The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

The Halogen Bond

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Light-Emitting Self-Assembled Materials Based on d(8) and d(10) Transition Metal Complexes.

Halogen Bonding in Supramolecular Chemistry.

Host immunity to mycobacterial infection is dependent on the activation of T lymphocytes and their recruitment with monocytes to form granulomas. These discrete foci of activated macrophages and lymphocytes provide a microenvironment for containing the infection. The cytokine, TNF, is essential for the formation and maintenance of granulomas, but the mechanisms by which TNF regulates these processes are unclear. We have compared the responses of TNF-deficient (TNF(-/-)) and wild-type C57BL/6 mice to infection with Mycobacterium smegmatis, a potent inducer of TNF, and virulent Mycobacterium tuberculosis to delineate the TNF-dependent and -independent components of the process. The initial clearance of M. smegmatis was TNF independent, but TNF was required for the early expression of mRNA encoding C-C and C-X-C chemokines and the initial recruitment of CD11b(+) macrophages and CD4(+) T cells to the liver during the second week of infection. Late chemokine expression and cell recruitment developed in TNF(-/-) mice associated with enhanced Th1-like T cell responses and mycobacterial clearance, but recruited leukocytes did not form tight granulomas. Infection of TNF(-/-) mice with M. tuberculosis also resulted in an initial delay in chemokine induction and cellular recruitment to the liver. Subsequently, increased mRNA expression was evident in TNF(-/-) mice, but the loosely associated lymphocytes and macrophages failed to form granulomas and prevent progressive infection. Therefore, TNF orchestrates early induction of chemokines and initial leukocyte recruitment, but has an additional role in the aggregation of leukocytes into functional granulomas capable of controlling virulent mycobacterial infection.

/pdf/tnf-regulates-chemokine-induction-essential-for-cell-371bg10a7q.pdf

TNF Regulates Chemokine Induction Essential for Cell Recruitment, Granuloma Formation, and Clearance of Mycobacterial Infection

The acoustic environment provides a rich source of information on the types of activity, communication modes, and people involved in many situations. It can be accurately classified using recordings from microphones commonly found in PDAs and other consumer devices. We describe a prototype HMM-based acoustic environment classifier incorporating an adaptive learning mechanism and a hierarchical classification model. Experimental results show that we can accurately classify a wide variety of everyday environments. We also show good results classifying single sounds, although classification accuracy is influenced by the granularity of the classification.

Acoustic environment classification

Going for gold: The first thermally stable gold(III) hydride [(C N C)*AuH] is presented. It undergoes regioselective insertions with allenes to give gold(III) vinyl complexes, and reductive condensation with [(C N C)*AuOH] to the air-stable Au(II) product, [(C N C)*(2)Au(2)], with a short nonbridged gold-gold bond.

A thermally stable gold(III) hydride: synthesis, reactivity, and reductive condensation as a route to gold(II) complexes.

https://www.rsc.org/suppdata/cc/c2/c2cc33104g/c2cc33104g.pdf

Cyclometallated gold(III) hydroxides as versatile synthons for Au–N, Au–C complexes and luminescent compounds

We used Mycobacterium avium infection in severe combined immunodeficiency (SCID) mice to examine T-cell-independent mechanisms of inflammatory cell recruitment. SCID mice infected with a virulent strain of M. avium (TMC724) were able to recruit macrophages to sites of mycobacterial replication and formed organized and coherent granulomas in the absence of functional T cells. Phagocyte recruitment was almost totally ablated by neutralization of either tumour necrosis factor-alpha (TNF-alpha) or interferon-gamma (IFN-gamma) in vivo demonstrating that granuloma formation was dependent on the presence of these cytokines. This was concomitant with a reduction in the in situ cytokine mRNA levels otherwise induced in infected mice, for chemokines, pro-inflammatory and regulatory cytokines, including TNF-alpha, IFN-gamma, macrophage inflammatory protein-1 alpha, interleukin-1 beta (IL-1 beta) and IL-10. Furthermore, in vivo treatment of infected mice with anti-asialo GM-1 antisera, which depletes natural killer (NK) cells, prevented recruitment of inflammatory cells. In vitro studies confirmed that M. avium was able to elicit IFN-gamma from SCID spleen in a dose-dependent manner. These data show for the first time that secretion of IFN-gamma from NK cells can mediate a T-cell-independent pathway of granuloma formation and cellular infiltration in response to mycobacteria.

https://onlinelibrary.wiley.com/doi/pdf/10.1046/j.1365-2567.1997.00384.x

T-cell-independent granuloma formation in response to Mycobacterium avium: role of tumour necrosis factor-alpha and interferon-gamma.

Context-awareness is essential to the development of adaptive information systems. Environmental noise can provide a rich source of information about the current context. We describe our approach for automatically sensing and recognising noise from typical environments of daily life, such as office, car and city street. In this paper we present our hidden Markov model based noise classifier. We describe the architecture of the system, compare classification results from the system with human listening tests, and discuss open issues in environmental noise classification for mobile computing.

/pdf/context-awareness-using-environmental-noise-classification-3cxrwog6i0.pdf

Dan Smith

Papers

Acoustic environment classification

A thermally stable gold(III) hydride: synthesis, reactivity, and reductive condensation as a route to gold(II) complexes.

Cyclometallated gold(III) hydroxides as versatile synthons for Au–N, Au–C complexes and luminescent compounds

T-cell-independent granuloma formation in response to Mycobacterium avium: role of tumour necrosis factor-alpha and interferon-gamma.

Context Awareness using Environmental Noise Classification