Photoisomerization of azobenzene derivatives in nanostructured silica

A series of derivatized azobenzene molecules are synthesized such that one of the phenyl groups can be chemically bonded to mesostructured silica and the other, derivatized with dendrons, is free to undergo large-amplitude light-driven motion. The silica frameworks on which the motion takes place are either 150 nm thick films containing ordered hexagonal arrays of tubes (inner diameter about 2 nm) containing the bonded azobenzenes, or particles (about 500 nm in diameter) containing the same ordered arrays of functionalized tubes. The photoisomerization yields and the rate constants for the thermal cis to trans back-reaction of the azobenzenes in the tubes are measured and compared to those of the molecules in solution. The rate constants decrease with increasing size of the dendrons. Fluorescence spectra of the cis and trans isomers in the pores show that the photoisomerization in the nanostructured materials is selectively driven by specific wavelengths of light and is reversible.     

Flow equivalence of sofic shifts

We classify certain sofic shifts (the irreducible Point Extension Type, or PET, sofic shifts) up to flow equivalence, using invariants of the canonical Fischer cover. There are two main ingredients.

1. (1)
   An extension theorem, for extending flow equivalences of subshifts to flow equivalent irreducible shifts of finite type which contain them.
    
2. (2)
   The classification of certain constant to one maps from SFTs via algebraic invariants of associated G-SFTs.
    

     

On Birman's sequence of Hardy–Rellich-type inequalities

In 1961, Birman proved a sequence of inequalities $\{I_n\}$, for $n\in \mathbb{N}$, valid for functions in $C_0^n((0,\infty ))?L^2((0,\infty ))$. In particular, $I_1$ is the classical (integral) Hardy inequality and $I_2$ is the well-known Rellich inequality. In this paper, we give a proof of this sequence of inequalities valid on a certain Hilbert space $H_n([0,\infty ))$ of functions defined on $[0,\infty )$. Moreover, $f\in H_n([0,\infty ))$ implies $f^{\prime }\in H_{n?1}([0,\infty ))$; as a consequence of this inclusion, we see that the classical Hardy inequality implies each of the inequalities in Birman's sequence. We also show that for any finite $b>0$, these inequalities hold on the standard Sobolev space $H_0^n((0,b))$. Furthermore, in all cases, the Birman constants ${[(2n?1)!!]}^2/2^{2n}$ in these inequalities are sharp and the only function that gives equality in any of these inequalities is the trivial function in $L^2((0,\infty ))$ (resp., $L^2((0,b))$). We also show that these Birman constants are related to the norm of a generalized continuous Cesàro averaging operator whose spectral properties we determine in detail.     

Towards Targeted Drug Delivery by Covalent Ligand-Modified Polymeric Nanocontainers

Here we present a novel strategy for specific cellular targeting of polymeric nanocontainers by using self-assembly of block copolymers consisting of either Polydimethoxysiloxane-b-Polymethyloxazoline-b-Polydimethoxysiloxane (PDMS-b-PMOXA-b-PDMS) or functionalized PDMS-b-PMOXA-b-PDMS. Covalent functionalization of the above copolymer was accomplished using either the fluorescent dye sulforhodamine B or a poly-guanosin ligand, the latter by using the Huisgen 1,3-dipolar cycloaddition. The success of the covalent modification of the block copolymer has been determined by studying functionalized sulforhodamine B by NMR and fluorescence correlation spectroscopy. The covalent click chemistry approach leads to efficiently functionalized polymeric nanocontainers which enables specific uptake by activated macrophages overexpressing the scavenger receptor A1.     

