Diiron and trinuclear NiFe2 dithiolate complexes chelating by PCNCP ligands: Synthetic models of [FeFe]- and [NiFe]-hydrogenases

2020 ◽  
Vol 210 ◽  
pp. 111126 ◽  
Author(s):  
Pei-Hua Zhao ◽  
Jian-Rong Li ◽  
Xiao-Li Gu ◽  
Xing-Bin Jing ◽  
Xu-Feng Liu
2020 ◽  
Author(s):  
Raku Irie ◽  
Kei Miyako ◽  
Satoko Matsunaga ◽  
Ryuichi Sakai ◽  
Masato Oikawa

<div>Here, we newly propose the structure of protoaculeine B, an N-terminal moiety of the marine peptide toxin aculeine B, as possessing the cis-disubstituted tetrahydro-beta-carboline framework. We prepared two truncated model compounds that lack long-chain polyamine by one-step Pictet-Spengler reaction of tryptophan, and compared the NMR and mass spectra and chemical reactivity with those of natural protoaculeine B. The synthetic models reproduced the profiles of the natural product well, which was conclusive for the structural revision.</div>


2019 ◽  
Author(s):  
Maurizio Milano ◽  
Maurizio Fedi ◽  
J. Derek Fairhead

Abstract. In the European region, the magnetic field at satellite altitudes (~ 350 km) is mainly defined by a long-wavelength magnetic-low called here the Central Europe Magnetic Low (CEML), located to the southwest of the Trans European Suture Zone (TESZ). We studied this area by a joint analysis of the magnetic and total gradient (∇T) anomaly maps, for a range of different altitudes of 5 km, 100 km and 350 km. Tests on synthetic models showed the usefulness of the joint analysis at various altitudes to identify reverse dipolar anomalies and to characterize areas in which magnetization is weak. By this way we identified areas where either reversely or normally magnetized sources are locally dominant. At a European scale these anomalies are sparse, with a low degree of coalescence effect. The ∇T map indeed presents generally small values within the CEML area, indicating that the Palaeozoic Platform is weakly magnetized. At 350 km altitude, the TESZ effect is largely dominant: with intense ∇T highs above the East European Craton (EEC) and very small values above the Palaeozoic Platform, this again denoting a weakly magnetized crust. Small coalescence effects are masked by the trend of the TESZ. Although we identified sparsely located reversely magnetized sources in the Palaeozoic Platform of the CEML, the joint analysis does not support a model of a generally reversely magnetized crust. Instead, our analysis strongly favors the hypothesis that the CEML anomaly is mainly caused by a sharp contrast between the magnetic properties of EEC and Palaeozoic Platform.


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
L. Alvarez ◽  
M. A. Fernandez-Rodriguez ◽  
A. Alegria ◽  
S. Arrese-Igor ◽  
K. Zhao ◽  
...  

AbstractSelf-propelling microparticles are often proposed as synthetic models for biological microswimmers, yet they lack the internally regulated adaptation of their biological counterparts. Conversely, adaptation can be encoded in larger-scale soft-robotic devices but remains elusive to transfer to the colloidal scale. Here, we create responsive microswimmers, powered by electro-hydrodynamic flows, which can adapt their motility via internal reconfiguration. Using sequential capillary assembly, we fabricate deterministic colloidal clusters comprising soft thermo-responsive microgels and light-absorbing particles. Light absorption induces preferential local heating and triggers the volume phase transition of the microgels, leading to an adaptation of the clusters’ motility, which is orthogonal to their propulsion scheme. We rationalize this response via the coupling between self-propulsion and variations of particle shape and dielectric properties upon heating. Harnessing such coupling allows for strategies to achieve local dynamical control with simple illumination patterns, revealing exciting opportunities for developing tactic active materials.


