Photoelectron imaging spectroscopy and theoretical investigation of ZrSi

The photoelectron spectrum of ZrSi(-) has been measured at two different photon energies: 2.33 eV and 3.49 eV, providing electron binding energy and photoelectron angular distribution information. The obtained vertical detachment energy of ZrSi(-) is 1.584(14) eV. The neutral ground and excited state terms are assigned based on experimental and theoretical results. The ground state of ZrSi is tentatively assigned as a (3)Σ(+) state with a configuration of 1σ(2) 1π(4) 1δ(0) 2σ(1) 3σ(1). A low lying (3)Π(i) neutral excited state is identified to be 0.238 eV (1919 cm(-1)) above the ground state. The anion ground state is designated as a (2)Σ(+) state with a 1σ(2) 1π(4) 1δ(0) 2σ(2) 3σ(1) valence electron configuration. A Franck-Condon (FC) simulation of the photoelectron spectrum has been carried out. For the (3)Σ(+) ← (2)Σ(+) band, theoretically calculated bond lengths and frequencies are used in the FC calculation which give good agreement with experiment, while for the (3)Π(i) ← (2)Σ(+) band, the ZrSi bond length is estimated from the FC spectrum. Comparisons are made with previously published theoretical studies and inconsistencies are pointed out. To the best of our knowledge, this study provides the first spectroscopic information on the transition metal-silicon diatomic, ZrSi.     

Surface Coating Rescues Proteins from Magnetite Nanoparticle Induced Damage

The presence of magnetic nanoparticles (NPs) in physiological systems induces toxicity through its effects on mitochondrial function and reactive oxygen species (ROS) imbalance. Magnetic NP induced cytotoxicity has been elaborately evaluated for impending threats, however, a detailed investigation is lacking. It is shown that the interaction of Fe₃O₄ NPs with cytochrome c can lead to different events based on the NPs to protein ratio, the solution conditions, and the type of surface protection. At low NPs concentration, rapid binding and subsequent electron transfer are the preferred events while at higher concentration slow oxidative modification of the protein is initiated. The slow event of protein modification yields conformational disorientation, loss of stability, and formation of amyloid‐like structures with cytochrome c. The possibility that the NP induced oxidative stress and age can work in concert to compromise different aspects of cellular quality control processes is discussed. Suitable surface modifications of the NPs inhibit their direct binding to the protein molecules and minimize NP induced toxicity.     

Direct Activation of Nucleobases with Small Molecules for the Conditional Control of Antisense Function

Conditionally controlled antisense oligonucleotides provide precise interrogation of gene function at different developmental stages in animal models. Only one example of small molecule-induced activation of antisense function exist. This has been restricted to cyclic caged morpholinos that, based on sequence, can have significant background activity in the absence of the trigger. Here, we provide a new approach using azido-caged nucleobases that are site-specifically introduced into antisense morpholinos. The caging group design is a simple azidomethylene (Azm) group that, despite its very small size, efficiently blocks Watson–Crick base pairing in a programmable fashion. Furthermore, it undergoes facile decaging via Staudinger reduction when exposed to a small molecule phosphine, generating the native antisense oligonucleotide under conditions compatible with biological environments. We demonstrated small molecule-induced gene knockdown in mammalian cells, zebrafish embryos, and frog embryos. We validated the general applicability of this approach by targeting three different genes.     

Synthesis and structural characterisation of new Re(III) complexes using aldimines of α-amino acids as coligands

Complexes of the general formula [Re^III(L)Cl(PPh₃)₂] have been synthesised by reacting H₂L and [ReOCl₃(PPh₃)₂] in ethanol. Here H₂L represents imines of α-amino acids (glycine, l-alanine, l-valine, l-phenylalanine) derived from salicylaldehyde and naphthaldehyde. The crystal structure of one complex has been determined. The complexes are mononuclear, paramagnetic and display paramagnetic ¹H NMR in CDCl₃ solution. Their spectral and redox properties are scrutinised.     