Quantification of fatty acid ethyl esters (FAEE) and ethyl glucuronide (EtG) in meconium from newborns for detection of alcohol abuse in a maternal health evaluation study

Fatty acid ethyl esters (FAEE) and ethyl glucuronide (EtG) were determined in 602 meconium samples in a maternal health evaluation study for detection of gestational alcohol consumption. A validated headspace solid phase microextraction method in combination with GC-MS was used for FAEE and the cumulative concentration of ethyl palmitate, ethyl linoleate, ethyl oleate, and ethyl stearate with a cut-off of 500 ng/g was applied for interpretation. A new and simple method was developed and validated for quantification of EtG from 10–20 mg meconium with D ₅-EtG as internal standard consisting of 30 min. extraction with methanol/water (1:1, v/v), evaporation of methanol, filtration of the aqueous solution through a cellulose filter and injection into LC-MS-MS. The limits of detection and quantification for EtG were 10 and 30 ng/g, the recovery 86.6 to 106.4% and the standard deviation of the concentrations ranged from 13% at 37 ng/g to 5% at 46,700 ng/g (N?=?6). FAEE above the cut-off were found in 43 cases (7.1%) with cumulative concentrations between 507 and 22,580 ng/g and with one outlier of about 150,000 ng/g (EtG not detected). EtG was detected in 97 cases (16.3%) and concentrations between LOD and 10,200 ng/g with another outlier of 82,000 ng/g (FAEE 10,500 ng/g). Optimal agreement between the two markers was obtained with a cut-off for EtG of 274 ng/g and 547 cases with both FAEE- and EtG-negative, 33 cases with both FAEE- and EtG-positive, nine cases with FAEE-positive and EtG-negative, and seven cases with FAEE-negative and EtG-positive. Differences in physical, chemical, and biochemical properties and in the pharmacokinetic behavior are discussed as reasons for the deviating cases. In none of the 602 cases, serious alcohol consumption was reported by the mothers and no evidence for gestational ethanol exposure was observed in the medical investigation of the newborns. It is concluded that the combined use of FAEE and EtG in meconium as markers for fetal alcohol exposure essentially increases the accuracy of the interpretation and helps to avoid false positive and false-negative results.     

A Dendrimer Chiroptical Switch Based on the Reversible Intramolecular Photoreaction of Anthracene and Benzene Rings

A series of Fréchet‐type dendrimers with 9‐benzyloxymethylanthracene cores were synthesized and characterized. The chiral source for the dendrimers was an (S)‐2‐methyl‐1‐butoxy group in the 3‐position of the benzene ring. Irradiation at 366 nm of a dilute benzene solution led to the formation of two diastereomers (1:1) through a quantitative intramolecular [4π+4π] cycloaddition between the central anthracene ring and the neighboring benzene ring. The process can be reversed with 254 nm UV light or heat. The benzene rings in the dendrons work as a light‐harvesting system. The optical rotation values measured for the reversible process showed fatigue resistance. Thus, a promising new type of chiroptical switch has been created that has optical rotation values as output signals.     

Farnesylation or geranylgeranylation? Efficient assays for testing protein prenylation <Emphasis Type="Italic">in vitro</Emphasis> and <Emphasis Type="Italic">in vivo</Emphasis>

Background  

Available in vitro and in vivo methods for verifying protein substrates for posttranslational modifications via farnesylation or geranylgeranylation (for example, autoradiography with ³H-labeled anchor precursors) are time consuming (weeks/months), laborious and suffer from low sensitivity.     

Heterogenization of an organorhenium(VII) oxide on a modified mesoporous molecular sieve

A novel route to heterogenize an organorhenium(VII) oxide, derived from the well examined methyltrioxorhenium(VII) (MTO), on the surface of an iodosilane-modified MCM-41 is applied. The successful grafting of the -CH(2)-ReO3 moiety on the surface was evidenced by 1H CP MAS NMR, IR spectroscopy, TG-MS, and elemental analysis. XRD and TEM analyses confirm the retaining of long-range ordering throughout the grafting process. The rhenium loading of the mesoporous material after heterogenization of MTO is found to be 1.25 wt%. Despite containing formally a derivative of the very sensitive benzyltrioxorhenium(VII) the material is stable at room temperature and applicable as a heterogeneous catalyst for aldehyde olefination reactions.     

Das Sublimieren von Jod im Laboratorium

Ohne Zusammenfassung