Equity-linked pension schemes with guarantees

This paper analyses the relationship between the level of a return guarantee in an equity-linked pension scheme and the proportion of an investor’s contribution needed to finance this guarantee. Three types of schemes are considered: investment guarantee, contribution guarantee and surplus participation. The evaluation of each scheme involves pricing an Asian option, for which relatively tight upper and lower bounds can be calculated in a numerically efficient manner.We find a negative (and for two contract specifications also concave) relationship between the participation in the surplus return of the investment strategy and the guarantee level in terms of a minimum rate of return. Furthermore, the introduction of the possibility of early termination of the contract (e.g. due to the death of the investor) has no qualitative and very little quantitative impact on this relationship.     

Synthesis,Dynamic Combinatorial Chemistry,and PCR Amplification of 3′–5′ and 3′–6′ Disulfide‐linked Oligonucleotides

Disulfide dithymidines linked 3′–5′ or 3′–6′ were synthesized and incorporated into oligonucleotides through a combined phosphotriester and phosphoramidite solid‐phase oligonucleotide synthesis approach. The disulfide links are cleaved and formed reversibly in the presence of thiols and oligonucleotides. This link was shown to be sequence‐adaptive in response to given templates in the presence of mercaptoethanol. The artificial 3′–5′ and 3′–6′ disulfide link was tolerated by polymerases in the polymerase chain reaction (PCR). By using sequencing analysis, we show that single mutations frequently occurred randomly in the amplification products of the PCR.     

Two-photon photosensitized production of singlet oxygen: sensitizers with phenylene-ethynylene-based chromophores

[reaction: see text] Singlet molecular oxygen (a(1)Delta(g)) has been produced and optically monitored in time-resolved experiments upon nonlinear two-photon excitation of photosensitizers that contain triple bonds as an integral part of the chromophore. Both experiments and ab initio computations indicate that the photophysical properties of alkyne-containing sensitizers are similar to those in the alkene-containing analogues. Most importantly, however, in comparison to the analogue that contains double bonds, the sensitizer containing alkyne moieties is more stable against singlet-oxygen-mediated photooxygenation reactions. This increased stability can be advantageous, particularly with respect to two-photon singlet oxygen imaging experiments in which data are collected over comparatively long time periods.     

Nucleophilic addition of nitrones to ketones: development of a new catalytic asymmetric nitrone-aldol reaction

A new organic reaction has been discovered in which nitrones react with carbonyl compounds in an aldoltype reaction to give functionalized beta-hydroxynitrones. The alpha-carbon atom of the nitrone undergoes a nucleophilic addition reaction to electron-deficient ketones, such as alpha-ketoesters, alpha,beta-diketones, and trifluoromethyl ketones, to afford the products in moderate to good yields. The scope and potential of the reaction have been investigated and developed. The reaction can also be catalyzed by secondary amines. The use of chiral cyclic amines, such as L-proline leads to optically active beta-hydroxynitrones in moderate yield and with moderate to high enantiomeric excess. The reaction mechanism was studied by kinetic measurements, intermediate and product analysis, and determination of the absolute configuration of the product; based on these investigations a mechanism for the new reaction is proposed.     

DNA-programmed control of photosensitized singlet oxygen production

DNA sequence-controlled on-and-off switching of a singlet oxygen sensitizer has been developed and demonstrated. The singlet oxygen photosensitizer pyropheophorbide-a (P) was attached to a 15-mer nucleotide sequence. A molecule that could quench the sensitizer, the so-called "black hole quencher 3" (Q), was attached to a complementary nucleotide strand. Upon hybridization of the two conjugates, singlet oxygen production from P was completely shut down. Upon the addition of a third DNA sequence that can displace and release the P-DNA conjugate from the P-Q pair, up to 85% of the singlet oxygen production was recovered. This system is a model for a benign drug that becomes active only in the presence of a specific targeted nucleotide sequence.     

Excess volumes of propanol-water mixtures at 5, 15, and 25°C

This paper reports on equipment for the automatic measurement of the density of binary mixtures as a function of concentration. The equipment is applied to mixtures of 1-propanol and water at 5, 15, and 25°C. An equilibrium mixture model, in which an alcohol-water solution is regarded as an ideal associated mixture, is fitted to the experimental data. Thermodynamic parameters characterizing the association of water to nonpolar alkyl groups (hydrophobic solvation) and to polar hydroxyl groups (hydrophilic solvation) are estimated.