Selection rules and Raman spectrum of a molecule with a degenerate ground state and zero spin-orbit coupling: VCl4

Two interesting features can normally be expected in the Raman spectrum of a molecule with a degenerate electronic ground state (i) the contribution of asymmetric or even antisymmetric tensors to the Raman intensity (ii) lifting of the electronic degeneracy due to Jahn-Teller distortion. The experimental data and discussion on VCl₄, presented here, show that this molecule does not show any deviations in the Raman selection rules. Further, its Raman spectrum closely resembles that of TiCl₄ which also has T_d geometry but a nondegenerate singlet ground state. This suggests the absence of any static Jahn-Teller distortion in VCl₄. However, we have observed a broadening of the ν₂ band of VCl₄ over TiCl₄ and we attribute this to a possible dynamic Jahn-Teller splitting.     

Synthesis and reactivity of sulfur and silyl substituted α-alkylidene-β-lactams

Synthetically valuable α-alkylidene-β-lactams are produced from the addition of chlorosulfonyl isocyanate to allenyl sulfides.     

A technique for simulating the amplifier-to-eardrum transfer function of an in situ hearing aid

There are numerous articles wherein mathematical models of various parts of an in situ hearing aid have been reported. Such parts include, for example, the microphone, receiver, cylindrical tubes carrying sound to the eardrum and out through the earmold vent, and the external path from the vent back to the microphone. This article extends these earlier works to include the hearing-aid amplifier. In particular, a mathematical technique for characterizing the amplifier in combination with the receiver is reported. Cascade parameters of a two-port model of one particular amplifier/receiver combination are obtained by this method. The cascade-parameter data and the method of obtaining this data are verified by two different experimental procedures. One procedure involves both computing and measuring the input driving-point impedance of the amplifier/receiver combination. In the second procedure, the amplifier-to-eardrum transfer function of a hearing aid incorporating this same amplifier/receiver combination and mounted on an artificial ear is both computed and measured. Experimental and computed values of this transfer function for three different earmold geometries are in reasonably close agreement. The amplifier/receiver model reported herein will be used in future studies of acoustic feedback in hearing aids.     

A simple synthesis of 8-(trifluoromethyl)-2,3,5,6,11,12,14,15-octahydro-1H,4H,10H, 13H-diquinolizino[9,9a,1-bc:9′,9a',1-hi] xanthylium perchlorate,an efficient dye

A one-step procedure is described for the preparation of the title compound I, an efficient laser dye operating in the red region.     

Carbon networks based on dehydrobenzoannulenes. 5. Extension of two-dimensional conjugation in graphdiyne nanoarchitectures

[structures: see text] The synthesis and optical properties of a series of multinanometer-sized substructures of the phenyl-diacetylene carbon allotrope, graphdiyne, are described. These molecules are among the largest and most complex annulenic systems yet prepared, with extension of linear conjugation in two-dimensions to over twice that of any previously reported planar macrocycle. The graphdiyne substructures are constructed through convergent syntheses, taking advantage of three key intermediates and silane-protected phenylacetylenes. Intramolecular macrocyclization of alpha,omega-polyyne precursors via Cu-mediated or Pd-catalyzed oxidative homocoupling affords five new graphdiyne "oligomers" possessing two to four fused 18-membered rings. The attempted synthesis of a six-ring analogue is also reported.     

Experimental probes of silver metal nanoparticle formation kinetics: Comparing indirect versus more direct methods

The kinetics of noble metal nanoparticle formation in bottom-up syntheses are important for controlling and optimizing these methods. Hence, experimental probes that are easily accessible to most laboratories are also of interest. We collected kinetic curves for the formation of silver nanoparticles in a modified Turkevich method with citrate acting as the reducing and stabilizing agent by (i) measuring the change in silver nanoparticle surface plasmon resonance by UV-visible spectroscopy, a somewhat indirect method, and then also by (ii) measuring the change in silver ion concentration by ion-selective electrode potentiometry and/or atomic absorption spectroscopy, two more direct methods. The resulting sigmoidal kinetic curves were curvefitted with the Finke-Watzky two-step kinetic model of slow, continuous nucleation and fast autocatalytic growth to extract average rate constants. We found that the kinetic curves obtained by following the change in silver ion concentration were apparent mirror images of those constructed by following the change in nanoparticle surface plasmon resonance, and that their respective curvefits displayed the same sigmoidal characteristics. The resultant values of the rate constants for nucleation and growth overlapped within experimental error between the methods and showed similar trends over the range of citrate concentrations studied. The use of multiple probes in this work to follow the kinetics of nanoparticle formation helps fill a need for the comparison and evaluation of different methods available to scientists, particularly those considered easily accessible.     

Dynamic proton-induced emission switching in donor-functionalized dehydrobenzopyrid[15]annulenes

An isomeric pair of 15-membered dehydrobenzopyridannulenes functionalized with -NBu(2) groups as pi-electron donors was prepared and their steady-state spectroscopic parameters investigated. The property differences arising from placement of the pyridine nitrogen relative to the macrocycle, as well as the differential effects of stepwise protonation of the acceptor and donor nitrogens, were examined. The macrocycles exhibited dynamic shifting in the emission spectra, which is believed to correlate to induced changes in the frontier molecular orbitals of the molecules.     

CuCl-induced formation and migration of isoindazolyl carbenoids

Two azo-ene-butadiyne conjugated systems undergo CuCl-mediated cyclization to afford isoindazolyl carbenoids that could be trapped with 2,3-dimethyl-2-butene as [2+1] cycloaddition products. X-ray structure analysis of the resultant cyclopropanes showed that formal migration to the distal carbenoid isomer and subsequent trapping had occurred. The possible CuCl-induced cyclization/migration pathways were explored using density functional theory, which indicated that the reaction most likely occurred via coordination of CuCl to the distal alkyne bond.     

Domain Analysis and Motif Matcher (DAMM): A Program to Predict Selectivity Determinants in Monosiga brevicollis PDZ Domains Using Human PDZ Data

Choanoflagellates are single-celled eukaryotes with complex signaling pathways. They are considered the closest non-metazoan ancestors to mammals and other metazoans and form multicellular-like states called rosettes. The choanoflagellate Monosiga brevicollis contains over 150 PDZ domains, an important peptide-binding domain in all three domains of life (Archaea, Bacteria, and Eukarya). Therefore, an understanding of PDZ domain signaling pathways in choanoflagellates may provide insight into the origins of multicellularity. PDZ domains recognize the C-terminus of target proteins and regulate signaling and trafficking pathways, as well as cellular adhesion. Here, we developed a computational software suite, Domain Analysis and Motif Matcher (DAMM), that analyzes peptide-binding cleft sequence identity as compared with human PDZ domains and that can be used in combination with literature searches of known human PDZ-interacting sequences to predict target specificity in choanoflagellate PDZ domains. We used this program, protein biochemistry, fluorescence polarization, and structural analyses to characterize the specificity of A9UPE9_MONBE, a M. brevicollis PDZ domain-containing protein with no homology to any metazoan protein, finding that its PDZ domain is most similar to those of the DLG family. We then identified two endogenous sequences that bind A9UPE9 PDZ with <100 μM affinity, a value commonly considered the threshold for cellular PDZ–peptide interactions. Taken together, this approach can be used to predict cellular targets of previously uncharacterized PDZ domains in choanoflagellates and other organisms. Our data contribute to investigations into choanoflagellate signaling and how it informs metazoan evolution.