Author(s):  
F. Riva ◽  
T. Fracasso ◽  
A. Guerra ◽  
P. Genet

AbstractIn shooting crimes, ballistics tests are often recommended in order to reproduce the wound characteristics of the involved persons. For this purpose, several “simulants” can be used. However, despite the efforts in the research of “surrogates” in the field of forensic ballistic, the development of synthetic models needs still to be improved through a validation process based on specific real caseworks. This study has been triggered by the findings observed during the autopsy performed on two victims killed in the same shooting incident, with similar wounding characteristics; namely two retained head shots with ricochet against the interior wall of the skull; both projectiles have been recovered during the autopsies after migration in the brain parenchyma. The thickness of the different tissues and structures along the bullets trajectories as well as the incident angles between the bullets paths and the skull walls have been measured and reproduced during the assemblage of the synthetic head models. Two different types of models (“open shape” and “spherical”) have been assembled using leather, polyurethane and gelatine to simulate respectively skin, bone and soft tissues. Six shots have been performed in total. The results of the models have been compared to the findings of post-mortem computed tomography (PMCT) and the autopsy findings.Out of the six shots, two perforated the models and four were retained. When the projectile was retained, the use of both models allowed reproducing the wounds characteristics observed on both victims in terms of penetration and ricochet behaviour. However, the projectiles recovered from the models showed less deformation than the bullets collected during the autopsies. The “open shape” model allowed a better controlling on the shooting parameters than the “spherical” model. Finally, the difference in bullet deformation could be caused by the choice of the bone simulant, which might under-represent either the strength or the density of the human bone. In our opinion, it would be worth to develop a new, more representative material for ballistic which simulates the human bone.


1978 ◽  
Vol 100 (9) ◽  
pp. 2899-2901 ◽  
Author(s):  
David A. Buckingham ◽  
Maxwell J. Gunter ◽  
Lewis N. Mander

Geophysics ◽  
2001 ◽  
Vol 66 (1) ◽  
pp. 308-319 ◽  
Author(s):  
Ivan Pšenčík ◽  
Joe A. Dellinger

In inhomogeneous isotropic regions, S-waves can be modeled using the ray method for isotropic media. In inhomogeneous strongly anisotropic regions, the independently propagating qS1- and qS2-waves can similarly be modeled using the ray method for anisotropic media. The latter method does not work properly in inhomogenous weakly anisotropic regions, however, where the split qS-waves couple. The zeroth‐order approximation of the quasi‐isotropic (QI) approach was designed for just such inhomogeneous weakly anisotropic media, for which neither the ray method for isotropic nor anisotropic media applies. We test the ranges of validity of these three methods using two simple synthetic models. Our results show that the QI approach more than spans the gap between the ray methods: it can be used in isotropic regions (where it reduces to the ray method for isotropic media), in regions of weak anisotropy (where the ray method for anisotropic media does not work properly), and even in regions of moderately strong anisotropy (in which the qS-waves decouple and thus could be modeled using the ray method for anisotropic media). A modeling program that switches between these three methods as necessary should be valid for arbitrary‐strength anisotropy.


2017 ◽  
Vol 73 (9) ◽  
pp. 703-709 ◽  
Author(s):  
Shayne Sorenson ◽  
Marina Popova ◽  
Atta M. Arif ◽  
Lisa M. Berreau

Metal–flavonolate compounds are of significant current interest as synthetic models for quercetinase enzymes and as bioactive compounds of importance to human health. Zinc–3-hydroxyflavonolate compounds, including those of quercetin, kampferol, and morin, generally exhibit bidentate coordination to a single ZnII center. The bipyridine-ligated zinc–flavonolate compound reported herein, namely bis(μ-4-oxo-2-phenyl-4H-chromen-3-olato)-κ3 O 3:O 3,O 4;κ3 O 3,O 4:O 3-bis[(2,2′-bipyridine-κ2 N,N′)zinc(II)] bis(perchlorate), {[Zn2(C15H9O3)2(C10H8N2)2](ClO4)2} n , (1), provides an unusual example of bridging 3-hydroxyflavonolate ligation in a dinuclear metal complex. The symmetry-related ZnII centers of (1) exhibit a distorted octahedral geometry, with weak coordination of a perchlorate anion trans to the bridging deprotonated O atom of the flavonolate ligand. Variable-concentration conductivity measurements provide evidence that, when (1) is dissolved in CH3CN, the complex dissociates into monomers. 1H NMR resonances for (1) dissolved in d 6-DMSO were assigned via HMQC to the H atoms of the flavonolate and bipyridine ligands. In CH3CN, (1) undergoes quantitative visible-light-induced CO release with a quantum yield [0.004 (1)] similar to that exhibited by other mononuclear zinc–3-hydroxyflavonolate complexes. Mass spectroscopic identification of the [(bpy)2Zn(O-benzoylsalicylate)]+ ion provides evidence of CO release from the flavonol and of ligand exchange at the ZnII center.


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