Eye‐safe UV stand‐off Raman spectroscopy for the ranged detection of explosives in the field

Increasing worldwide terrorist attacks involving explosives presents a growing need for a rapid and ranged explosive detection method that can safely be deployed in the field. Stand‐off Raman spectroscopy shows great promise; however, the radiant exposures of lasers required for adequate signal generation are often much greater than what is safe for the eye or the skin, restricting use of the technique to unpopulated areas. Here, by determining the safe exposure levels for lasers typically used in Raman spectroscopy, optimal parameter values are identified, which produce the largest possible detection range using power densities that do not exceed the eye‐safe limit. It is shown that safe ultraviolet pulse energies can be more than three orders of magnitude greater than equivalent safe visible pulse energies. Coupling this to the 16‐fold increase in Raman signal obtained in the ultraviolet at 266 nm over that at 532 nm results in a 131 times larger detection range for the eye‐safe 266‐nm system over an equivalent eye‐safe 532‐nm laser system. For the Raman system described here, this translates to a maximum range of 42 m for detecting Teflon with a 266‐nm laser emitting a 100‐mm diameter beam of 23.5‐mJ nanosecond pulses. Copyright © 2015 John Wiley & Sons, Ltd.     

Uncovering the Neglected Similarities of Arynes and Donor–Acceptor Cyclopropanes

Arynes and donor–acceptor (D–A) cyclopropanes are two classes of strained systems having the potential for numerous applications in organic synthesis. The last two decades have witnessed a renaissance of interest in the chemistry of these species primarily because of the mild and robust methods for their generation or activation. Commonly, arynes as easily polarizable systems result in 1,2‐disubstitution, whereas D‐A cyclopropanes as polarized systems lead to 1,3‐bisfunctionalization thereby showing striking similarities. Transformations with 1,2‐ and 1,3‐dipoles afford cyclic structures. With arynes, emerging four‐membered rings as intermediates might react further, whereas the analogous five‐membered rings obtained from D–A cyclopropanes are most often the final products. However, there are a few cases where these intermediates behave surprisingly differently. This Minireview highlights the parallels in reactivity between arynes and D–A cyclopropanes thereby shedding light on the neglected similarities of these two reactive species.     

Anti-inflammatory and anticancer activities of erythrodiol-3-acetate and 2,4-di-tert-butylphenol isolated from Humboldtia unijuga

Abstract

Humboldtia unijuga Bedd., endemic to Agasthyamala in Western Ghats in India, is traditionally used by local Kani tribes for chicken pox, head ache and snake bite. This study reports the isolation of erythrodiol-3-acetate (HU-1) and 2,4-di-tert-butylphenol (HU-2) from H. unijuga roots and their anti-inflammatory and anticancer activities in macrophage, skin and breast cancer cell lines. Effects of HU-1 and HU-2 treatments (50, 100?µg/mL) on gene expression profiles of pro-inflammatory cytokines TNFα, IL-6 and IL-1β, and apoptosis genes p53 and caspase 7 were studied. HU-2 exerted a significantly superior anti-inflammatory effect compared to HU-1 in all three pro-inflammatory genes. HU-2 showed a superior dose dependent anticancer effect through activation of p53 gene over HU-1 in MCF-7 cells. HU-1 exhibited a dose dependent effect on caspase 7 gene in both cell lines while HU-2 was more effective in A431. HU-2 has potential for development as a novel anti-inflammatory and anticancer agent.     

Photochemical Deoxygenative Hydroalkylation of Unactivated Alkenes Promoted by a Nucleophilic Organocatalyst

The direct utilization of simple and abundant feedstocks in carbon-carbon bond-forming reactions to embellish sp³-enriched chemical space is highly desirable. Herein, we report a novel photochemical deoxygenative hydroalkylation of unactivated alkenes with readily available carboxylic acid derivatives. The reaction displays broad functional group tolerance, accommodating carboxylic acid-, alcohol-, ester-, ketone-, amide-, silane-, and boronic ester groups, as well as nitrile-containing substrates. The reaction is operationally simple, mild, and water-tolerant, and can be carried out on multigram-scale, which highlights the utility of the method to prepare value-added compounds in a practical and scalable manner. The synthetic application of the developed method is further exemplified through the synthesis of suberanilic acid, a precursor of vorinostat, a drug used for the treatment of cutaneous T-cell lymphoma. A novel mechanistic approach was identified using thiol as a nucleophilic catalyst, which forms a key intermediate for this transformation. Furthermore, electrochemical studies, quantum yield, and mechanistic experiments were conducted to support a proposed catalytic cycle for the transformation.     

Working group report: Low energy and flavour physics

This is a report of the low energy and flavour physics working group at WHEPP-8, held at the Indian Institute of Technology, Mumbai, India, during 5–16 January 2004.     

