Generating Self-Map Monoids of Infinite Sets

Let be a countably infinite set, the group of permutations of , and the monoid of self-maps of . Given two subgroups , let us write if there exists a finite subset such that the groups generated by and are equal. Bergman and Shelah showed that the subgroups which are closed in the function topology on S fall into exactly four equivalence classes with respect to . Letting denote the obvious analog of for submonoids of E, we prove an analogous result for a certain class of submonoids of E, from which the theorem for groups can be recovered. Along the way, we show that given two subgroups which are closed in the function topology on S, we have if and only if (as submonoids of E), and that for every subgroup (where denotes the closure of G in the function topology in S and its closure in the function topology in E).     

Discovery of beta-LnNiSb3 (Ln = La, Ce): crystal growth, structure, and magnetic and transport behavior

A new polymorph of CeNiSb3 has been grown from a Sn flux and characterized by single-crystal X-ray diffraction. beta-CeNiSb3 crystallizes in the orthorhombic space group Pbcm (No. 57) with Z = 8. The unit cell parameters are a = 12.9170(2) A, b = 6.1210(5) A, c = 12.0930(6) A, and V = 956.13(9) A3. Its layered structure contains structural motifs similar to that of the first form of CeNiSb3 and consists of Ce atoms inserted between anionic layers of nearly square infinity2[Sb] nets and distorted infinity2[NiSb2] octahedra. We report the synthesis, magnetization, electrical resistivity, and specific heat of the new form of CeNiSb3 and compare the structures and physical properties of both polymorphs.     

Switchable Ambient‐Temperature Singlet–Triplet Dual Emission in Nonconjugated Donor–Acceptor Triarylboron–PtII Complexes

Double the fun! Singlet–triplet dual emission at ambient temperature has been achieved in compounds containing a triarylboron acceptor and an N‐(2′‐pyridyl)‐7‐azaindolyl donor group bridged by a tetrahedral Si linker (see figure). Pt^II chelation and chelate‐mode switching from N,N to N,C have been found to greatly enhance phosphorescent emission. Furthermore, both singlet and triplet emission bands are responsive to fluoride ions.

     

Flux growth and structure of two compounds with the EuIn2P2 structure type,AIn2P2 (A = Ca and Sr), and a new structure type,BaIn2P2

Single crystals of the new Zintl phases AIn₂P₂ [A = Ca (calcium indium phosphide), Sr (strontium indium phosphide) and Ba (barium indium phosphide)] have been synthesized from a reactive indium flux. CaIn₂P₂ and SrIn₂P₂ are isostructural with EuIn₂P₂ and crystallize in the space group P6₃/mmc. The alkaline earth cations A are located at a site with m symmetry; In and P are located at sites with 3m symmetry. The structure type consists of layers of A²⁺ cations separated by [In₂P₂]²⁻ anions that contain [In₂P₆] eclipsed ethane‐like units that are further connected by shared P atoms. This yields a double layer of six‐membered rings in which the In—In bonds are parallel to the c axis and to one another. BaIn₂P₂ crystallizes in a new structure type in the space group P2₁/m with Z = 4, with all atoms residing on sites of mirror symmetry. The structure contains layers of Ba²⁺ cations separated by [In₂P₂]²⁻ layers of staggered [In₂P₆] units that form a mixture of four‐, five‐ and six‐membered rings. As a consequence of this more complicated layered structure, both the steric and electronic requirements of the large Ba²⁺ cation are met.     

Directed ortho metallation of deep cavity cavitands: functionalizing molecular concavity

Directed ortho metallation (DOM) processes have been used to functionalize the cavity and rim of title cavitand 1. The preorganization of the host resulted in a considerable reduction in the range of products produced. Thus, whereas sixty-nine products are possible from per-functionalization, only twelve were observed when the host was treated with three different alkyllithiums.     

Metal-binding properties of human centrin-2 determined by micro-electrospray ionization mass spectrometry and UV spectroscopy

We analyzed the metal-binding properties of human centrin-2 (HsCen-2) and followed the changes in HsCen-2 structure upon metal-binding using micro-electrospray ionization mass spectrometry (muESI-MS). Apo-HsCen-2 is mostly monomeric. The ESI spectra of HsCen-2 show two charge-state distributions, representing two conformations of the protein. HsCen-2 binds four moles calcium/mol protein: one mol of calcium with high affinity, one additional mol of calcium with lower affinity, and two moles of calcium at low affinity sites. HsCen-2 binds four moles of magnesium/mol protein. The conformation giving the lower charge-state HsCen-2 by ESI, binds calcium and magnesium more readily than does the higher charge-state HsCen-2. Both conformations of HsCen-2 bind calcium more readily than magnesium. Calcium was more effective in displacing magnesium bound to HsCen-2 than vice versa. Binding of a peptide from a known binding partner, the xeroderma pigmentosum complementation group protein C (XPC), to apo-HsCen-2, occurs in the presence or the absence of calcium. Near and far-UV CD spectra of HsCen-2 show little difference with addition of calcium or magnesium. Minor changes in secondary structure are noted. Melting curves derived from temperature dependence of molar ellipticity at 222 nm for HsCen-2 show that calcium increases protein stability whereas magnesium does not. Delta 25 HsCen-2 behaves similarly to HsCen-2. We conclude that HsCen-2 binds calcium and magnesium and that calcium modulates HsCen-2 structure and function by increasing its stability without undergoing significant changes in secondary or tertiary structure.     

Exploitation of the Ornithine Effect Enhances Characterization of Stapled and Cyclic Peptides

A method to facilitate the characterization of stapled or cyclic peptides is reported via an arginine-selective derivatization strategy coupled with MS/MS analysis. Arginine residues are converted to ornithine residues through a deguanidination reaction that installs a highly selectively cleavable site in peptides. Upon activation by CID or UVPD, the ornithine residue cyclizes to promote cleavage of the adjacent amide bond. This Arg-specific process offers a unique strategy for site-selective ring opening of stapled and cyclic peptides. Upon activation of each derivatized peptide, site-specific backbone cleavage at the ornithine residue results in two complementary products: the lactam ring-containing portion of the peptide and the amine-containing portion. The deguanidination process not only provides a specific marker site that initiates fragmentation of the peptide but also offers a means to unlock the staple and differentiate isobaric stapled peptides.

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