Synthesis and characterization of water-soluble phenylene-vinylene-based singlet oxygen sensitizers for two-photon excitation

[reaction: see text] The synthesis and characterization of water-soluble singlet oxygen sensitizers with a phenylene-vinylene motif is presented. The principal motivation for this study was to better understand specific features of a water-soluble molecule that influence the photosensitized production of singlet oxygen upon nonlinear, two-photon excitation of that molecule. To achieve water solubility, sensitizers were synthesized with ionic as well as nonionic substituents. In the ionic approach, salts of N-methylated pyridine, benzothiazole, and 1-methyl-piperazine moieties were used, as were aryl-substituted sulfonic acid moieties. In the nonionic approach, aryl-substituted triethylene glycol moieties were used. Selected photophysical properties of the compounds synthesized were determined, including singlet oxygen quantum yields. Of the molecules examined, the most efficient singlet oxygen sensitizers had triethylene glycol units as the functional group that imparted water solubility. Molecules containing the ionic moieties did not make singlet oxygen in appreciable yield nor did they efficiently fluoresce. Rather, for these latter molecules, rapid charge-transfer-mediated non-radiative processes appear to dominate excited state deactivation.     

Improved excitation schemes for multiple-quantum magic-angle spinning for quadrupolar nuclei designed using optimal control theory

We have investigated the use of optimal control theory for the design of improved multiple-quantum excitation schemes for the popular multiple-quantum magic-angle spinning NMR experiment for quadrupolar nuclei with half-integer quadrupolar spin. The advantage of the new low-power experiments, termed OCFASTER, is demonstrated by sensitivity improvements approaching 50% for 87Rb in RbClO4 and RbNO3 as compared to FASTER and standard strong-pulse excitation schemes.     

Direct transitions among atomic states of negative reflection symmetry in the scattering plane: Li(2P 0, 3p 0, 3d ±1)-He collisions

This paper reports coupled channel model calculations of direct transitions in Li-He collisions among excited Li-states of negative reflection symmetry in the scattering plane. Using the natural coordinate frame, transition probabilities and orientation and alignment parameters are predicted as functions of impact energy and impact parameter for various initial states. It is found that for geometrical reasons transition probabilities are one to two orders of magnitude smaller than for corresponding states with positive reflection symmetry. Some experimental consequences of this finding are pointed out.     

Vibrational and high pressure conformational studies of 1,1,2-trichloroethane

The infrared spectra of 1,1,2-trichloroethane were recorded from 4000 to 50 cm^?1 in the vapour and liquid states. Additional spectra above 200 cm^?1 of the low temperature crystal and of two crystalline solids, prepared by compressing the sample in a diamond anvil cell, were obtained. Also, infrared spectra of the liquid and of the compound dissolved in CS₂ were recorded at increased pressures. Raman spectral data of the liquid (including polarization measurements) and of the low temperature crystal were obtained.The fundamental frequencies for each of the two conformers, C₁ and C_s, were assigned and the results checked by normal coordinate analysis. The same diagonal and off-diagonal force constants were employed for the two conformers and the force fields were derived by means of a least squares refinement, including data for chloroethane, 1,1-dichloroethane and various deuterated species. A standard deviation of 3 % was obtained in the final fit.From the changes in relative intensities for infrared bands belonging to the C₁ and C_s conformers with increasing pressure, the volume differences (ΔV¯between the conformers were determined in CS₂ solution and in the pure liquid.     

Optical constants of HNO3/H2O and H2SO4/HNO3/H2O at low temperatures in the infrared region

The complex index of refraction of liquid HNO3/H2O and H2SO4/HNO3/H2O has been obtained at different temperatures and acid concentrations. FT-IR specular reflectance spectra were obtained for 30, 54, and 64 wt % aqueous HNO3 and for four different H2SO4/HNO3/H2O mixtures in the temperature region from 293 to 183 K. The complex index of refraction was obtained from the reflectance spectra with the Kramers-Kronig transformation. The optical constants of the binary and ternary mixtures vary with the acid concentration and the temperature. The results demonstrate that vibrational bands originating from the sulfate species are more sensitive to changes in temperature than the bands originating from vibrations in the nitrate species; only minor changes in the nitrate vibrational bands are observed as the temperature decreases below 248 K.     

Aquaporin-11: A channel protein lacking apparent transport function expressed in brain

Background  

The aquaporins are a family of integral membrane proteins composed of two subfamilies: the orthodox aquaporins, which transport only water, and the aquaglyceroporins, which transport glycerol, urea, or other small solutes. Two recently described aquaporins, numbers 11 and 12, appear to be more distantly related to the other mammalian aquaporins and aquaglyceroporins.     

Synthetic protocols and building blocks for molecular electronics

Simple and readily accessible aryl bromides are useful building blocks for thiol end-capped molecular wires. Thus, 4-bromophenyl tert-butyl sulfide and 1-bromo-4-(methoxymethyl)benzene serve as precursors for a variety of oligo(phenylenevinylene) and oligo(phenyleneethynylene) wires via efficient synthetic transformations as presented in this paper.     

Optimizing pig marketing decisions under price fluctuations

In the manufacturing of fattening pigs, pig marketing refers to a sequence of culling decisions until the production unit is empty. The profit of a production unit is highly dependent on the price of pork, the cost of feeding and the cost of buying piglets. Price fluctuations in the market consequently influence the profit, and the optimal marketing decisions may change under different price conditions. Most studies have considered pig marketing under constant price conditions. However, because price fluctuations have an influence on profit and optimal marketing decisions it is relevant to consider pig marketing under price fluctuations. In this paper we formulate a hierarchical Markov decision process with two levels which model sequential marketing decisions under price fluctuations in a pig pen. The state of the system is based on information about pork, piglet and feed prices. Moreover, the information is updated using a Bayesian approach and embedded into the hierarchical Markov decision process. The optimal policy is analyzed under different patterns of price fluctuations. We also assess the value of including price information into the model.

     

Rhombi inscribed in simple closed curves

We show that given any simple closed curveJ in ² and any lineL, the curveJ contains the four vertices of some rhombusR with two sides parallel toL. Furthermore, the cyclic order of the vertices ofR agrees with their cyclic order onJ. We also show that the diameters of the rhombi so produced (one for each lineL) may be bounded away from zero.     

Rectangles inscribed in symmetric continua

LetQ be any rectangle and letK ^d (d 2) be a continuum which is either symmetric across a hyperplane or symmetric through a pointz K. We show thatK contains the vertices of a rectangle similar toQ which exhibits the same symmetry as doesK.