Lewis Acid Catalyzed Selective Reactions of Donor–Acceptor Cyclopropanes with 2‐Naphthols

Lewis acid‐catalyzed reactions of 2‐substituted cyclopropane 1,1‐dicarboxylates with 2‐naphthols is reported. The reaction exhibits tunable selectivity depending on the nature of Lewis acid employed and proceed as a dearomatization/rearomatization sequence. With Bi(OTf)₃ as the Lewis acid, a highly selective dehydrative [3+2] cyclopentannulation takes place leading to the formation of naphthalene‐fused cyclopentanes. Interestingly, engaging Sc(OTf)₃ as the Lewis acid, a Friedel–Crafts‐type addition of 2‐naphthols to cyclopropanes takes place, thus affording functionalized 2‐naphthols. Both reactions furnished the target products in high regioselectivity and moderate to high yields.     

Carbon–Nitrogen Bond‐Forming Reactions of Dialkyl Azodicarboxylate: A Promising Synthetic Strategy

Azodicarboxylates have found applications in electrophilic amination reactions and in pericyclic reactions. The nucleophilic trigger in Mitsunobu reactions, that is, the zwitterion formed from triphenylphosphine and dialkyl azodicarboxylate, has been utilized recently in various heterocyclic constructions. This Focus Review summarizes the potential utility of azodicarboxylates in various carbon–nitrogen bond‐forming reactions.     

Directing Group-Free Regioselective meta-C−H Functionalization of Pyridines

The pyridine core is among the most common motifs found in pharmaceuticals and agrochemicals. Consequently, the C−H functionalization of pyridine is a prized reaction, as it can help access a broad spectrum of valuable chemicals. However, the intrinsic electronic properties of pyridines hinder their meta-C−H functionalization, requiring drastic conditions affecting functional group compatibility. A synthetic manoeuvre to overcome this challenge involves the temporary conversion of pyridines into electron-rich intermediates and subsequent regioselective electrophilic functionalization. This was recently accomplished by a ring-opening ring-closing sequence via Zincke imine intermediates by McNally and co-workers, and a dearomatization-rearomatization sequence via oxazino-pyridine intermediates by the Studer group. The mildness and simplicity of these protocols enable them to work with complex molecular setups for synthesizing natural products and bioactive molecules.     

Halide Perovskite Single Crystals and Nanocrystal Films as Electron Donor-Acceptor Heterojunctions

Halide perovskites are materials for future optical displays and solar cells. Electron donor-acceptor perovskite heterostructures with distinguishing halide compositions are promising for transporting and harvesting photogenerated charge carriers. Combined e-beam lithography and anion exchange are promising to develop such heterostructures but challenging to prepare multiple heterojunctions at desired locations in single crystals. We demonstrate swift laser trapping-assisted band gap engineering at the desired locations in MAPbBr₃ microrods, microplates, or nanocrystal thin films. The built-in donor-acceptor double and multi-heterojunction structures let us transport and trap photogenerated charge carriers from wide-band gap bromide to narrow-band gap iodide domains. We discuss the charge carrier transport and trapping mechanisms from the viewpoints of engineered bands and band continuity. This work offers a convenient method for designing single-, double- and multi-heterojunction donor-acceptor halide perovskites for photovoltaic, photonic, and electronic applications.     

One-, two-, and three-dimensional arrays of Eu3+-4,4,5,5,5-pentafluoro-1-(naphthalen-2-yl)pentane-1,3-dione complexes: synthesis, crystal structure and photophysical properties

A novel beta-diketone, 4,4,5,5,5-pentafluoro-1-(naphthalen-2-yl)pentane-1,3-dione (HPFNP), which contains polyfluorinated alkyl group, as well as the long conjugated naphthyl group, has been used for the synthesis of a series of new tris(beta-diketonate)europium(III) complexes of the general formula Eu(PFNP)3 x L [where L = H2O, 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 4,7-diphenyl-1,10-phenanthroline (bath)] and characterized by various spectroscopic techniques. The single-crystal X-ray diffraction analysis of Eu(PFNP) 3.bpy revealed that the complex is mononuclear, the central Eu(3+) ion is coordinated by six oxygen atoms furnished by three beta-diketonate ligands, and two nitrogen atoms from a bidentate bipyridyl ligand, in an overall distorted square prismatic geometry. Further, analysis of the X-ray crystal data of the above complex also revealed interesting 1D, 2D, and 3D networks based on intra- and intermolecular hydrogen bonds. The room-temperature PL spectra of the complexes are composed of typical Eu(3+) red emissions, assigned to transitions between the first excited state ((5)D0) and the multiplet ((7)F(0-4)). The results demonstrate that the substitution of solvent molecules by bidentate nitrogen ligands in Eu(PFNP)3 x H2O x EtOH greatly enhances the quantum yields and lifetime values.