Induced Self‐Assembly of Platinum(II) Alkynyl Complexes through Specific Interactions between Citrate and Guanidinium for Proof‐of‐Principle Detection of Citrate and an Assay of Citrate Lyase

Water‐soluble alkynylplatinum(II) terpyridine complexes appended with guanidinium moieties, [Pt(tpy)(C?C?Ar)][OTf]₂ (tpy=terpyridine; OTf=trifluoromethanesulfonate; Ar=C₆H₄‐{NHC(?NH₂⁺)(NH₂)}‐4 ( 1 ), C₆H₄‐{CH₂NHC(?NH₂⁺)(NH₂)}‐4 ( 2 )), and [Pt(tBu₃tpy)(C?CC₆H₄‐{NHC(?NH₂⁺)(NH₂)}‐4)][OTf]₂ ( 3 ; tBu₃tpy=4,4′,4′′‐tri‐tert‐butyl‐2,2′:6′,2′′‐terpyridine), have been synthesized and characterized. The photophysical properties of the complexes have been studied. Based on the results of UV/Vis absorption, resonance light scattering, and dynamic light scattering experiments, in aqueous buffer solutions complexes 1 and 2 undergo aggregation in the presence of citrate through strong and specific electrostatic and hydrogen‐bonding interactions with citrate. The emergence of a triplet metal–metal‐to‐ligand charge transfer (³MMLCT) emission in the near‐infrared (NIR) region brought on by the induced self‐assembly of complex 1 has been demonstrated for proof‐of‐principle detection of citrate with good sensitivity and selectivity over other mono‐ and dicarboxylate substrates in the tricarboxylic acid (TCA) cycle as well as phosphate and lactate anions. Such a good selectivity toward citrate has been rationalized by the high charge density of citrate under physiological conditions and specific interactions between the guanidinium moiety on complex 1 and citrate. Extension of the work to citrate detection in fetal bovine serum and real‐time monitoring of the activity of citrate lyase by the NIR emission of complex 1 have also been demonstrated.     

Crystallographic and structural characterization of heterometallic platinum complexes Part V. Heteropentanuclear complexes

This review classifies and analyzes over eighty heteropentanuclear Pt complexes. There are eight types of metal combinations: Pt₄M, Pt₃M₂, Pt₂M₃, PtM₄, Pt₃MM′, Pt₂M₂M′, PtM₂M′₂ and PtM₃M′. The five metal atoms are in a wide variety of arrangements: trigonal-bipyramidal (most common), square-pyramidal, spike-triangular, butterfly, cubane, linear and one unique. Platinum bonds to a variety of triad partner metal atoms, soft, through borderline to hard. The shortest Pt-M bond distances for non-transition and transition M are 2.406(4) Å (M = Ge) and 2.30(1) Å (M = Co). The shortest Pt-Pt bond distance is 2.580(1) Å. Several relationships between the structural parameters were found and are discussed. Several complexes exist in two isomeric forms and others contain two crystallographically independent molecules. Both the isomers as well as independent molecules are examples of distortion isomerism.      

Nature of the band gap of silicon and germanium nanowires

Nanowires of both Si and Ge have been predicted to have band gaps that are either direct or indirect depending upon the crystallographic direction along which the nanowire is oriented. We use a sp³d⁵s^* tight binding model to calculate the band structures for both Ge and Si nanowires oriented along the (1 0 0), (1 1 0) and (1 1 1) directions. We show that the nature of the band gap and the variation of the zone centre band gap with nanowire width depends upon the nanowire stacking direction for both Si and Ge nanowires. We then show, by considering bulk unit cells along the (1 0 0), (1 1 0) and (1 1 1) directions, that it is possible to accurately predict whether a nanowire stacked in the same direction as one of these bulk unit cells has a direct or indirect band structure.     

Direct reductive aminations with catalytic molybdenum dioxide dichloride and phenylsilane

A powerful direct reductive amination (DRA) method is developed, using catalytic MoO₂Cl₂ and phenylsilane (PhSiH₃) as the reducing agent. The alkylation of a range of amines (pK_a 0-7.8) with both an electron-deficient and two electron-rich-aldehydes is achieved in good to excellent yields. The novel employment of this DRA in alcoholic solvents significantly improves the reaction scope and excellent functional group selectivity is exhibited.     

Synthesis and evaluation of potential CT (computer tomography) contrast agents for bone structure and microdamage analysis

The design and synthesis of several novel X-ray contrast agents 1-3, developed for targeting bone structures, and in particularly microcracks in bones, using CT (Computer Tomography) detection is described. These contrast agents are based on the use of the well known triiodobenzene platform, which was conjugated into one or more phenyliminodiacetate moieties, which can be used to 'lock' onto bone matrices. Compounds 1-3 were all tested for their ability to visualise cracks in bone structures (bovine bones) using micro-CT imaging.     

The role of nonlinear effects in the propagation of noise from high-power jet aircraft

To address the question of the role of nonlinear effects in the propagation of noise radiated by high-power jet aircraft, extensive measurements were made of the F-22A Raptor during static engine run-ups. Data were acquired at low-, intermediate-, and high-thrust engine settings with microphones located 23-305 m from the aircraft along several angles. Comparisons between the results of a generalized-Burgers-equation-based nonlinear propagation model and the measurements yield favorable agreement, whereas application of a linear propagation model results in spectral predictions that are much too low at high frequencies. The results and analysis show that significant nonlinear propagation effects occur for even intermediate-thrust engine conditions and at angles well away from the peak radiation angle. This suggests that these effects are likely to be common in the propagation of noise radiated by high-power aircraft.