Experimental and Theoretical Studies on Arene‐Bridged Metal–Metal‐Bonded Dimolybdenum Complexes

The bis(hydride) dimolybdenum complex, [Mo₂(H)₂{HC(N‐2,6‐iPr₂C₆H₃)₂}₂(thf)₂], 2 , which possesses a quadruply bonded Mo₂^II core, undergoes light‐induced (365 nm) reductive elimination of H₂ and arene coordination in benzene and toluene solutions, with formation of the Mo^I₂ complexes [Mo₂{HC(N‐2,6‐iPr₂C₆H₃)₂}₂(arene)], 3?C₆H₆ and 3?C₆H₅Me , respectively. The analogous C₆H₅OMe, p‐C₆H₄Me₂, C₆H₅F, and p‐C₆H₄F₂ derivatives have also been prepared by thermal or photochemical methods, which nevertheless employ different Mo₂ complex precursors. X‐ray crystallography and solution NMR studies demonstrate that the molecule of the arene bridges the molybdenum atoms of the Mo^I₂ core, coordinating to each in an η² fashion. In solution, the arene rotates fast on the NMR timescale around the Mo₂‐arene axis. For the substituted aromatic hydrocarbons, the NMR data are consistent with the existence of a major rotamer in which the metal atoms are coordinated to the more electron‐rich C?C bonds.     

Highly Stable Water‐Soluble Platinum Nanoparticles Stabilized by Hydrophilic N‐Heterocyclic Carbenes

Controlling the synthesis of stable metal nanoparticles in water is a current challenge in nanochemistry. The strategy presented herein uses sulfonated N‐heterocyclic carbene (NHC) ligands to stabilize platinum nanoparticles (PtNPs) in water, under air, for an indefinite time period. The particles were prepared by thermal decomposition of a preformed molecular Pt complex containing the NHC ligand and were then purified by dialysis and characterized by TEM, high‐resolution TEM, and spectroscopic techniques. Solid‐state NMR studies showed coordination of the carbene ligands to the nanoparticle surface and allowed the determination of a ¹³C–¹⁹⁵Pt coupling constant for the first time in a nanosystem (940 Hz). Additionally, in one case a novel structure was formed in which platinum(II) NHC complexes form a second coordination sphere around the nanoparticle.     

Structural Insights into the Design of Synthetic Nanobody Libraries

Single domain antibodies from camelids, or nanobodies, are a unique class of antibody fragments with several advantageous characteristics: small monomeric size, high stability and solubility and easy tailoring for multiple applications. Nanobodies are gaining increasing acceptance as diagnostic tools and promising therapeutic agents in cancer and other diseases. While most nanobodies are obtained from immunized animals of the camelid family, a few synthetic nanobody libraries constructed in recent years have shown the capability of generating high quality nanobodies in terms of affinity and stability. Since this synthetic approach has important advantages over the use of animals, the recent advances are indeed encouraging. Here we review over a dozen synthetic nanobody libraries reported so far and discuss the different approaches followed in their construction and validation, with an emphasis on framework and hypervariable loop design as critical issues defining their potential as high-class nanobody sources.     

Along the Lines of Nonadditive Entropies: q-Prime Numbers and q-Zeta Functions

The rich history of prime numbers includes great names such as Euclid, who first analytically studied the prime numbers and proved that there is an infinite number of them, Euler, who introduced the function ζ(s)≡∑n=1∞n−s=∏pprime11−p−s, Gauss, who estimated the rate at which prime numbers increase, and Riemann, who extended ζ(s) to the complex plane z and conjectured that all nontrivial zeros are in the R(z)=1/2 axis. The nonadditive entropy Sq=k∑ipilnq(1/pi)(q∈R;S1=SBG≡−k∑ipilnpi, where BG stands for Boltzmann-Gibbs) on which nonextensive statistical mechanics is based, involves the function lnqz≡z1−q−11−q(ln1z=lnz). It is already known that this function paves the way for the emergence of a q-generalized algebra, using q-numbers defined as 〈x〉q≡elnqx, which recover the number x for q=1. The q-prime numbers are then defined as the q-natural numbers 〈n〉q≡elnqn(n=1,2,3,⋯), where n is a prime number p=2,3,5,7,⋯ We show that, for any value of q, infinitely many q-prime numbers exist; for q≤1 they diverge for increasing prime number, whereas they converge for q>1; the standard prime numbers are recovered for q=1. For q≤1, we generalize the ζ(s) function as follows: ζq(s)≡〈ζ(s)〉q (s∈R). We show that this function appears to diverge at s=1+0, ∀q. Also, we alternatively define, for q≤1, ζq∑(s)≡∑n=1∞1〈n〉qs=1+1〈2〉qs+⋯ and ζq∏(s)≡∏pprime11−〈p〉q−s=11−〈2〉q−s11−〈3〉q−s11−〈5〉q−s⋯, which, for q<1, generically satisfy ζq∑(s)<ζq∏(s), in variance with the q=1 case, where of course ζ1∑(s)=ζ1∏(s).     

Electron and X-ray diffraction studies of chemically deposited thin films of cadmium selenide following reaction with mercury(II) chloride solution

The reaction between thin films of CdSe and aqueous HgCl₂ was studied using electron diffraction (ED) powder X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). It was found that α-Hg₃Se₂Cl₂ is formed in the CdSe film following its reaction with 0.01 M HgCl₂ for a period of 5 minutes. Upon completion of the reaction of CdSe powder with 0.01 M HgCl₂, Hg₂Cl₂ is present in addition to α-Hg₃Se₂Cl₂ in a molar ratio of 1:3.1. The effect of air annealing on CdSe powder was also studied. Heating in air to 450°C for 1 hour resulted in an XRD pattern corresponding to the hexagonal form of CdSe.     

Positron spectroscopy analysis in metallocene propylene/1‐octadecene copolymers: Parameters dependence on monoclinic and mesomorphic polymorphs

Copolymers of propylene and 1‐octadecene synthesized by a metallocene catalyst were characterized by PALS, WAXD, DSC, and density measurements. The change in the sizes and the number density of free‐volume holes as a function of the 1‐octadecene content were compared to the master laws published for copolymers of propylene with α‐olefins of shorter lengths. It was found that the samples were separated into two groups. The first set of samples obeyed the master laws while the second group deviated. This behavior was explained by the difference in the copolymer structure. The WAXD analysis confirmed the separation as well. The deviation was explained as due to the mesomorphic crystalline structure of the second group of samples, in contrast to the monoclinic one for the first group, which was a result of the relatively fast cooling from the molten state and from the high comonomer molar content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1994–2002, 2010     

Complete NMR assignment of 3, 4‐seco‐lup‐20(29)‐en‐3‐oic acid from Decatropis bicolor

Complete ¹H and ¹³C NMR chemical shift assignments for 3,4‐seco‐lup‐20(29)‐en‐3‐oic acid ( 1 ) have been established by means of two‐dimensional COSY, HSQC, HMBC and NOESY spectroscopic experiments as well as by analysis of MS data. Compound 1 was isolated from Decatropis bicolor (Zucc.) Radlk. (Rutaceae) in addition to six coumarins and one alkaloid of known structure. Copyright © 2012 John Wiley & Sons, Ltd.