An efficient one step dihydroxylation of 1,2-glycals with oxone in acetone

A number of glycals have been converted into the corresponding 1,2-diols in fair to good yields. The reaction appears to proceed via the corresponding epoxide which opens in situ.     

CAESAR: a new conformer generation algorithm based on recursive buildup and local rotational symmetry consideration

A highly efficient conformer search algorithm based on a divide-and-conquer and recursive conformer build-up approach is presented in this paper. This approach is combined with consideration of local rotational symmetry so that conformer duplicates due to topological symmetry in the systematic search can be efficiently eliminated. This new algorithm, termed CAESAR (Conformer Algorithm based on Energy Screening and Recursive Buildup), has been implemented in Discovery Studio 1.7 as part of the Catalyst Component Collection. CAESAR has been validated by comparing the conformer models generated by the new method and Catalyst/FAST. CAESAR is consistently 5-20 times faster than Catalyst/FAST for all data sets investigated. The speedup is even more dramatic for molecules with high topological symmetry or for molecules that require a large number of conformers to be sampled. The quality of the conformer models generated by CAESAR has been validated by assessing the ability to reproduce the receptor-bound X-ray conformation of ligands extracted for the Protein Data Bank (PDB) and assessing the ability to adequately cover the pharmacophore space. It is shown that CAESAR is able to reproduce the receptor-bound conformation slightly better than the Catalyst/FAST method for a data set of 918 ligands retrieved from the PDB. In addition, it is shown that CEASAR covers the pharmacophore space as well or better than Catalyst/FAST.     

6‐(Diazomethyl)‐1,3‐bis(methoxymethyl)uracil,Synthesis and Transformation into Annulated Pyrimidinediones

6‐(Diazomethyl)‐1,3‐bis(methoxymethyl)uracil ( 5 ) was prepared from the known aldehyde 3 by hydrazone formation and oxidation. Thermolysis of 5 and deprotection gave the pyrazolo[4,3‐d]pyrimidine‐5,7‐diones 7a and 7b . Rh₂(OAc)₄ catalyzed the transformation of 5 into to a 2 : 1 (Z)/(E) mixture of 1,2‐diuracilylethenes 9 (67%). Heating (Z)‐ 9 in 12n HCl at 95° led to electrocyclisation, oxidation, and deprotection to afford 73% of the pyrimido[5,4‐f]quinazolinetetraone 12 . The Rh₂(OAc)₄‐catalyzed reaction of 5 with 3,4‐dihydro‐2H‐pyran and 2,3‐dihydrofuran gave endo/exo‐mixtures of the 2‐oxabicyclo[4.1.0]heptane 13 (78%) and the 2‐oxabicyclo[3.1.0]hexane 15 (86%), Their treatment with AlCl₃ or Me₂AlCl promoted a vinylcyclopropane–cyclopentene rearrangement, leading to the pyrano‐ and furanocyclopenta[1,2‐d]pyrimidinediones 14 (88%) and 16 (51%), respectively. Similarly, the addition product of 5 to 2‐methoxypropene was transformed into the 5‐methylcyclopenta‐pyrimidinedione 18 (55%). The Rh₂(OAc)₄‐catalyzed reaction of 5 with thiophene gave the exo‐configured 2‐thiabicyclo[3.1.0]hexane 19 (69%). The analoguous reaction with furan led to 8‐oxabicyclo[3.2.1]oct‐2‐ene 20 (73%), and the reaction with (E)‐2‐styrylfuran yielded a diastereoisomeric mixture of hepta‐1,4,6‐trien‐3‐ones 21 (75%) that was transformed into the (1E,4E,6E)‐configured hepta‐1,4,6‐trien‐3‐one 21 (60%) at ambient temperature.     

Nonlinear optical response of chloroaluminiumphthalocyanine encapsulated by silica core-shell particles

We report for the first time on the synthesis of core-shell particles containing chloroaluminiumphthalocyanine (ClAlPc) prepared using a sol-gel technique. These particles have the dye molecules at the core, encapsulated by silica shell. The mean size of the particle is determined from HRTEM studies and is found to be approximately 0.08 microm. The surface and bulk compositions of the core-shell particles are studied by XPS and EDAX measurements, respectively. Time-resolved fluorescent measurements indicate a decrease in fluorescence lifetime for the core-shell particles as compared to that of bare dye dissolved in ethanol. This is analyzed on the basis of available theoretical models. Third-order nonlinear optical effects are investigated by the Z-scan technique using 8 ns pulses at a wavelength of 532 nm from a frequency-doubled Nd:YAG laser. The analysis indicates that both singlet and triplet excited-state absorption contribute to nonlinear absorption.     

Can super-resolution microscopy become a standard characterization technique for materials chemistry?

