Ultrafast dynamics and temperature effects on the quantum efficiency of the ring-opening reaction of a photochromic indolylfulgide

The ultrafast ring-opening reaction of the molecular switch 1,2-Dimethyl-3-indolylfulgide dissolved in acetonitrile is investigated by temperature dependent quantum efficiency measurements and time-resolved transient absorption spectroscopy in the ultraviolet and visible spectral range. The photoreaction is found to be thermally activated with an activation energy of about 1640 cm^− 1. The transient absorption signal is bi-exponential with the time constants τ₁ = 0.7 ps and τ₂ = 12 ps. The fast time constant is due to solvation dynamics, while the main component τ₂ is attributed to the excited state lifetime and product formation. A long-lived intermediate state in the photoreaction can be excluded.     

Effect of chitosan and thiolated chitosan coating on the inhibition behaviour of PIBCA nanoparticles against intestinal metallopeptidases

Surface modified nanoparticles composed of poly(isobutylcyanoacrylate) (PIBCA) cores surrounded by a chitosan and thiolated chitosan gel layer were prepared and characterized in previous works. The presence of such biopolymers on the nanoparticle surface conferred those nanosystems interesting characteristics that might partially overcome the gastrointestinal enzymatic barrier, improving the oral administration of pharmacologically active peptides. In the present work, the antiprotease behaviour of this family of core–shell nanoparticles was in vitro tested against two model metallopeptidases present in the gastrointestinal tract (GIT): Carboxypeptidase A -CP A- (luminal protease) and Leucine Aminopeptidase M -LAP M- (membrane protease). As previous step, the zinc-binding capacity of these nanoparticles was evaluated. Interestingly, an improvement of both the zinc-binding capacity and the antiprotease effect of chitosan was observed when the biopolymers (chitosan and thiolated chitosan) were used as coating component of the core–shell nanoparticles, in comparison with their behaviour in solution, thanks to the different biopolymer chains rearrangement. The presence of amino, hydroxyl and thiol groups on the nanoparticle surface promoted zinc binding and hence the inhibition of the metallopeptidases analysed. On the contrary, the occurrence of a cross-linked structure in the gel layer surrounding the PIBCA cores of thiolated formulations, due to the formation of interchain and intrachain disulphide bonds, partially limited the inhibition of the proteases. The low accessibility of cations to the active groups of the cross-linked polymeric shell was postulated as a possible explanation of this behaviour. Results obtained in this work make this family of surface-modified nanocarriers promising candidates for the successfull administration of pharmacologically active peptides and proteins by the oral route.     

Beryllium-tetrakis-[trimethylsilyl]-diamid-eine Verbindung mit zweibindigem Beryllium

Monomeres [(CH₃)₃Si]₂NBeN[Si(CH₃)₃]₂ (I) entsteht in 68% Ausb. bei der Reaktion von BeCl₂-Ätherat mit NaN[Si(CH₃)₃]₂. Eigenschaften, IR-, Raman- und¹H-NMR-Spektren sprechen für einen NBeN-Winkel von 180°. Die SiN- und BeN-Valenzkraftkonstanten werden zu 3,40 bzw. 2,96 mdyn/Å errechnet.Monomeric I has been prepared (yield 68%) by the reaction of BeCl₂ with NaN[Si(CH₃)₃]₂ in ether. Properties, infrared, raman and¹H-NMR-spectra support a NBeN angle of 180°. SiN and BeN force constants were calculated to be 3,40 and 2,96 mdyn/Å, respectively.

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9. Mitt. über silylsubstituierte Metallamide; 8. Mitt.:H. Bürger, W. Sawodny undU. Wannagat, J. Organometall. Chem.2, 113, (1965).     

Supramolecular main-chain liquid crystalline polymers and networks with competitive hydrogen bonding

A series of supramolecular polymers and networks with variable liquid crystalline characteristics have been created. These species are formed though the benzoic acid/pyridine associations of a flexible bisacid and a mixture of a rigid bispyridyl and a non-mesogenic tetrapyridyl. The networked systems displayed liquid crystalline characteristics up to and including 22.5% netpoint inclusion. Above this concentration, only crystalline and melting behaviours were observed. This observed phenomenon would seem to be linked to the statistical correlation of hydrogen bond acceptors and donors. There was also no observed phase segregation of the species after multiple heat/cool cycles and extended periods of time in the isotropic state. This would indicate that the thermodynamically more stable mesogenic phase cannot out-compete the non-liquid crystalline network. Computational analysis indicates no significant difference in hydrogen bond strength between the two different hydrogen bond acceptors.     

