Electrical Behaviour of Heterobimetallic [MM′(EtCS2)4] (MM′=NiPd,NiPt, PdPt) and MM′X‐Chain Polymers [PtM(EtCS2)4I] (M=Ni,Pd)

Herein, we report the isolation of new heterobimetallic complexes [Ni_0.6Pd_1.4(EtCS₂)₄] ( 1 ), [NiPt(EtCS₂)₄] ( 2 ) and [Pd_0.4Pt_1.6(EtCS₂)₄] ( 3 ), which were constructed by using transmetallation procedures. Subsequent oxidation with iodine furnished the MM′X monodimensional chains [Ni_0.6Pt_1.4(EtCS₂)₄I] ( 4 ) and [Ni_0.1Pd_0.3Pt_1.6(EtCS₂)₄I] ( 5 ). The physical properties of these systems were investigated and the chain structures 4 and 5 were found to be reminiscent of the parent [Pt₂(EtCS₂)₄I] species. However, they were more sensitively dependent on the localised nature of the charge on the Ni ion, which caused spontaneous breaking of the conduction bands.     

Semi-active friction tendons for vibration control of space structures

Semi-active vibration control systems are becoming popular because they offer both the reliability of passive systems and the versatility of active control without high power demands. In this work, a new semi-active control system is proposed and studied numerically. The system consists of variable-friction dampers linked to the structure through cables. Auxiliary soft springs in parallel with these friction dampers allow them to return to their initial pre-tensioned state. Using cables makes the system suitable for deployable, flexible and lightweight structures, such as space structures (spacecraft). A control system with three control laws applied to a single-degree-of-freedom structure is studied. Two of these laws are derived by using Lyapunov theory, whereas the third one is developed heuristically. In order to assess the performance of the control system, a parametric study is carried out through numerical simulations. An application of the proposed method to multi-degree-of-freedom structures is also presented and demonstrated through a numerical example. The system in semi-active mode is more effective than in passive mode and its effectiveness is less sensitive to loss of pre-tension.     

Extended WKB Method,Resonances and Supersymmetric Radial Barriers

Semiclassical approximations are implemented in the calculation of position and width of low-energy resonances for radial barriers. The numerical integrations are delimited by τ/τ _life≪8, with τ the period of a classical particle in the barrier trap and τ _life the resonance lifetime. These energies are used in the construction of ‘haired’ short-range potentials as the supersymmetric partners of a given radial barrier. The new potentials could be useful in the study of the transient phenomena which give rise to the Moshinsky’s diffraction in time.     

Nonholonomic Hamilton–Jacobi theory via Chaplygin Hamiltonization

We develop Hamilton–Jacobi theory for Chaplygin systems, a certain class of nonholonomic mechanical systems with symmetries, using a technique called Hamiltonization, which transforms nonholonomic systems into Hamiltonian systems. We give a geometric account of the Hamiltonization, identify necessary and sufficient conditions for Hamiltonization, and apply the conventional Hamilton–Jacobi theory to the Hamiltonized systems. We show, under a certain sufficient condition for Hamiltonization, that the solutions to the Hamilton–Jacobi equation associated with the Hamiltonized system also solve the nonholonomic Hamilton–Jacobi equation associated with the original Chaplygin system. The results are illustrated through several examples.     

Rapid detection of apoptosis in mammalian cells by using intact cell MALDI mass spectrometry

Detection of cell death has extensive applications and is of great commercial value. However, most current high-throughput cell viability assays cannot distinguish the two major forms of cell death: apoptosis and necrosis. Many apoptosis-specific detection methods exist but they are time consuming and labour intensive. In this work, we proposed a novel approach based on Matrix-Assisted Laser Desorption/Ionization Time-Of-Flight Mass Spectrometry (MALDI-TOF-MS) for the specific detection of apoptosis in cultured mammalian cells. Buffer washed cells were directly mixed with a matrix solution and subsequently deposited onto the stainless steel target for MALDI analysis. The resulting mass spectrometric profiles were highly reproducible and can be used to reflect cell viability. Remarkably, the mass spectrometric profiles generated from apoptotic cells were distinct from those from either normal or necrotic cells. The apoptosis-specific features of the mass spectra were proportional to the percentage of apoptotic cells in the culture, but are independent of the drugs used to stimulate apoptosis. This is the first report on the utilization of intact cell MALDI mass spectrometry in detecting mammalian cell apoptosis, and can be used as a basis for the development of a reliable, fast, label-free and high-throughput method for detecting apoptotic cell death.     

Differential ESI-MS behaviour of highly similar metallothioneins

ESI-MS can only be accepted as a quantification method when using standards with a high resemblance to the analyte(s). Unfortunately, this is usually not applicable to metallothioneins (MTs), a superfamily of singular metal-binding cysteine-rich proteins, present in all living organisms, since the absence of suitable reference material due to the high diversity among metal-MT species precludes their quantification by molecular mass spectrometry. Even thus, it is widely assumed that the intensities of the ESI-MS peaks of similar species are directly correlated with their relative concentration in the sample, and this has been extended to the determination of different MT proteins coexisting in a sample.Practically all organisms contain several MT isoforms, some of them exhibiting highly similar sequences, with conserved coordinating Cys residues. For the current analysis, we used as a model system the MT isoforms of two terrestrial snails (Helix pomatia and Cornu aspersum). Hence, distinct samples were prepared by mixing, at different molar ratios, the recombinant HpCuMT and HpCdMT isoforms from H. pomatia, or the recombinant CaCuMT, CaCdMT and CaCdCuMT isoforms from C. aspersum, and they were analyzed by ESI-MS both at neutral pH (for Zn-loaded MT forms) and at acidic pH (for the corresponding apo-forms). The results here presented reveal that the ESI-MS peak intensity of a single MT species strongly depends on its sensitivity to be ionized, and thus, on the presence or absence of metal ions bound. Furthermore, our data demonstrate that very similar MT isoforms of the same organism with similar pI (ranging from 7.9 to 8.3) can show a clear different sensitivity to ES ionization, something that cannot be readily predicted only by consideration of their amino acid content. In conclusion, even in this optimum case, deductions about quantity features of MT samples drawn from ESI-MS measurements should be carefully considered.     

Low temperature neutron diffraction studies in [Mn3(suc)2(ina)2]n: an homometallic molecular 3D ferrimagnet

Neutron diffraction techniques have been used to determine the low temperature crystal structure and to shed light on the magnetic behavior of the [Mn(3)(suc)(2)(ina)(2)](n) (suc = succinate and ina = isonicotinate) complex. The ferromagnetic signal observed below T(c) ≈ 5 K in this compound is due to a noncompensation of homometallic spins in the 3D framework. The Mn(II) magnetic moments obtained from neutron diffraction refinements are slightly lower than those observed for isolated Mn(II) ions; this can be due to covalent spin delocalization or geometrical magnetic fluctuations. A small discrepancy between the value of the magnetic moments of each Mn(II) site is also observed [Mn(1) 4.1(2) μ(B) and the Mn(2) 3.9(1) μ(B)]. These differences between the theoretical and observed manganese magnetic moments are not unexpected in this large spin metal complex, and qualitatively reasonable given the synergistic interaction between the metal ions through oxo-bridge. The competition among different interactions, principally those covalent through organic ligands and dipolar interaction, drive to a final 3D ferrimagnetic order.