The characterization of newly synthesized materials is a cornerstone of all chemistry and nanotechnology laboratories. For this purpose, a wide array of analytical techniques have been standardized and are used routinely by laboratories across the globe. With these methods we can understand the structure, dynamics and function of novel molecular architectures and their relations with the desired performance, guiding the development of the next generation of materials. Moreover, one of the challenges in materials chemistry is the lack of reproducibility due to improper publishing of the sample preparation protocol. In this context, the recent adoption of the reporting standard MIRIBEL (Minimum Information Reporting in Bio–Nano Experimental Literature) for material characterization and details of experimental protocols aims to provide complete, reproducible and reliable sample preparation for the scientific community. Thus, MIRIBEL should be immediately adopted in publications by scientific journals to overcome this challenge. Besides current standard spectroscopy and microscopy techniques, there is a constant development of novel technologies that aim to help chemists unveil the structure of complex materials. Among them super-resolution microscopy (SRM), an optical technique that bypasses the diffraction limit of light, has facilitated the study of synthetic materials with multicolor ability and minimal invasiveness at nanometric resolution. Although still in its infancy, the potential of SRM to unveil the structure, dynamics and function of complex synthetic architectures has been highlighted in pioneering reports during the last few years. Currently, SRM is a sophisticated technique with many challenges in sample preparation, data analysis, environmental control and automation, and moreover the instrumentation is still expensive. Therefore, SRM is currently limited to expert users and is not implemented in characterization routines. This perspective discusses the potential of SRM to transition from a niche technique to a standard routine method for material characterization. We propose a roadmap for the necessary developments required for this purpose based on a collaborative effort from scientists and engineers across disciplines.

SRM, an advanced nanoscopy technique demands a transition from being a niche sophisticated technique to standard routine method for material characterization. The roadmap of necessary developments through multidisciplinary collaboration is discussed.     

Chitin Isolation and Chitosan Production from House Crickets (Acheta domesticus) by Environmentally Friendly Methods

Alternative methods were evaluated for chitin isolation from Acheta domesticus. Chemical demineralization was compared to fermentation with Lactococcus lactis, citric acid treatment, and microwave treatment, leading to a degree of demineralization of 91.1 ± 0.3, 97.3 ± 0.8, 70.5 ± 3.5, and 85.8 ± 1.3%, respectively. Fermentation with Bacillus subtilis, a deep eutectic solvent, and enzymatic digestion were tested for chitin isolation, generating materials with less than half the chitin content when compared to alkaline deproteinization. Chitosan was produced on a large scale by deacetylation of the chitinous material obtained from two selected processes: the chemical treatment and an alternative process combining L. lactis fermentation with bromelain deproteinization. The chemical and alternative processes resulted in similar chitosan content (81.9 and 88.0%), antioxidant activity (59 and 49%), and degree of deacetylation (66.6 and 62.9%), respectively. The chitosan products had comparable physical properties. Therefore, the alternative process is appropriate to replace the chemical process of chitin isolation for industrial applications.     

Urea nitrate–catalyzed C-N and C-S bond formation: A mechanochemical approach for 5-chloro-2-arylbenzo[d]thiazole derivatives

A series of substituted 5-chloro-2-arylbenzo[d]thiazoles were synthesized using 4-chloro-2-aminothiophenol and aromatic aldehydes in the presence of urea nitrate as a catalyst using the mechanochemical grindstone technique. This protocol was effectively carried out under metal-free conditions at room temperature, and the desired products were obtained in high to excellent yields in short reaction time (30–60 s). The structure of all the synthesized derivatives was confirmed by spectral characterization. The designed protocol has several benefits like eco-friendly, solvent-free, high yields, easy workup, and recyclability of catalyst. The catalyst was reusable at least four times without significant loss of activity. The good functional group tolerance with a series of derivatives has been demonstrated.     

Study of intermixing and Zr-silicide formation using swift heavy ion irradiation

Swift heavy ion (SHI) beam induced irradiation is an established technique for investigating structural modifications in thin films depending on the S _e sensitivity of material. Intermixing due to 120 MeV Au ion irradiation at different fluences from 10¹² to 10¹⁴ ions/cm² has been reported as a function of ion fluence in a-Si/Zr/a-Si thin films on Si substrate. The samples are characterized before (pristine) and after irradiation using Grazing Incident X-ray Diffraction (GIXRD) and Rutherford Backscattering Spectroscopy (RBS), which confirm the formation of ZrSi at thin film interface. It is suggested that mixing is mainly due to electronic energy loss since the energy transferred from high energy ions seems to create a transient molten zone along the ion track. It is found that the interface mixing increases linearly with the increase in ion fluence. The mixing effect explained in the framework of Thermal spike model. The irradiation effect on the surface roughness of the system is measured using Atomic Force Microscopy (AFM) technique. The current conduction mechanism and Schottky barrier height are also calculated by taking I–V curves across the Metal/Si junction.     

Efficient Ring Opening of Aziridines with Carboxylic Acids

An efficient ring cleavage of aziridines with acids has been studied in the absence of any catalyst. The hydrolysis of the products, amino esters, leads to the corresponding amino alcohols. The reaction has been extended to chiral cycloalkyl aziridines, leading to the formation of diastereomers. After separation, these diastereomers have been converted to optically pure amino alcohols in two steps.