Towards quantitatively reproducible substrates for SERS

There is a need for a method to facilitate the development of novel, reproducible colloidal surface-enhanced Raman scattering (SERS) substrates to encourage the use of SERS in applied studies. In this study we show for the first time that by using suitably designed SERS experiments in conjunction with multivariate analysis of variance (MANOVA), an objective assessment of colloidal SERS reproducibility can be made. This is demonstrated with the analyte cresyl violet, but could be extended to any analyte of interest for which reproducible SERS data are needed.     

Triosmium clusters derived from the reactions of thioureas with dodecacarbonyltriosmium: Crystal structures of [Os3(CO)11{η 1-SC(NMe2)2}], [Os3(CO)9(μ-OH)(μ-OMeOCO){η 1-SC(NMe2)2}] and [(μ-H)Os3(CO)9{μ 3-NHC(S)NH2}]

The reaction of [Os₃(CO)₁₂] with tetramethylthiourea in the presence of a methanolic solution of Me₃NO·2H₂O at 60° yields the compounds [Os₃(CO)₁₁{η ¹-SC(NMe₂)₂}] (1) in 56% yield and [Os₃(CO)₉(μ-OH)(μ-MeOCO){η ¹-SC(NMe₂)₂}] (2) in 10% yield in which the tetramethylthiourea ligand is coordinatedvia the sulfur atom at an equatorial position. Compound2 is a 50 e^? cluster with two metal-metal bonds and the hydroxy and methoxycarbonyl ligands bridging the open metal-metal edge. In contrast, the analogous reaction of [Os₃(CO)₁₂] with thiourea gives the compounts [(μ-H)Os₃(CO)₁₀{μ-NHC(S)NH₂}] (3) in 8% yield and [(μ-H)Os₃(CO)₉{₃-NHC(S)NH₂}] (4) in 30% yield. In3, the thioureato ligand bridges two osmium atomsvia the sulfur atom, whereas in4 in addition to the sulfur bridge, one of the nitrogen atoms of thioureato moiety bonds to the remaining osmium atom. The decacarbonyl compounds 3 can also be obtained in 50% yield from the reaction of [Os₃(CO)₁₀(MeCN)₂] with thiourea at ambient temperature. Compound3 converts to4 (65%) photochemically. Compound1 reacts with PPh₃ and acetonitrile at ambient temperature to give the simple substitution products [Os₃(CO)₁₁(PPh₃)] and [Os₃(CO)₁₁(MeCN)], respectively, while with pyridine, the oxidative addition product [(μ-H)Os₃(CO)₁₀(μ-NC₅H₄] is formed at 80°C. All the new compounds are characterized by IR,¹-H-NMR and elemental analysis together with the X-ray crystal structures of1,2 and4. Compound1 crystallizes in the triclinic space group P $P\bar 1$ with unit cell parametersa = 8.626(3) Å,b = 11.639(3) Å,c = 12.568(3_ Å,α = 84.67(2)°,β = 75.36(2)°,γ = 79.49(3)°,V = 1199(1) ų, andZ = 2. Least-squares refinement of 4585 reflections gave a final agreement factor ofR = 0.0766 (R _w = 0.0823). Compound2 crystallizes in the monoclinic space group P2_1/n with unit cell parametersa = 9.149(5) Å,b = 17.483(5) Å,c = 15.094(4) Å,β = 91.75(2)°,V = 2413(2) ų, andZ = 4. Least-squares refinement of 3632 reflections gave a final agreement factor ofR = 0.0603 (R _w = 0.0802). Compound4 crystallizes in the monoclinic space group C2/c with unit cell parametersa = 13.915(7) Å,b = 14.718(6) Å,c = 17.109(6) Å,β = 100.44(3)°,V = 3446(5) ų, andZ = 8. Least-squares refinement of 2910 reflections gave a final agreement factor ofR = 0.0763 (R _w = 0.0863).     

Diamond Lattice in the Space of Coordination Spheres

An algorithm has been developed for calculating radii, direction vectors, and coordination numbers (c.n.) for an arbitrary number of coordination spheres (CS) of the diamond lattice. It is established that the space of CS of the diamond lattice has imaginary CS in addition to real ones. The imaginary CS are defined by a direction vector, one of the components of which is an imaginary value. The coordination numbers of such CS are zero. For a great number of tabulated CS, we have studied the hierarchies of structural groups (motifs), forming in the space of coordination spheres and determining the X-ray spectra of lattice CS, the crystallomorphological growth forms of diamond crystals, and the forms of diamond fragmentation induced by thermal destruction and melting.     

