Electrophilic aryl-halogenation using N-halosuccinimides under ball-milling

We report here a methodology of chemo- and regio-selective aryl bromination and iodination using respective N-halosuccinimides at room temperature in the absence of any solvents, catalyst/additives under ball-milling condition. However, for chlorination ceric ammonium nitrate was used as additive. The coupled product succinimide, produced from the reactions, was recycled via regeneration of NBS. This methodology works with the electron-donor substituted or unsubstituted arenes.     

Treatment of sugar processing industry wastewater using copper electrode by electrocoagulation: Performance and economic study

This paper demonstrates the use of copper electrode for the treatment of sugar processing industry wastewater (SPIW) in terms of chemical oxygen demand (COD) by applying electrocoagulation (EC) method. EC process was carried out in batch mode with electrode effective area of 0.0112 m², supplied current intensity (CI) of 44.64 A/m² - 223.21 A/m², electrode gap (EG) of 0.5–2.5 cm, electrolyte (NaCl) dose (ED) of 0.5–2.5 g/L to treat SPIW with initial chemical oxygen demand (COD) of 6000 mg/L. The maximum COD removal 73% of SPIW is achieved at optimized condition of SPIW pH: 7, CI: 89.28 A/m², EG: 1.5 cm & ED: 1.5 g/L. Sludge and scum generated during EC process were characterized by FTIR, TGA/DTA/DTG, proximate & ultimate analysis to find its applicability and their disposal. Additionally, economic study of EC treatment process at optimum condition suggest treatment cost was 11.2 US$/m³ and it indicate economic results as comparison to other available treatment processes.     

Diastereoselectivity is in the Details: Minor Changes Yield Major Improvements to the Synthesis of Bedaquiline**

Bedaquiline is a crucial medicine in the global fight against tuberculosis, yet its high price places it out of reach for many patients. Herein, we describe improvements to the key industrial lithiation-addition sequence that enable a higher yielding and therefore more economical synthesis of bedaquiline. Prioritization of mechanistic understanding and multi-lab reproducibility led to optimized reaction conditions that feature an unusual base-salt pairing and afford a doubling of the yield of racemic bedaquiline. We anticipate that implementation of these improvements on manufacturing scale will be facile, thereby substantially increasing the accessibility of this essential medication.     

Regio- and stereoselective synthesis of aziridino epoxides from cyclic dienes

Two different routes for the regio- and stereoselective synthesis of aziridino epoxides from cyclic dienes have been explored. The first strategy involves regiospecific aziridination of cyclic diene derivatives and subsequent epoxidation with m-CPBA to yield cis-aziridino epoxides as major products. The second strategy utilizes regiospecific epoxidation of cyclic diene derivatives followed by Sharpless aziridination to provide exclusively trans-aziridino epoxides. Synthesis of both enantiomers of cis-aziridino epoxides from (R)-(-)- and (S)-(+)-carvones are also reported.     

Effect of ring fusion stereochemistry on double bond geometry. Unexpected formation of nine-membered cyclic ether with E-configurated double bond through RCM

Formation of a nine-membered cyclic ether with E-configurated double bond was observed during construction of 5-9-5 tricycles through RCM of dienes. Ring fusion stereochemistry in the products oxonenes was found to have profound influence on the olefin geometry. cis-anti-cis 5-9-5 tricycle was obtained with Z-configurated olefin while cis-syn-cis 5-9-5 system was obtained with E- as well as Z-configurated double bond with the former predominating.     

Characterization of the tryptophan residues of human placental ribonuclease inhibitor and its complex with bovine pancreatic ribonuclease A by steady-state and time-resolved emission spectroscopy

Human placental ribonuclease inhibitor (hRI) containing six tryptophan (Trp) residues located at positions 19, 261, 263, 318, 375, and 438 and its complex with RNase A have been studied using steady-state and time-resolved fluorescence (298 K) as well as low-temperature phosphorescence (77 K). Two Trp residues in wild-type hRI and also in the protein-protein complex with RNase A are resolved optically. The accessible surface area values of Trp residues in the wild-type hRI and its complex and consideration of inter-Trp energy transfer in the wild-type hRI reveal that one of the Trp residues is Trp19, which is located in a hydrophobic buried region. The other Trp residue is tentatively assigned as Trp375 based on experimental results on wild-type hRI and its complex. This residue in the wild-type hRI is more or less solvent exposed. Both the Trp residues are perturbed slightly on complex formation. Trp19 moves slightly toward a more hydrophobic region, and the environment of Trp375 becomes less solvent exposed. The complex formation also results in a more heterogeneous environment for both the optically resolved Trp residues.     

A Comparative Study of the Nonlinear Optical Properties of Cd<Subscript>n</Subscript>X<Subscript>n</Subscript> (X: S,Se and Te) Clusters

We report results of hyperpolarizability calculations on Cd_nX_n (X: S, Se and Te; n = 1–10) clusters. Our results show that the geometric configurations of different types of clusters under investigation are quite similar at specific values of n. Both static and frequency dependent components of first and second order hyperpolarizability tensors of Cd_nS_n, Cd_nSe_n and Cd_nTe_n are compared. It is observed that in general nonlinear optical coefficients show identical variation in all the cluster materials. The present investigation also manifests the improvement of these coefficients due to the introduction of asymptotically correct generalized gradient approximation functional over the local density functional and normal gradient corrected functional. Symmetrized fragment orbital analysis has been performed to provide explanation of the observed hyperpolarizability variation. We also analyse how geometries with closely lying energy values influence the hyperpolarizabilities of these cluster materials.     

Towards the total synthesis of neurotrophically active tashironins: rapid construction of the tetracyclic core through a tandem oxidative dearomatization-IMDA reaction-RCM protocol

An exceptionally short (three step) strategy involving tandem oxidative dearomatization, intramolecular Diels-Alder (IMDA) reaction and RCM has been devised to generate the complete carbon framework present in tashironin-type sesquiterpenoid natural products.     

Role of positional isomers on receptor-anion binding and evidence for resonance energy transfer

New urea-based sensors show a strong affinity for F⁻, CH₃COO⁻, and H₂PO₄⁻ with an appreciable color change in the presence of excess F⁻. The position of the nitro group in the urea derivative influences the relative affinity toward anionic analytes. Spectral and ab initio studies showed the difference in the deprotonation sites for the ortho- and meta/para-isomers in these cases. Photophysical studies confirmed the resonance energy transfer in the case of the ortho-isomer. The ortho-isomer can act as a dual emission probe for F⁻.     

Construction of the 3-prenyl-4-oxa-tricyclo[4.3.1.0]dec-8-en-2-one core of caged xanthonoid natural products via tandem Wessely oxidation-intramolecular [4+2] cycloaddition

A two-step protocol based on tandem Wessely oxidation/intramolecular Diels-Alder reaction to provide general access to the 3-prenyl-4-oxa-tricyclo[4.3.1.0^3,7]dec-8-en-2-one core present in the caged Garcinia xanthonoids is demonstrated. These readily accessible tricyclic scaffolds also provide ready entry into a variety of substituted γ-lactones through a photochemical 1,3-acyl shift and decarbonylation.