Dissociation energies of the Cu and Ag monohalides and of Ni monofluoride

Gaseous isomolecular equilibria of the type CuX + Ag = Cu + AgX, where X = F, Cl, Br, and I, were studied by effusion-beam mass spectrometry at elevated temperatures, and the differences between the dissociation energies of the CuX and AgX molecular species were determined with relatively high accuracy from thermochemical analysis of the equilibrium data. Analysis of literature data, plus new information on AgBr, yielded accurate values of D degrees 0 in kcal mol(-1) for CuF (102.0), AgCl (74.4), AgBr (66.4), and AgI (59.7), from which values were derived for AgF (81.5), CuCl (89.6), CuBr (79.2), and CuI (69.4), all +/-1 kcal mol(-1). The result is a consistent set of dissociation energies for all eight of the Cu and Ag monohalides that will be useful in checking the reliability of quantum chemical calculations for these molecular species containing elements of increasing atomic number. Also, the isomolecular exchange equilibrium between CuF and NiF was studied in a similar fashion, leading to D degrees 0(NiF) = 104.4 +/- 1.4 kcal mol(-1).     

A new cross-linking route via the unusual collision kinematics of hyperthermal protons in unsaturated hydrocarbons: the case of poly(trans-isoprene)

The bombardment of a approximately 18 nm film of poly(trans-isoprene) molecules (approximately 300,000 carbon atoms per molecule) with a mass-separated proton beam at 10 eV has been shown to induce highly efficient cross-linking of several macromolecules per incident proton. In this new method using physical means to conduct synthetic chemistry, the hyperthermal protons preferentially cleave C-H bonds because of their unusual kinematics in hydrocarbons, and the carbon radicals thus created initiate a polymerization chain reaction of the isoprene C[double bond, length as m-dash]C bonds. The method produces ultrathin polymeric films via cross-linking with a dry process having high chemical selectivity and reactivity but requiring no thermal cost and no chemical additives, conditions that are commonly required in the fabrication of microelectronics and photonics.     

Open-access microfluidic patch-clamp array with raised lateral cell trapping sites

A novel open-access microfluidic patch-clamp array chip with lateral cell trapping sites raised above the bottom plane of the chip was developed by combining both a microscale soft-lithography and a macroscale polymer fabrication method. This paper demonstrates the capability of using such an open-access fluidic system for patch-clamp measurements. The surface of the open-access patch-clamp sites prepared by the macroscale hole patterning method of soft-state elastic polydimethylsiloxane (PDMS) is examined; the seal resistances are characterized and correlated with the aperture dimensions. Whole cell patch-clamp measurements are carried out with CHO cells expressing Kv2.1 ion channels. Kv2.1 ion channel blocker (TEA) dosage response is characterized and the binding activity is examined. The results demonstrate that the system is capable of performing whole cell measurements and drug profiling in a more efficient manner than the traditional patch-clamp set-up.     

Coherent ultrafast photoelectron spectroscopy in Br2: an alternative method for measuring Delta v not equal 0 transitions in Rydberg-to-Rydberg excitations

A two-state vibrational wave packet is prepared in a low-lying 4d[12](1 or 2) Rydberg state of jet cooled Br(2) (4d, v(')=3 and v(')=4) by two-photon excitation with 266.5 nm pulses from an ultrafast laser. The wave packet is detected by autoionization following excitation with time-delayed 800 nm pulses to the n=8 (v(+)=4) and n=9 (v(+)=3) Rydberg states in the (2)Pi(12) angular momentum core state. Autoionization of each state occurs to the (2)Pi(32) state of the ion through spin-orbit ionization. Photoelectron spectroscopy is used to differentiate between the n=8 and n=9 ejected photoelectrons. Detection of the wave packet recurrences via the n=8 and n=9 Rydberg states reveals a pi phase-shift difference of the recurrences between the two final states. In each case, Delta v not equal 0 transitions are observed since wave packet recurrences are detected. By fitting the observed phase change of the recurrences with a simple model for the overlap amplitudes and assumptions about the potentials, we estimate, within the context of the model, that approximately 0.6% of the transitions may be attributed to Delta v= +/- 1 transitions between the initial Rydberg superposition state and the final Rydberg detection state.     

