Nuclear Spin Singlet States in Photoactive Molecules: From Fluorescence/NMR Bimodality to a Bimolecular Switch for Spin Singlet States

Nuclear spin singlet states are silent states in nuclear magnetic resonance (NMR). However, they can be probed indirectly and offer great potential for the development of contrast agents for magnetic resonance imaging (MRI). Introduced here are two novel concepts: Firstly, the bimodal NMR/fluorescence properties of ¹³C₂‐tetraphenylethylene. It possesses a long‐lived singlet state in organic solvents, and it shortens upon the addition of water. This simultaneously increases the aggregation‐induced emission (AIE) of the molecule, resulting in a substantial enhancement of fluorescence. Secondly, introduced is a bimolecular switch for singlet states based on 3‐²H‐coumarin containing an isolated proton. Upon UV‐light exposure, a dimer forms, leading to a coupling between two previously isolated protons. A nuclear spin singlet state can now be populated. Excitation with a wavelength of 254 nm results in partial ring cleavage of the molecule back to its monomer.     

Selective determination of organofluorine compounds by capillary column gas chromatography with an atmospheric pressure helium microwave-induced plasma detector

Fluorinated analogs of compounds typical of those found in metabolic and other biological studies are detected with high selectivity using a gas chromatograph/microwave-induced plasma detector (GC-MIPD), which permits fluorine-selective detection by monitoring the emission at 685.6 nm. Using the described atmospheric pressure helium-sustained plasma detector, the minimum detectable level, fluorine selectivity (relative to carbon), and linear dynamic range of this GC-MIPD system were determined to be 4.8 pg-F/s, 1060, and 5000, respectively. The utility of this GC-MIPD system for the selective detection of organofluorine compounds is demonstrated by its application in the analysis of the metabolic fate of a fluorinated substrate administered to a mixture of wheat germ phosphatase and potato apyrase, as well as by analysis of synthetic mixtures.     

Numerical evaluation of optical single-scattering properties using multiple-scattering inverse transport methods

Five inverse methods for determining the single-scattering properties from monochromatic optical experiments in a homogeneous multiple-scattering slab geometry are presented and compared using analytical calculations. The methods require only measurements of the specific intensities entering and leaving the target.One method requires the pulsed irradiation of the target by a non-normally incident beam, followed by measurements for all times of the time-dependent specific intensities over both the polar and azimuthal angles. Two other methods are based on normally-incident irradiation and require measurements over only the polar angle; one method requires time-dependent measurements for all times following a laser pulse, while the second permits use of a continuous-working laser but requires experiments on targets of different thicknesses. The last two methods are obtained from the Laplace-transform of time dependent specific intensities; one method requires that the Laplace transform variable s be very large, while the other requires using a set of negative s-values tending to the limit for which Laplace transformed specific intensity becomes unbounded.     

Determination of loads applied perpendicularly to the outer boundary of a ring using coefficients of influence

A procedure is explained to determined the amount of several pairs of diametrical loads applied to the outside boundary of a ring when stresses at selected points of the inside or outside boundaries are known. Coefficients of influence are used, following an approach similar to the one presented in a previous paper. Examples of application are given and the possible increase in precision is shown when the number of points of measurements is larger than the number of loads to be determined.     

A hierarchical algorithm for making sparse matrices sparser

IfA is the (sparse) coefficient matrix of linear equality constraints, for what nonsingularT is ≡TA as sparse as possible, and how can it be efficiently computed? An efficient algorithm for thisSparsity Problem (SP) would be a valuable pre-processor for linearly constrained optimization problems. In this paper we develop a two-pass approach to solve SP. Pass 1 builds a combinatorial structure on the rows ofA which hierarchically decomposes them into blocks. This determines the structure of the optimal transformation matrixT. In Pass 2, we use the information aboutT as a road map to do block-wise partial Gauss-Jordan elimination onA. Two block-aggregation strategies are also suggested that could further reduce the time spend in Pass 2. Computational results indicate that this approach to increasing sparsity produces significant net reductions in simplex solution time.     

The ChatterVox™ Portable Voice Amplifier: A Means to Vibration Dose Reduction?

