Rhythmic pattern formations in gels and Matalon—Packter law: A fresh perspective

The periodic precipitation pattern formation in gelatinous media is interpreted as a moving boundary problem. The time law, spacing law and width law are revisited on the basis of the new scenario. The explicit dependence of the geometric structure on the initial concentrations of the reactants is derived. Matalon—Packter law, which relates the spacing coefficient with the initial concentrations is reformulated removing many ambiguities and impractical parameters. Experimental results are discussed to establish the significance of moving boundary concept in the diffusion controlled pattern forming systems     

Non-negative scalar curvature

We study topological obstructions to the existence of Riemannian metrics of non-negative scalar curvature on almost spin manifolds using the Dirac operator, the Bochner technique, C ^* algebras and von Neumann algebras. We also derive some obstructions in terms of the eta invariants of Atiyah, Patodi and Singer. Next, we prove vanishing theorems for the Atiyah-Milnor genus. Finally, we derive obstructions to the existence of metrics of non-negative scalar curvature along the leaves of a leafwise non-amenable foliation on a spin manifold.     

Alpha-sulfinyl carbanions as a new source of olefins

[reaction: see text] Secondary alpha-lithiosulfinyl carbanions react either intermolecularly, after transmetalation into an organocopper derivative in an S(N)2-type process with zinc carbenoid, or intramolecularly via higher-order zincate to give, through a tandem zinc homologation-beta-elimination reaction the corresponding alkenes. alpha,alpha-Disubstituted alkenes are only formed from tertiary alpha-lithiosulfinyl carbanions via the 1,2-metalate rearrangement.     

Copper(II) azide complexes of aliphatic and aromatic amine based tridentate ligands: novel structure, spectroscopy, and magnetic properties

Copper(II) azide complexes of three tridentate ligands namely 2,6-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L), 2,6-(pyrazol-1-ylmethyl)pyridine (L'), and dipropylenetriamine (dpt) yield three kinds of complexes with different azide-binding modes. The ligand L forms two end-on-end (mu-1,3) diazido-bridged binuclear complexes, [CuL(mu-N(3))](2)(ClO(4))(2) (1) and [CuL(mu-N(3))(ClO(4))](2).2CH(3)CN (2), and L' forms a perchlorato-bridged quasi-one-dimensional chain complex, [CuL'(N(3))(ClO(4))](n)() (3) with monodentate azide coordination. The ligation of dipropylenetriamine (dpt) gives a end-on (mu-1,1) diazido-bridged binuclear copper complex [Cu(dpt)(mu-N(3))](2)(ClO(4))(2) (4). The crystal and molecular structures of these complexes have been solved. Variable-temperature EPR results of 1 and 2 are identical and indicate the presence of both ferromagnetic and antiferromagnetic interactions within the dimer, the former dominating at low temperatures and the latter at high temperatures. The unusual temperature-dependent magnetic moment and EPR spectra of this dimer reveal the presence of temperature-dependent population of two triplet states, one being caused by antiferromagnetic and the other by ferromagnetic interaction, the former transforming to the latter on cooling. While the interaction of ground spin doublets of the two metal centers gives rise to a ferromagnetic coupling of J(g) = 90.73 cm(-1), the other coupling of J(e) = -185.64 cm(-1) is suggested to be caused by the interaction between an electron in one metal center and an electron from the azide of the other monomer by excitation of a d-electron to the empty ligand orbital. The ferromagnetic state is energetically favored by 104.39 cm(-1). Compound 3 exhibits axial spectra at room temperature and 77 K, and variable-temperature magnetic susceptibility data indicate that the copper centers form a weakly antiferromagnetic one-dimensional chain with J = -0.11 cm(-1). In the case of 4, the unique presence of two nonidentical dimeric units with different bond lengths and bond angles within the unit cell as inferred by crystal structure is proved by single-crystal EPR spectroscopy.     

From symmetry breaking to symmetry swapping: is Kasha's rule violated in multibranched phenyleneethynylenes?

The phenomenon of excited-state symmetry breaking is often observed in multipolar molecular systems, significantly affecting their photophysical and charge separation behavior. As a result of this phenomenon, the electronic excitation is partially localized in one of the molecular branches. However, the intrinsic structural and electronic factors that regulate excited-state symmetry breaking in multibranched systems have hardly been investigated. Herein, we explore these aspects by adopting a joint experimental and theoretical investigation for a class of phenyleneethynylenes, one of the most widely used molecular building blocks for optoelectronic applications. The large Stokes shifts observed for highly symmetric phenyleneethynylenes are explained by the presence of low-lying dark states, as also established by two-photon absorption measurements and TDDFT calculations. In spite of the presence of low-lying dark states, these systems show an intense fluorescence in striking contrast to Kasha''s rule. This intriguing behavior is explained in terms of a novel phenomenon, dubbed “symmetry swapping” that describes the inversion of the energy order of excited states, i.e., the swapping of excited states occurring as a consequence of symmetry breaking. Thus, symmetry swapping explains quite naturally the observation of an intense fluorescence emission in molecular systems whose lowest vertical excited state is a dark state. In short, symmetry swapping is observed in highly symmetric molecules having multiple degenerate or quasi-degenerate excited states that are prone to symmetry breaking.

