Z → E Photoisomerization of Homoactivated Carbon Carbon Double Bonds

Z-configured 1,4-diene or β, γ-unsaturated carbonyl systems are readily available by the Wittig reaction. Isomerization required for access into the E-series can easily be accomplished by irradiation using an ordinary tungsten lamp and diphenyl disulphide sensitizer. There is very little formatation of conjugated isomers (less than 1%).     

Predictors and Limitations of the Penetration Depth of Photodynamic Effects in the Rodent Brain

Fluorescence-guided surgery (FGS) is routinely utilized in clinical centers around the world, whereas the combination of FGS and photodynamic therapy (PDT) has yet to reach clinical implementation and remains an active area of translational investigations. Two significant challenges to the clinical translation of PDT for brain cancer are as follows: (1) Limited light penetration depth in brain tissues and (2) Poor selectivity and delivery of the appropriate photosensitizers. To address these shortcomings, we developed nanoliposomal protoporphyrin IX (Nal-PpIX) and nanoliposomal benzoporphyrin derivative (Nal-BPD) and then evaluated their photodynamic effects as a function of depth in tissue and light fluence using rat brains. Although red light penetration depth (defined as the depth at which the incident optical energy drops to 1/e, ~37%) is typically a few millimeters in tissues, we demonstrated that the remaining optical energy could induce PDT effects up to 2 cm within brain tissues. Photobleaching and singlet oxygen yield studies between Nal-BPD and Nal-PpIX suggest that deep-tissue PDT (>1 cm) is more effective when using Nal-BPD. These findings indicate that Nal-BPD-PDT is more likely to generate cytotoxic effects deep within the brain and allow for the treatment of brain invading tumor cells centimeters away from the main, resectable tumor mass.     

FTIR and millimeter wave investigation of the 7 and 9 states of formic acid HCOOH and HCOOH

High resolution FTIR spectra of the two overlapping bands ν₇ and ν₉ of the ¹³C species of formic acid have been measured and analyzed. Rotational transitions in the millimeter wave region were measured and included in the analysis. As in the parent species, there is a strong Coriolis interaction between the 7¹ and 9¹ states. The corresponding IR bands of the parent species have been remeasured and new MMW transitions recorded. The analysis of the spectra for the two species provides an opportunity to consider a reduction of the Hamiltonian employed for the analysis of this type of interacting system of states. Parameters with low correlations could be obtained. Several interstellar features coincide with transitions predicted from these parameters.     

Quantitative determination of acetylcholine in microdialysis samples using liquid chromatography/atmospheric pressure spray ionization mass spectrometry

A fast, simple and sensitive liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed for the determination of acetylcholine in rat brain microdialysis samples. The chromatographic separation was achieved in 3 min on a reversed-phase column with isocratic conditions using a mobile phase containing 2% (v/v) of acetonitrile and 0.05% (v/v) of trifluoroacetic acid (TFA). A stable isotope-labeled internal standard was included in the analysis and detection was carried out with a linear ion trap mass spectrometer using selected reaction monitoring (SRM). Analyte ionization was performed with an atmospheric pressure chemical ionization (APCI) source without applying discharge current (atmospheric pressure spray ionization). This special ionization technique offered significant advantages over electrospray ionization for the analysis of acetylcholine with reversed-phase ion-pairing chromatography. The lower limit of quantification was 0.15 nM (1.5 fmol on-column) and linearity was maintained over the range of 0.15-73 nM, providing a concentration range that is significantly wider than that of the existing LC/MS methods. Good accuracy and precision were obtained for concentrations within the standard curve range. The method was validated and has been used extensively for the determination of acetylcholine in rat brain microdialysis samples.     

Form sums of nonnegative selfadjoint operators

Summary The sum of two unbounded nonnegative selfadjoint operators is a nonnegative operator which is not necessarily densely defined. In general its selfadjoint extensions exist in the sense of linear relations (multivalued operators). One of its nonnegative selfadjoint extensions is constructed via the form sum associated with A and B. Its relations to the Friedrichs and Krein--von Neumann extensions of A+Bare investigated. For this purpose, the one-to-one correspondence between densely defined closed semibounded forms and semibounded selfadjoint operators is extended to the case of nondensely defined semibounded forms by replacing semibounded selfadjoint operators by semibounded selfadjoint relations. In particular, the inequality between two closed nonnegative forms is shown to be equivalent to a similar inequality between the corresponding nonnegative selfadjoint relations.</o:p>     

Atmospheric pressure thermospray ionization using a heated microchip nebulizer

When a standard atmospheric pressure chemical ionization (APCI) or atmospheric pressure photoionization (APPI) ion source is used without applying the corona discharge or photoirradiation, atmospheric pressure thermospray ionization (APTSI) of various compounds can be achieved. Although largely ignored, this phenomenon has recently gained interest as an alternative ionization technique. In this study, this technique is performed for the first time on a miniaturized scale using a microchip nebulizer. Sample ionization with the presented microchip‐APTSI (µAPTSI) is achieved by applying only heat and gas flow to a nebulizer chip, without any other methods to promote gas‐phase ionization. To evaluate the performance of the described µAPTSI setup, ionization efficiency for a set of test compounds was monitored as the microchip positioning, temperature, nebulizer gas flow rate, sample solution composition, and solvent flow rate were varied. The µAPTSI mass spectra of the test compounds were also compared to those obtained with ESI and APCI. The µAPTSI produces ESI‐like spectra with low background noise, favoring the formation of protonated or deprotonated molecules of compounds that are ionizable in solution. Multiple charging of peptides without in‐source fragmentation was also observed. Unlike ESI, however, the µAPTSI source can tolerate the presence of mobile phase additives like trifluoroacetic acid (TFA) without significant ion suppression. The µAPTSI source can be used with standard mass spectrometer ion source hardware, being a unique alternative to the present interfacing techniques. Copyright © 2009 John Wiley & Sons, Ltd.     

Uniqueness and existence results for ordinary differential equations

We establish some uniqueness and existence results for first-order ordinary differential equations with constant-signed discontinuous nonlinear parts. Several examples are given to illustrate the applicability of our work.     

An addendum to the multiplication and factorization theorems of brodskiǐ—livšic—potapov

In this paper the classical Brodskiǐ—Liv?ic— operator colligation is generalized to certain pairs of bounded linear operators and the corresponding characteristic operator—valued (transfer) function is introduced. The fundamental results due to M.S. Brodskiǐ, M.S. Liv?ic, and V.P. Potapov are then extended to such colligations. These new types of colligations can be used to obtain, for instance, realization results for general Herglotz—Nevanlinna functions.     

Extensional viscosity in uniaxial extension and contraction flow—Comparison of experimental methods and application of the molecular stress function model

Extensional viscosity of a low-density polyethylene was measured at three temperatures in uniaxial extension by Sentmanat Extension Rheometer, and in contraction flow using the Cogswell analysis. The molecular stress function model was applied to describe the experimental results. The achieved maximum values from uniaxial transient tests were in accordance with the ones obtained by Cogswell method at similar strain level, and the molecular stress function model was able to describe the experimental transient uniaxial extensional data. The steady-state extensional viscosity was not reached in the experiments.