Fulvenes, fulvalenes, and azulene: are they aromatic chameleons?

On the basis of the theory of Baird on reversal of Hückel's rule for aromaticity and antiaromaticity of annulenes when going from the electronic ground state (S0) to the lowest pipi* triplet state (T1) (J. Am. Chem. Soc. 1972, 94, 4941), we argue that fulvenes, fulvalenes, and azulene are "aromatic chameleons". The dipole moments of fulvenes in T1 should be of comparable magnitude to those of S0, but due to the reversal of Hückel's aromaticity rule in T1, their dipole should be in the opposite direction. Thereby, they are capable of adopting some aromaticity in both the T1 and S0 states as they adapt their dipolar resonance structures. The same applies to fulvalenes and azulene in their lowest quintet states (Q1) when compared to S0. Our hypothesis on chameleon behavior is supported by quantum chemical OLYP, CASSCF, and CASPT2 calculations of dipole moments, pi-orbital populations, and energies.     

Determination of Polychlorinated Biphenyls and Chlorinated Pesticides in Environmental Biological Samples Using Focused Microwave-assisted Extraction

Abstract

Organochlorine compounds such as polychlorinated biphenyls (PCBs) and chlorinated pesticides have been analysed in environmental biological samples using focused microwave-assisted extraction (FMW). The analytical procedure is presented and the results for two Standard Reference Materials, a cod liver oil and a freeze-dried mussel tissue, are reported. The average recoveries for the sum of the PCBs are between 93% and 106%, and for the sum of the chlorinated pesticides are between 109 to 115% for all the certified compounds analysed. The developped analytical procedure is highly reproducible with an average standard deviation of 8% for the sum of the PCBs and 9.7% for the sum of the chlorinated pesticides in the two matrices.     

Chiral δ-Hydroxyalkyl Wittig Reagents: Synthesis and Reactivity

Abstract

enantioselective reduction of ketophosphonium salts give chiral synthons used in WITTIG reactions to prepare opticaly active ethylenic alcohols.     

Decay scheme of92m Nb

The beta decay of the 2^{+ 92m} Nb was reinvestigated via⁹³Nb(γ, n) reaction. The feeding of the 2⁺ 2,067 keV level of⁹²Zr was determined measuring the intensity of the 1,132 keV gamma-ray transition.     

Beta decay of57Ni

The decay of⁵⁷Ni was studied using both single and coincidence gamma-ray spectroscopy. Four new low-intensity transitions were observed in the single spectra. The energies and intensities of these transitions related to the 1378 keV transition were determined as 304.1 keV, 0.002%; 696.0 keV, 0.001%, 1350.5 keV, 0.002% and 1603.3 keV, 0.005%. Weak transitions at 541.9, 755.3 and 1279.9 keV were confirmed in agreement to earlier works, and their intensities related to 1378 keV were determined as 0.005%, 0.007% and 0.0012%, respectively.     

Admissible sequences and the preprojective component of a quiver

This paper concerns indecomposable preprojective modules over the path algebra of a finite connected quiver without oriented cycles. For each such module, an explicit formula in terms of the geometry of the quiver gives a unique, up to a certain equivalence, shortest (+)-admissible sequence such that the corresponding composition of reflection functors annihilates the module. An efficient way to compute the module is to recover it from its shortest (+)-admissible sequence. The set of equivalence classes of the above sequences has a natural structure of a partially ordered set. For a large class of quivers, the Hasse diagram of the partially ordered set is isomorphic to the preprojective component of the Auslander-Reiten quiver. The techniques of (+)-admissible sequences yield a new result about slices in the preprojective component.     

NMR and theoretical calculations: a unified view of the cis/trans isomerization of 2-substituted thiazolidines containing peptides

The cis/trans isomerization of peptides containing the pseudoproline (4R)-thiazolidine-4-carboxylic acid Cys(Psi (R1,R2) pro) is investigated from both an experimental and a theoretical point of view by NMR and DFT calculations. A series of Ac-Cys(Psi(R1,R2) pro)-OCH3 and Ac-Cys(Psi(R1,R2) pro)-NHCH3 peptides were prepared to assess the influence of the substitution at the C2 position as well as of the amide following the thiazolidine residue. For each compound, the cis/trans ratio along with free energy, the puckering of the thiazolidine ring and the free rotational energy barrier are reported and discussed. We observe there is a pronounced effect of the C2 substituents and of the chirality upon the cis/trans ratio with the population of the cis content in the order (2R)-Cys(Psi(CH3,H) pro)<(2S)-Cys(Psi(H,CH3) pro)相似文献   

3D Bioprinting of Tissue/Organ Models

In vitro tissue/organ models are useful platforms that can facilitate systematic, repetitive, and quantitative investigations of drugs/chemicals. The primary objective when developing tissue/organ models is to reproduce physiologically relevant functions that typically require complex culture systems. Bioprinting offers exciting prospects for constructing 3D tissue/organ models, as it enables the reproducible, automated production of complex living tissues. Bioprinted tissues/organs may prove useful for screening novel compounds or predicting toxicity, as the spatial and chemical complexity inherent to native tissues/organs can be recreated. In this Review, we highlight the importance of developing 3D in vitro tissue/organ models by 3D bioprinting techniques, characterization of these models for evaluating their resemblance to native tissue, and their application in the prioritization of lead candidates, toxicity testing, and as disease/tumor models.     

A microfluidic device for parallel 3-D cell cultures in asymmetric environments

We demonstrate a concept for how a miniaturized 3-D cell culture in biological extracellular matrix (ECM) or synthetic gels bridges the gap between organ-tissue culture and traditional 2-D cultures. A microfluidic device for 3-D cell culture including microgradient environments has been designed, fabricated, and successfully evaluated. In the presented system stable diffusion gradients can be generated by application of two parallel fluid flows with different composition against opposite sides of a gel plug with embedded cells. Culture for up to two weeks was performed showing cells still viable and proliferating. The cell tracer dye calcein was used to verify gradient formation as the fluorescence intensity in exposed cells was proportional to the position in the chamber. Cellular response to an applied stimulus was demonstrated by use of an adenosine triphosphate gradient where the onset of a stimulated intracellular calcium release also depended on cell position.