Automated Synthesis of 68Ga-Labeled DOTA-MGS8 and Preclinical Characterization of Cholecystokinin-2 Receptor Targeting

The new minigastrin analog DOTA-MGS8 targeting the cholecystokinin-2 receptor (CCK2R) used in this study displays the combination of two site-specific modifications within the C-terminal receptor binding sequence together with an additional N-terminal amino acid substitution preventing fast metabolic degradation. Within this study, the preparation of ⁶⁸Ga-labeled DOTA-MGS8 was validated using an automated synthesis module, describing the specifications and analytical methods for quality control for possible clinical use. In addition, preclinical studies were carried out to characterize the targeting potential. [⁶⁸Ga]Ga-DOTA-MGS8 showed a high receptor-specific cell internalization into AR42J rat pancreatic cells (~40%) with physiological expression of rat CCK2R as well as A431-CCK2R cells transfected to stably express human CCK2R (~47%). A favorable biodistribution profile was observed in BALB/c nude mice xenografted with A431-CCK2R cells and mock-transfected A431 cells as control. The high tumor uptake of ~27% IA/g together with low background activity and limited uptake in non-target tissue confirms the potential for high-sensitivity positron emission tomography of stabilized MG analogs in patients with MTC and other CCK2R-related malignancies.     

Spectroscopies and Electron Microscopies Unravel the Origin of the First Colour Photographs

The first colour photographs were created by a process introduced by Edmond Becquerel in 1848. The nature of these photochromatic images colours motivated a debate between scientists during the XIX^th century, which is still not settled. We present the results of chemical analysis (EDX, HAXPES and EXAFS) and morphology studies (SEM, STEM) aiming at explaining the optical properties of the photochromatic images (UV-visible spectroscopy and low loss EELS). We rule out the two hypotheses (pigment and interferences) that have prevailed since 1848, respectively based on variations in the oxidation degree of the compound forming the sensitized layer and periodically spaced photolytic silver planes. A study of the silver nanoparticles dispersions contained in the coloured layers showed specific localizations and sizes distributions of the nanoparticles for each colour. These results allow us to formulate a plasmonic hypothesis on the origin of the photochromatic images colours.     

Linked Primes and Orders in Artinian Rings

It is shown that prime ideals of a Noetherian ring are linked if and only if certain corresponding prime ideals are linked in an associated Artinian ring. Furthermore, it is shown that there is a canonical linking ideal, which can be found by using a construction based on middle annihilator ideals.     

Network Dynamics in Elemental Assimilation and Metabolism

Metabolism and physiology frequently follow non-linear rhythmic patterns which are reflected in concepts of homeostasis and circadian rhythms, yet few biomarkers are studied as dynamical systems. For instance, healthy human development depends on the assimilation and metabolism of essential elements, often accompanied by exposures to non-essential elements which may be toxic. In this study, we applied laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to reconstruct longitudinal exposure profiles of essential and non-essential elements throughout prenatal and early post-natal development. We applied cross-recurrence quantification analysis (CRQA) to characterize dynamics involved in elemental integration, and to construct a graph-theory based analysis of elemental metabolism. Our findings show how exposure to lead, a well-characterized toxicant, perturbs the metabolism of essential elements. In particular, our findings indicate that high levels of lead exposure dysregulate global aspects of metabolic network connectivity. For example, the magnitude of each element’s degree was increased in children exposed to high lead levels. Similarly, high lead exposure yielded discrete effects on specific essential elements, particularly zinc and magnesium, which showed reduced network metrics compared to other elements. In sum, this approach presents a new, systems-based perspective on the dynamics involved in elemental metabolism during critical periods of human development.     

An Approach to Loop Quantum Cosmology Through Integrable Discrete Heisenberg Spin Chains

The quantum evolution equation of Loop Quantum Cosmology (LQC)—the quantum Hamiltonian constraint—is a difference equation. We relate the LQC constraint equation in vacuum Bianchi I separable (locally rotationally symmetric) models with an integrable differential-difference nonlinear Schrödinger type equation, which in turn is known to be associated with integrable, discrete Heisenberg spin chain models in condensed matter physics. We illustrate the similarity between both systems with a simple constraint in the linear regime.