On the solutions of the Wick-Cutkosky model in the instantaneous approximation

By reexamining the analysis of Basu and Biswas, based on the stereographic projection method of Fock and Levy, it is shown that the general solution of the Wick-Cutkosky model in the instantaneous approximation, hitherto unreported, involves only one quantum number; this is contrasted with the well-known solution which involves two quantum numbers, but for which the spectrum is degenerate with respect to one of them. The latter situation is shown to hold under a rather special circumstance.     

Synthesis and spectral study of biologically active macrocyclic complexes of divalent transition metal ions

The condensation reaction of succinyldihydrazide with glyoxal in the presence of divalent metal ions (1: 1: 1) results in the formation of the complexes of type [M(C₆H₈N₄O₂)X₂], where M = Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and X = Cl⁻, NO₃⁻, CH₃COO⁻. The complexes have been characterized with the aid of elemental analyses, conductance measurements and electronic, NMR, infrared spectral studies. On the basis of these studies, a six-coordinated distorted octahedral geometry in which two nitrogen and two carbonyl oxygen atoms are suitably placed for coordination toward metal ion, has been proposed for all the complexes. The complexes were tested for their in vitro antibacterial activity. Some of the complexes showed remarkable antibacterial activities against some selected bacterial strains.     

BRST analysis of topologically massive gauge theory: novel observations

A dynamical non-Abelian 2-form gauge theory (with B∧F term) is endowed with the “scalar” and “vector” gauge symmetry transformations. In our present endeavor, we exploit the latter gauge symmetry transformations and perform the Becchi–Rouet–Stora–Tyutin (BRST) analysis of the four (3+1)-dimensional (4D) topologically massive non-Abelian 2-form gauge theory. We demonstrate the existence of some novel features that have, hitherto, not been observed in the context of BRST approach to 4D (non-)Abelian 1-form as well as Abelian 2-form and 3-form gauge theories. We comment on the differences between the novel features that emerge in the BRST analysis of the “scalar” and “vector” gauge symmetries.     

Potential energy surfaces and lifetimes for spontaneous fission of heavy and superheavy elements from a variable density dependent mass formula

The potential energy surface for spontaneous fission is calculated using realistic density distributions for finite nuclei. Particular emphasis is placed on the region of the potential between the saddle and scission point. The method involves computing the energy of the system using an energy density functional consistent with varible density distributions and nuclear masses and obtained from a statistical many body theory. The results show that there exists an external or scission barrier to the fission process. Lifetimes and mass distributions which are computed using these potential energy surfaces are found to be in adequate agreement with observations for ²³⁴U, ²³⁶U, ²⁴⁰Pu, ²⁴⁴Cm, ²⁴⁸Cf, and ²⁵²Cf. Our predicted upper limit for the spontaneous fission half-lives of elements 112 and 114 is one year but the calculation indicates that these could be considerably shorter than a year.     

Notoph gauge theory: Superfield formalism

We derive absolutely anticommuting Becchi-Rouet-Stora-Tyutin (BRST) and anti-BRST symmetry transformations for the 4D free Abelian 2-form gauge theory by exploiting the superfield approach to BRST formalism. The antisymmetric tensor gauge field of the above theory was christened as the “notoph” (i.e. the opposite of “photon”) gauge field by Ogievetsky and Palubarinov way back in 1966–67. We briefly outline the problems involved in obtaining the absolute anticonimutativity of the (anti-) BRST transformations and their resolution within the framework of geometrical superfield approach to BRST formalism. One of the highlights of our results is the emergence of a Curci-Ferrari type of restriction in the context of 4D Abelian 2-form (notoph) gauge theory which renders the nilpotent (anti-) BRST symmetries of the theory to be absolutely anticommutative in nature.     

Ion acoustic solitons in a relativistic warm plasma with densitygradient

Modified Korteweg-deVries equation (mK-dV), which governs the behavior of ion acoustic solitons in a relativistic warm plasma with density gradient, is derived. The electron inertia is also taken into account which is important when the streaming ions are present in the plasma. A solution of the mK-dV equation is obtained for the constant density gradient. When the ion acoustic soliton propagates into the lower plasma density region, its amplitude and energy increase, but the width decreases; the same is the case for the stronger density gradients