Univalent gallium and indium phosphane complexes: from pyramidal M(PPh3)3(+) to carbene-analogous bent M(PtBu3)2(+) (M=Ga, In) complexes

In a new oxidative route, Ag(+)[Al(OR(F))(4)](-) (R(F)=C(CF(3))(3)) and metallic indium were sonicated in aromatic solvents, such as fluorobenzene (PhF), to give a precipitate of silver metal and highly soluble [In(PhF)(n)](+) salts (n=2, 3) with the weakly coordinating [Al(OR(F))(4)](-) anion in quantitative yield. The In(+) salt and the known analogous Ga(+)[Al(OR(F))(4)](-) were used to synthesize a series of homoleptic PR(3) phosphane complexes [M(PR(3))(n)](+), that is, the weakly PPh(3)-bridged [(Ph(3)P)(3)In-(PPh(3))-In(PPh(3))(3)](2+) that essentially contains two independent [In(PPh(3))(3)](+) cations or, with increasing bulk of the phosphane, the carbene-analogous [M(PtBu(3))(2)](+) (M=Ga, In) cations. The M(I)-P distances are 27 to 29 pm longer for indium, and thus considerably longer than the difference between their tabulated radii (18 pm). The structure, formation, and frontier orbitals of these complexes were investigated by calculations at the BP86/SV(P), B3LYP/def2-TZVPP, MP2/def2-TZVPP, and SCS-MP2/def2-TZVPP levels.     

Aureolic acids: similar antibiotics with different biosynthetic gene clusters

In this issue of Chemistry & Biology, Méndez and colleagues describe the sequence and organization of the chromomycin gene cluster. Unexpectedly, the arrangement is starkly different from the mithramycin biosynthetic cluster, despite similarity in the individual genes and the near identical structures of the two antibiotic aureolic acids.     

Spectrophotometric Determination of Ammonia in Estuarine Waters by Hybrid Reagent‐Injection Gas‐Diffusion Flow Analysis

Abstract

A flow‐injection gas‐diffusion technique is described for the online determination of ammonia in estuarine waters covering a salinity range of S=0 to 36. The flow analysis system, which is a hybrid of reagent injection and conventional sample‐injection flow systems, avoids the need for a rotary injection valve. Whereas gas‐diffusion techniques have been widely applied in conventional sample‐injection flow analysis, reagent‐injection flow analysis involving gas diffusion has been little used because it is susceptible to interference from dissolved gaseous species such as carbon dioxide coexisting with ammonia in the sample. This source of interference has been overcome by online adjustment of sample to pH 8.4 prior to the injection of the base that initiates gas diffusion of ammonia. The pore sizes of hydrophobic membranes used in gas diffusion were characterized by a bubble‐point test prior to use in the flow analysis system. These showed wide variation in pore size, and grading and careful selection was necessary in order to obtain reliable gas diffusion measurements of ammonia. The proposed flow‐injection system can be operated in a continuous flow mode, at a sample throughput of 135 measurements hr^?1 with a typical limit of detection (LOD) of 9 µg N L^?1, or in stopped‐flow mode at 60 measurements hr^?1 with a LOD of 3 µg N L^?1. The technique was validated using water samples containing a wide range of dissolved carbon dioxide concentrations, salinity, and pH. Excellent agreement (r=0.999) was observed between results obtained using the reagent‐injection system and an approved reference method.     

Sexual dimorphism in the human brain: evidence from neuroimaging

In recent years, more and more emphasis has been placed on the investigation of sex differences in the human brain. Noninvasive neuroimaging techniques represent an essential tool in the effort to better understand the effects of sex on both brain structure and function. In this review, we provide a comprehensive summary of the findings that were collected in human neuroimaging studies in vivo thus far: we explore sexual dimorphism in the human brain at the level of (1) brain structure, in both gray and white matter, observed by voxel-based morphometry (VBM) and diffusion tensor imaging (DTI), respectively; (2) baseline neural activity, studied using resting-state functional magnetic resonance imaging (rs-fMRI) and positron emission tomography (PET); (3) neurochemistry, visualized by means of neuroreceptor ligand PET; and (4) task-related neural activation, investigated using fMRI. Functional MRI findings from the literature are complemented by our own meta-analysis of fMRI studies on sex-specific differences in human emotional processing. Specifically, we used activation likelihood estimation (ALE) to provide a quantitative approach to mapping the consistency of neural networks involved in emotional processing across studies. The presented evidence for sex-specific differences in neural structure and function highlights the importance of modeling sex as a contributing factor in the analysis of brain-related data.     

Asymptotic Growth of Associated Primes of Certain Graph Ideals

We specify a class of graphs, H _t , and characterize the irreducible decompositions of all powers of the cover ideals. This gives insight into the structure and stabilization of the corresponding associated primes; specifically, providing an answer to the question “For each integer t ≥ 0, does there exist a (hyper) graph H _t such that stabilization of associated primes occurs at n ≥ (χ(H _t ) ?1) + t?” [4 Francisco , C. A. , Hà , H. T. , Van Tuyl , A. ( 2011 ). Colorings of hypergraphs, perfect graphs, and associated primes of powers of monomial ideals . J. Algebra 331 : 224 – 242 .[Crossref], [Web of Science ®] , [Google Scholar]]. For each t, H _t has chromatic number 3 and associated primes that stabilize at n = 2 + t.     

The Limiting Shape of the Generic Initial System of a Complete Intersection

Consider a complete intersection I of type (d ₁,…, d _r ) in a polynomial ring over a field of characteristic 0. We study the graded system of ideals {gin(I ⁿ )} _n obtained by taking the reverse lexicographic generic initial ideals of the powers of I and describe its asymptotic behavior. This behavior is nicely captured by the limiting shape which is shown to depend only on the type of the complete intersection.     

Auxiliary Variables in Multiple Imputation When Data Are Missing Not at Random

Most current implementations of multiple imputation (MI) assume that data are missing at random (MAR), but this assumption is generally untestable. We performed analyses to test the effects of auxiliary variables on MI when the data are missing not at random (MNAR) using simulated data and real data. In the analyses we varied (a) the correlation, (b) the level of missing data, (c) the pattern of missing data, and (d) sample size. Results showed that MI performed adequately without auxiliary variables but they also had a modest impact on bias in the real data and improved efficiency in both data sets. The results of this study suggest that, counter to the concern about the violation of the MAR assumption, MI appears to be quite robust to missing data that are MNAR in analytic situations such as the ones presented here. Further, results can be made even better via the use of auxiliary variables, particularly when efficiency is a primary concern.