By speaking loudly for extended periods, teachers are vulnerable to laryngeal and voice changes associated with vocal fold “vibration overdose.” Voice clinicians frequently recommend voice amplification ostensibly designed to reduce vibration dose and improve voice. However, there are few data regarding the degree of vocal loudness attenuation achieved by specific amplification devices. The purpose of this investigation was to examine the effectiveness of the ChatterVox™ Portable Voice Amplification System (Siemens Hearing Instruments) for reducing the sound pressure level (SPL) of a speaker's voice during a simulated classroom lecture. Ten participants were instructed to continuously read one of two phonetically balanced passages while amplified and unamplified. Voice intensity measurements were obtained at three inches from the mouth (i.e., mouth level) and at the back of a classroom in both amplified and unamplified conditions. When amplified with the ChatterVox™, speakers experienced an average decrease in vocal intensity at mouth-level of 6.03 dB SPL (p < 0.002). Furthermore, an average increase of 2.55 dB SPL (p < 0.038) at the back of the classroom was observed. Collectively, these results indicate that the ChatterVox™ amplification device reduced the speaker's vocal intensity level at the microphone, while it augmented the voice heard at the back of the classroom. By inference, this degree of vocal attenuation at mouth level should contribute to a desirable reduction in vibration dose, thus lowering the risk of vibration overdose.     

COMPLEXING OF RIBOFLAVIN AND ITS 2-SUBSTITUTED ANALOGS WITH ADENOSINE AND OTHER 6-SUBSTITUTED PURINE DERIVATIVES*

Abstract Fluorescence properties of riboflavin and its 2-substituted analogs and the quenching of fluorescence which occurs upon complexing with adenosine and other 6-substituted purine derivatives have been examined at different concentrations of interactants and hydrogen ion. The 6-substituted purines and their ribosides show varying degrees of association with riboflavin. Successive N-alkylation of the 6-amino group of purine ribosides leads to more stable complexing in the order ethyl > methyl > propyl with riboflavin and its analog. These results suggest that such groups, including the 6-amino group of adenine or adenine moiety of FAD, do not directly interact with flavins by hydrophobic or hydrogen bonding. Lowering the pH to above that required to protonate the isoalloxazine system disrupts the intermolecular complexes. Hence, only the unprotonated bases can form such complexes. The 2-substituted aminoriboflavins, as well as FAD, exhibit fluorescence optima upon changing pH. The species involved appear to be a non-fluorescent form with protonated isoalloxazine and amine or adenine portions at low pH, a fluorescent form with only the amine or adenine portions protonated at moderately acid pH, and a non-fluorescent form which is intramolecularly quenched at higher pH. The general electron donating properties of the amines may be the common reason for their quenching of fluorescence in inter- and intramolecular complexes with flavins.     

Evaluation of a novel hydrophilic derivatized capillary for protein analysis by capillary electrophoresis —electrospray mass spectrometry

A new type of hydrophilic derivatized capillary has been used to enable the on-line capillary electrophoresis separation and electrospray mass spectrometric detection of a mixture of proteins containing bovine cytochrome c, tuna cytochrome c and horse heart myoglobin. Less than 40 fmol of each compound were loaded into the capillary. Baseline resolution of components was achieved, as were accurate assignments of molecular masses. The hydrophilic derivatized capillaries were taken through extensive testing procedures to characterize their performance and capabilities for protein analysis. A mixture of six proteins (cytochrome c, ribonuclease A, -chymotrypsinogen, myoglobin, carbonic anhydrase II and -lactalbumin) in acetic acid—sodium acetate buffer was used to delineate the relationships between migration time and pH, along with migration time and buffer concentration for each protein. The variations in capillary efficiency as a function of pH and as a function of buffer concentration were also characterized for the same six proteins in the acetic acid–sodium acetate system. A pH of 4.8 was found to offer an excellent compromise between separation efficiency (up to 500 000 theoretical plates) and analysis time. Capillary efficiencies were also found to be very good when employing a Tris · HCl electrolyte adjusted to pH 4.8. Lastly, electropherogram reproducibility and capillary durability were examined with the finding that little deterioration of the capillary occurred over the course of 400 injections (200 h run time). This represents a notable improvement over previously documented derivatization procedures designed to reduce protein adsorption to fused-silica capillary walls