Highly symmetric multibranched phenyleneethynylenes exhibit intense fluorescence despite the presence of low-lying dark states. The inversion of the energy order of excited states is explained in terms of a novel phenomenon dubbed “symmetry swapping”.     

Fabrication of highly ordered TiO2 nanotube arrays using an organic electrolyte

Anodization of titanium in a fluorinated dimethyl sulfoxide (DMSO) and ethanol mixture electrolyte is investigated. The prepared anodic film has a highly ordered nanotube-array surface architecture. Using a 20 V anodization potential (vs Pt) nanotube arrays having an inner diameter of 60 nm and 40 nm wall thickness are formed. The overall length of the nanotube arrays is controlled by the duration of the anodization, with nanotubes appearing only after approximately 48 h; a 72 h anodization results in a nanotube array approximately 2.3 mum in length. The photoelectrochemical response of the nanotube-array photoelectrodes is studied using a 1 M KOH solution under both UV and visible (AM 1.5) illumination. Enhanced photocurrent density is observed for samples obtained in the organic electrolyte, with an UV photoconversion efficiency of 10.7%.     

η4‐HBCC‐σ,π‐Borataallyl Complexes of Ruthenium Comprising an Agostic Interaction

Thermolysis of [Cp*Ru(PPh₂(CH₂)PPh₂)BH₂(L₂)] 1 (Cp*=η⁵‐C₅Me₅; L=C₇H₄NS₂), with terminal alkynes led to the formation of η⁴‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)B{R‐C=CH₂}(L)₂] ( 2 a – c ) and η²‐vinylborane complexes [Cp*Ru(R‐C=CH₂)BH(L)₂] ( 3 a – c ) ( 2 a , 3 a : R=Ph; 2 b , 3 b : R=COOCH₃; 2 c , 3 c : R=p‐CH₃‐C₆H₄; L=C₇H₄NS₂) through hydroboration reaction. Ruthenium and the HBCC unit of the vinylborane moiety in 2 a – c are linked by a unique η⁴‐interaction. Conversions of 1 into 3 a – c proceed through the formation of intermediates 2 a – c . Furthermore, in an attempt to expand the library of these novel complexes, chemistry of σ‐borane complex [Cp*RuCO(μ‐H)BH₂L] 4 (L=C₇H₄NS₂) was investigated with both internal and terminal alkynes. Interestingly, under photolytic conditions, 4 reacts with methyl propiolate to generate the η⁴‐σ,π‐borataallyl complexes [Cp*Ru(μ‐H)BH{R‐C=CH₂}(L)] 5 and [Cp*Ru(μ‐H)BH{HC=CH‐R}(L)] 6 (R=COOCH₃; L=C₇H₄NS₂) by Markovnikov and anti‐Markovnikov hydroboration. In an extension, photolysis of 4 in the presence of dimethyl acetylenedicarboxylate yielded η⁴‐σ,π‐borataallyl complex [Cp*Ru(μ‐H)BH{R‐C=CH‐R}(L)] 7 (R=COOCH₃; L=C₇H₄NS₂). An agostic interaction was also found to be present in 2 a – c and 5 – 7 , which is rare among the borataallyl complexes. All the new compounds have been characterized in solution by IR, ¹H, ¹¹B, ¹³C NMR spectroscopy, mass spectrometry and the structural types were unequivocally established by crystallographic analysis of 2 b , 3 a – c and 5 – 7 . DFT calculations were performed to evaluate possible bonding and electronic structures of the new compounds.     

Correlation of ultrasonic scatterer size estimates for the statistical analysis and optimization of angular compounding

Ultrasonic scatterer size estimates generally have large variances due to the inherent noise of spectral estimates used to calculate size. Compounding partially correlated size estimates associated with the same tissue, but produced with data acquired from different angles of incidence, is an effective way to reduce the variance without making dramatic sacrifices in spatial resolution. This work derives theoretical approximations for the correlation between these size estimates, and the coherence between their associated spectral estimates, as functions of ultrasonic system parameters. A Gaussian spatial autocorrelation function is assumed to adequately model scatterer shape. Both approximations compare favorably with simulation results, which consider validation near the focus. Utilization of the correlation/coherence expressions for statistical analysis and optimization is discussed. Approximations, such as the invariance of phase and amplitude terms with angle, are made to obtain closed-form solutions to the derived spectral coherence near the focus and permit analytical optimization analysis. Results indicate that recommended parameter adjustments for performance improvement generally depend upon whether, for the system under consideration, the primary source of change in total coherence with rotation is phase term variation due to the change in the relative position of scattering sites, or field amplitude term variation due to beam movement.     

Dense layers of vertically oriented WO3 crystals as anodes for photoelectrochemical water oxidation

Films of crystalline WO(3) nanosheets oriented perpendicular to tungsten substrates were grown by a surfactant-free hydrothermal method, followed by sintering. The films exhibit photoelectrochemical oxygen evolution at low overpotential.