Chemoselective Oxidation of Benzyl,Amino, and Propargyl Alcohols to Aldehydes and Ketones under Mild Reaction Conditions

Catalytic oxidation reactions often suffer from drawbacks such as low yields and poor selectivity. Particularly, selective oxidation of alcohols becomes more difficult when a compound contains more than one oxidizable functional group. In order to deliver a methodology that addresses these issues, herein we report an efficient, aerobic, chemoselective and simplified approach to oxidize a broad range of benzyl and propargyl alcohols containing diverse functional groups to their corresponding aldehydes and ketones in excellent yields under mild reaction conditions. Optimal yields were obtained at room temperature using 1 mmol substrate, 10 mol % copper(I) iodide, 10 mol % 4-dimethylaminopyridine (DMAP), and 1 mol % 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) in acetonitrile, under an oxygen balloon. The catalytic system can be applied even when sensitive and oxidizable groups such as alkynes, amines, and phenols are present; starting materials and products containing such groups were found to be stable under the developed conditions.     

Ruthenium-caged antisense morpholinos for regulating gene expression in zebrafish embryos

Photochemical approaches afford high spatiotemporal control over molecular structure and function, for broad applications in materials and biological science. Here, we present the first example of a visible light responsive ruthenium-based photolinker, Ru(bipyridine)₂(3-ethynylpyridine)₂ (RuBEP), which was reacted stoichiometrically with a 25mer DNA or morpholino (MO) oligonucleotide functionalized with 3′ and 5′ terminal azides, via Cu(i)-mediated [3+2] Huisgen cycloaddition reactions. RuBEP-caged circular morpholinos (Ru-MOs) targeting two early developmental zebrafish genes, chordin and notail, were synthesized and tested in vivo. One-cell-stage zebrafish embryos microinjected with Ru-MO and incubated in the dark for 24 h developed normally, consistent with caging, whereas irradiation at 450 nm dissociated one 3-ethynylpyridine ligand (Φ = 0.33) and uncaged the MO to achieve gene knockdown. As demonstrated, Ru photolinkers provide a versatile method for controlling structure and function of biopolymers.     

Wavelength selection framework for classifying food and pharmaceutical samples into multiple classes

Near infrared (NIR) spectroscopy is an efficient, low‐cost analytical technique widely applied to identify the origin of food and pharmaceutical products. NIR spectra‐based classification strategies typically use thousands of equally spaced wavelengths as input information, some of which may not carry relevant information for product classification. When that is the case, the performance of predictive and exploratory multivariate techniques may be undermined by such noisy information. In this paper, we propose an iterative framework for selecting subsets of NIR wavelengths aimed at classifying samples into categories. For that matter, we integrate Principal Components Analysis (PCA) and three classification techniques: k‐Nearest Neighbor (KNN), Probabilistic Neural Network (PNN) and Linear Discriminant Analysis (LDA). PCA is first applied to NIR data, and a wavelength importance index is derived based on the PCA loadings. Samples are then categorized using the wavelength with the highest index and the classification accuracy is calculated; next, the wavelength with the second highest index is inserted into the dataset and a new classification is performed. This forward‐based iterative procedure is carried out until all original wavelengths are inserted into the dataset used for classification. The subset of wavelengths leading to the maximum accuracy is chosen as the recommended subset. Our propositions performed remarkably well when applied to four datasets related to food and pharmaceutical products. Copyright © 2016 John Wiley & Sons, Ltd.     

Cucurbit[8]uril-induced diarylethene thermally activated delay fluorescence supramolecular switch for sequential energy transfer

Constructing molecular switches based on supramolecular assembly strategy is a research hotspot. In this work, we constructed an all visible-light-regulated supramolecular photo-switch based on pyridinium-modified diarylethene derivative (DTE-Me) and cucurbit[8]uril (CB[8]). CB[8] not only accelerated the photochromic process under 365 nm ultraviolet light but also shifted the absorption of open formed DTE-Me to the visible region, which led to efficient photocyclization under 450 nm visible light irradiation, while DTE-Me and DTE-Me/CB[7] remained unchanged under the same irradiating condition. Moreover, the complexation with CB[8] could induce the strong thermally activated delayed fluorescence (TADF) of guest molecular at 550 nm, which further shifted to 670 nm through two-step sequential energy transfer with sulforhodamine B (SRB) and Cy5. This energy transfer process could also be regulated with visible light, and the application for information encryption was also demonstrated. This assembly provides a convenient approach to construct all visible light-regulated TADF photo-switch.     

Collisional Cross-Sections with T-Wave Ion Mobility Spectrometry without Experimental Calibration

A method for relating traveling-wave ion mobility spectrometry (TWIMS) drift times with collisional cross-sections using computational simulations is presented. This method is developed using SIMION modeling of the TWIMS potential wave and equations that describe the velocity of ions in gases induced by electric fields. The accuracy of this method is assessed by comparing the collisional cross-sections of 70 different reference ions obtained using this method with those obtained from static drift tube ion mobility measurements. The cross-sections obtained here with low wave velocities are very similar to those obtained using static drift (average difference?=?0.3%) for ions formed from both denaturing and buffered aqueous solutions. In contrast, the cross-sections obtained with high wave velocities are significantly greater, especially for ions formed from buffered aqueous solutions. These higher cross-sections at high wave velocities may result from high-order factors not accounted for in the model presented here or from the protein ions unfolding during TWIMS. Results from this study demonstrate that collisional cross-sections can be obtained from single TWIMS drift time measurements, but that low wave velocities and gentle instrument conditions should be used in order to minimize any uncertainties resulting from high-order effects not accounted for in the present model and from any protein unfolding that might occur. Thus, the method presented here eliminates the need to calibrate TWIMS drift times with collisional cross-sections measured using other ion mobility devices.

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The importance of glyceraldehyde radiolysis in chemical evolution

Studies in chemical evolution are intended to demonstrate how compounds of biological importance are generated from substances that could have been found in abiotic conditions on the primitive Earth or in extraterrestrial environments. In this context, the aim of the present work was to examine the behavior of dl-glyceraldehyde in both aqueous solution and solid samples under gamma irradiation. We irradiated dl-glyceraldehyde at different doses and temperatures with a gamma source; even at low doses and temperature (77 K), free radicals were detected. Among the products formed were ethylene glycol and glycolaldehyde. Some sugar-like compounds were also detected.

     

On the geometric–arithmetic index by decompositions-CMMSE

The concept of geometric–arithmetic index was introduced in the chemical graph theory recently, but it has shown to be useful. There are many papers studying different kinds of indices (as Wiener, hyper–Wiener, detour, hyper–detour, Szeged, edge–Szeged, PI, vertex–PI and eccentric connectivity indices) under particular cases of decompositions. The main aim of this paper is to show that the computation of the geometric-arithmetic index of a graph G is essentially reduced to the computation of the geometric-arithmetic indices of the so-called primary subgraphs obtained by a general decomposition of G. Furthermore, using these results, we obtain formulas for the geometric-arithmetic indices of bridge graphs and other classes of graphs, like bouquet of graphs and circle graphs. These results are applied to the computation of the geometric-arithmetic index of Spiro chain of hexagons, polyphenylenes and polyethene.