benzene selectivity, we also observed that mesoporous silicate SBA-16 exhibited a high (>6) benzene selectivity from toluene and xylene even in a pseudo-atmospheric environment. A benzene detection limit of about 100 ppb was achieved by introducing SBA-16 into a microfluidic device originally developed for the separate detection of benzene, toluene, and xylene gases.     

A new strategy toward the total synthesis of stachyflin,a potent anti-influenza A virus agent: concise route to the tetracyclic core structure

[reaction: see text] A new strategy directed toward the total synthesis of stachyflin, a potent and novel anti-influenza A virus agent isolated from a microorganism, has been presented through the enantioselective synthesis of the tetracyclic core structure. The synthetic method features a BF(3) x Et(2)O-induced domino epoxide-opening/rearrangement/cyclization reaction as the key step.     

Synthesis,Structures, and Some Reactions of [(Thioacyl)thio]‐ and (Acylseleno)antimony and ‐bismuth Derivatives ((RCSS)xMR$\rm{_{{\bf 3 - }{\bf x}}^{\bf 1} }$ and (RCOSe)xMR$\rm{_{{\bf 3 - }{\bf x}}^{\bf 1} }$ with M = Sb,Bi and x = 1–3)

A series of [(thioacyl)thio]‐ and (acylseleno)antimony and [(thioacyl)thio]‐ and (acylseleno)bismuth, i.e., (RCSS)_xMR and (RCOSe)_xMR (M = Sb, Bi, R¹ = aryl, x = 1–3), were synthesized in moderate to good yields by treating piperidinium or sodium carbodithioates and ‐selenoates with antimony and bismuth halides. Crystal structures of (4‐MeC₆H₄CSS)₂Sb(4‐MeC₆H₄) ( 9b′ ), (4‐MeOC₆H₄COSe)₂Sb(4‐MeC₆H₄) ( 12c′ ), (4‐MeOC₆H₄COS)₂Bi(4‐MeC₆H₄) ( 15c′ ), and (4‐MeOC₆H₄CSS)₂BiPh ( 18c ) along with (4‐MeC₆H₄COS)₂SbPh ( 6b ) and (4‐MeC₆H₄COS)₃Sb ( 7b ) were determined (Figs. 1 and 2). These compounds have a distorted square pyramidal structure, where the aryl or carbothioato (= acylthio) ligand at the central Sb‐ or Bi‐atom is perpendicular to the plane that includes the two carbodithioato (= (thioacyl)thio), carboselenato (= acylseleno), or carbothioato ligand and exist as an enantiomorph pair. Despite the large atomic radii, the C?S ??? Sb distances in (RCSS)₂MR¹ (M = As, Sb, Bi; R¹ = aryl) and the C?O ??? Sb distances in (RCOS)_xMR (M = As, Sb, Bi; x = 2, 3) are comparable to or shorter than those of the corresponding arsenic derivatives (Tables 2 and 3). A molecular‐orbital calculation performed on the model compounds (MeC(E)E¹)_3?xMMe_x (M = As, Sb, Bi; E = O, S; E¹ = S, Se; x = 1, 2) at the RHF/LANL2DZ level supported this shortening of C?E ??? Sb distances (Table 4). Natural‐bond‐orbital (NBO) analyses of the model compounds also revealed that two types of orbital interactions n_S → σ and n_S → σ play a role in the (thioacyl)thio derivatives (MeCSS)_3?xMMe_x (x = 1, 2) (Table 5). In the acylthio‐MeCOSMMe₂ (M = As, Sb, Bi), n_O → σ contributes predominantly to the orbital interactions, but in MeCOSeSbMe₂, none of n_O → σ and n_O → σ contributes to the orbital interactions. The n_S → σ and n_S → σ orbital interactions in the (thioacyl)thio derivatives are greater than those of n_O → σ and n_O → σ in the acylthio and acylseleno derivatives (MeCOE)_3?xMMe_x (E = S, Se; M = As, Sb, Bi; x = 1, 2). ?The reactions of RCOSeSbPh₂ (R = 4‐MeC₆H₄) with piperidine led to the formation of piperidinium diphenylselenoxoantimonate(1?) (= piperidinium diphenylstibinoselenoite) (H₂NC₅H₁₀)⁺Ph₂SbSe^?, along with the corresponding N‐acylpiperidine (Table 6). Similar reactions of the bis‐derivatives (RCOSe)₂SbR¹ (R, R¹ = 4‐MeC₆H₄) with piperidine gave the novel di(piperidinium) phenyldiselenoxoantimonate(2?) (= di(piperidinium) phenylstibonodiselenoite), [(H₂NC₅H₁₀)⁺]₂(PhSbSe₂)^2?, in which the negative charges are delocalized on the SbSe₂ moiety (Table 6). Treatment of RCOSeSbR (R, R¹ = 4‐MeC₆H₄) with N‐halosuccinimides indicated the formation of Se‐(halocyclohexyl) arenecarboselenoates (Table 8). Pyrolysis of bis(acylseleno)arylbismuth at 150° gave Se‐aryl carboselenoates in moderate to good yields (Table 9).