PMN-PT single crystal thick films on silicon substrate for high-frequency micromachined ultrasonic transducers

In this work, a novel high-frequency ultrasonic transducer structure is realized by using PMNPT-on-silicon technology and silicon micromachining. To prepare the single crystalline PMNPT-on-silicon wafers, a hybrid processing method involving wafer bonding, mechanical lapping and wet chemical thinning is successfully developed. In the transducer structure, the active element is fixed within the stainless steel needle housing. The measured center frequency and −6 dB bandwidth of the transducer are 35 MHz and 34%, respectively. Owing to the superior electromechanical coupling coefficient (k _t ) and high piezoelectric constant (d ₃₃) of PMNPT film, the transducer shows a good energy conversion performance with a very low insertion loss down to 8.3 dB at the center frequency.     

CRTH2 antagonist MK-7246: a synthetic evolution from discovery through development

In this paper, we report the development of different synthetic routes to MK-7246 (1) designed by the Process Chemistry group. The syntheses were initially designed as an enabling tool for Medicinal Chemistry colleagues in order to rapidly explore structure-activity relationships (SAR) and to procure the first milligrams of diverse target molecules for in vitro evaluation. The initial aziridine opening/cyclodehydration strategy was also directly amenable to the first GMP deliveries of MK-7246 (1), streamlining the transition from milligram to kilogram-scale production needed to support early preclinical and clinical evaluation of this compound. Subsequently a more scalable and cost-effective manufacturing route to MK-7246 (1) was engineered. Highlights of the manufacturing route include an Ir-catalyzed intramolecular N-H insertion of sulfoxonium ylide 41 and conversion of ketone 32 to amine 31 in a single step with excellent enantioselectivity through a transaminase process. Reactions such as these illustrate the enabling impact and efficiency gains that innovative developments in chemo- and biocatalysis can have on the synthesis of pharmaceutically relevant target molecules.     

Synthesis and evaluation of glucosamine-6-phosphate analogues as activators of glmS riboswitch

The glmS riboswitch is a ribozyme found in numerous Gram-positive bacteria and responds to the cellular concentrations of glucosamine 6-phosphate (GlcN6P). Given the importance of GlcN6P for cell wall biosynthesis, the glmS riboswitch has become a new drug target for the development of antibiotics. Herein, we describe the efficient synthesis of three GlcN6P analogues and their evaluation on inducing self-cleavage of the glmS riboswitch from Bacillus subtilis. Our results provide valuable information for further elucidation of the structure-activity relationships and drug design for glmS riboswitch antibiotics.     

An experimental setup for the measurement of nonthermal effects during water-filtered infrared A-irradiation of mammalian cell cultures

In many recent publications, supposed athermal effects of water-filtered infrared A (wIRA) irradiation are discussed. Those effects are mainly attributed to wavelengths in the range from 780 to 1440 nm, and should not result from warming of cellular water or any aqueous medium surrounding the irradiated sample caused by wIRA absorption. Athermal effects are considered to be induced directly by absorption of different wavelengths of the wIRA spectrum by cellular molecules or structures except water. To distinguish between thermal and athermal effects, irradiated samples have to be subjected to a very effective and precise temperature homeostasis. Any experimental effects can only be attributed to pure athermal effects, if the temperature of the irradiated samples is verifiably constant and does not result in hyperthermia. Here, data of temperature distribution in Petri dishes of different types filled with aqueous medium are presented which were estimated by model calculation for different setups of cooling. Additionally, the real temperature development was directly measured. Such a cooling unit enables long-term application of high wIRA irradiances and large doses without any detectable warming of the irradiated samples, in single cell layers. Using such a setup, thermal and athermal effects can be compared and in addition to that quantified.     

Three revenue-sharing variants: their significant performance differences under system-parameter uncertainties

In the widely studied ‘revenue sharing’ (hereafter [RS]) contract format, the manufacturer of a product not only charges the retailer a unit wholesale price w, but also requires the retailer to share part of the product's revenue (ie, the unit retail price p) with him. For a product with price-dependent demand, it is well known that if a dominant manufacturer knows the system parameters deterministically, then [RS] gives him the perfect power of simultaneously coordinating the channel and allocating profit arbitrarily. Unfortunately, [RS]'s power deteriorates as the manufacturer's knowledge of the system parameters becomes increasingly uncertain. This paper shows that this deterioration can be substantially reduced by using slightly modified versions of [RS]; these modifications roughly amount to sharing a retailer's gross profit instead of revenue. In other words, this paper presents simple modifications to the classical [RS], leading to contract formats that perform substantially better under system-parameter uncertainty.