Spectroscopy of 62Ni with the 61Ni(d, p) reaction

Differential cross sections, vector and tensor analysing powers have been measured for the ⁶¹Ni(d, p) reaction at a deuteron energy of 12.3 MeV. Most of the 30 transitions observed below 8.5 MeV excitation are dominated by a single j-value, which was determined from behaviour of the analysing power data. For a number of transitions it was possible to make unambiguous j-assignment relying on the established j-dependence of the T₂₂ tensor analysing power. The deduced spectroscopic factors indicate that the full strength of neutron transfer to the ($\text{2p, 1f}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$) and $\text{1}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ orbits was found and seven $\text{5}\text{2}{}^{\mathrm{+}}$ transitions were located above 5.3 MeV. The separated strengths of the $\text{3}\text{2}{}^{\mathrm{?}}\text{,}\text{1}\text{2}{}^{\mathrm{?}}\text{and}\text{5}\text{2}{}^{\mathrm{?}}$ transitions are compared with shell-model calculations for the low-lying states of ⁶²Ni.     

Morphological mapping and analysis of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] and its clay nanocomposites by atomic force microscopy

Atomic force microscopy was successfully applied for comprehensive nanoscale surface and bulk morphological characterization of thermoplastic elastomeric triblock copolymers: poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) having different block lengths and their clay based nanocomposites. Commercially available Cloisite®20A and octadecyl (C₁₈) ammonium ion modified montmorillonite clay (OC) prepared in our laboratory by cation exchange reaction were used. The phase detected images in the tapping mode atomic force microscopy exhibited a well‐ordered phase separated morphology consisting of bright nanophasic domains corresponding to hard component and darker domains corresponding to softer rubbery ethylene‐co‐butylene (PEB) lamella for all the neat triblock copolymers. This lamellar morphology gave a domain width of 19–23 nm for styrenic nanophase and 12–15 nm for ethylene‐co‐butylene phase of SEBS having end to mid block length ratio of 30:70 and block molecular weights of 8800–41,200–8800. On increasing the ratio of block lengths of the polymer matrix and the selectivity of the solvent toward the blocks used for casting, the morphological features of the resultant films altered along with change in domain thickness. The phase images showed position and distribution of the brightest clay stacks in the dark‐bright contrast of the base matrix of the nanocomposite. Exfoliated and intercalated‐exfoliated morphology obtained in the case of Cloisite®20A and OC‐based SEBS nanocomposites, respectively, is further supported by X‐ ray diffraction and transmission electron microscopy studies. The lamellar thickness of the soft phases widened to 50–75 nm, where the layered clay silicates (40–54 nm in length and 4–17 nm in width) were embedded in the soft rubbery phases in the block copolymeric matrix of the nanocomposite. The marginally thicker width of the hard styrenic phases and slightly shrinked width of the soft rubbery lamella can be observed from the regions where no nanofiller is present. Distinct differences in bulk morphologies of the nanocomposites prepared in the melt and the solution processes were obtained with nanocomposites. The presence of clay particles was evident from the almost zero pull‐off and snap‐in force in the force‐distance analysis of SEBS based nanocomposite. This analysis also revealed stronger tip interaction resulting in highest contact and adhesive forces with the softer PEB region relative to the harder PS region. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 52–66, 2007     

Tensor analysing powers of (d,p) reactions on 28Si, 67Zn, 90Zr and 208Pb at 12.3 MeV

The tensor analysing powers T₂₀ and T₂₂ of(d, p) reactions leading to several states of the final nuclei ²⁹Si, ⁶⁸Zn, ⁹¹Zr and ²⁰⁹Pb were measured at 12.3 MeV deuteron beam energy. The measured tensor analysing powers together with the vector analysing power and cross-section data are compared with DWBA calculations with and without the deuteron D-state. The D-state effects and j-dependence of the tensor analysing powers are discussed. The spin transfers involved in populating the 1.08, 1.88 and 3.30 MeV states in ⁶⁸Zn in the ⁶⁷Zn(d, p)⁶⁸Zn reaction are deduced to be predominantly $\text{1}\text{2}{}^{\mathrm{?}}$. This implies an assignment for the 3.287 MeV level of ⁶⁸Zn of J^π = 2⁺.