Polarization squeezing in polarized light

It is shown that polarized light can be polarization squeezed only if it exhibits sub-Poissonian statistics with the Mandel's Q factor less than − 1/2.     

1,3-Diynes: A Versatile Precursor in Transition-Metal Catalyzed (Mediated) C−H Functionalizations

Transition metal-catalyzed C−H functionalization of diverse arenes with alkyne units has attracted enormous attention for decades since they provide straightforward access to various functionalization/annulations, which are commonly present in bioactive compounds and natural products. Recently, conjugated alkynes (1,3-diynes) have been utilized as key coupling partner in many C−H activation reactions due to their versatile characteristic properties. The presence of two C≡C bonds in conjugated 1,3-diyne brings the new diversity in synthetic transformations, such as chemo-, regioselective pathways, mono-bis functionalizations, cascade annulations, etc. Herein, we summarized the latest developments in the realm of transition-metal-catalyzed C−H functionalizations of diverse arenes with 1,3-diynes. Moreover, we highlighted the diverse transformations, conditions, mechanisms and applications of the corresponding reaction in detail.     

Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods

The self‐assembled structures of atomically precise, ligand‐protected noble metal nanoclusters leading to encapsulation of plasmonic gold nanorods (GNRs) is presented. Unlike highly sophisticated DNA nanotechnology, this strategically simple hydrogen bonding‐directed self‐assembly of nanoclusters leads to octahedral nanocrystals encapsulating GNRs. Specifically, the p‐mercaptobenzoic acid (pMBA)‐protected atomically precise silver nanocluster, Na₄[Ag₄₄(pMBA)₃₀], and pMBA‐functionalized GNRs were used. High‐resolution transmission and scanning transmission electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly of silver nanoclusters via H‐bonding, leading to octahedral symmetry. The use of water‐dispersible gold nanoclusters, Au_≈250(pMBA)_n and Au₁₀₂(pMBA)₄₄, also formed layered shells encapsulating GNRs. Such cluster assemblies on colloidal particles are a new category of precision hybrids with diverse possibilities.     

Conformational analysis of 18-azacrown-6 and its bonding with late first transition series divalent metals: insight from DFT combined with NPA and QTAIM analyses

Density functional theory calculations, together with quantum theory of atoms in molecules (QTAIM) analyses, have been performed to investigate 18-azacrown-6 complexes of the high-spin late first transition series divalent metal ions in the gas phase and, in some cases, in aqueous solution simulated by a polarizable continuum model. Six intramolecular H-H bonding interactions in the meso-complexes are found to arise from folding of the ligand upon its electrostatic interaction with the metal ions, which are largely absent in the lowest-energy C(2h) conformer of the free ligand. The ligand-to-metal charge transfer obtained from QTAIM analysis, among other things, is found to be an important factor that controls the stability of these complexes. The inter-relationship between the ligand preorganization energy, the zero-point corrected formation energy of the metal complexes, and the H-H bonding pair distances, as well as the dependence of the electron density and the total energy density at the H-H bond critical points on the H-H bonding pair distances, provides a physical basis for understanding and explaining the stabilizing nature of these closed-shell interactions, which are often viewed as steric clashes that lead to complex destabilization.     

Temperature-Dependent Dielectric Relaxation of 2-Ethoxyethanol, Ethanol, and 1-Propanol in Dimethylformamide Solution Using the Time-Domain Technique

Complex reflection coefficients for 2-ethoxyethanol–dimethylformamide (DMF), ethanol–DMF, and 1-propanol–DMF mixtures at several temperatures from 20 to 50° and the frequency range 10 MHz to 10 GHz were determined by time-domain spectroscopy in reflection mode. Fourier transforms and least-squares fitting were used to obtain complex permittivity, static dielectric constant, and relaxation time. The excess dielectric parameters, Kirkwood correlation factors, and thermodynamic properties for the binary mixtures were also determined. The static dielectric constant for the mixtures was fitted well with the modified Bruggeman model.     

Formation of bifunctional cross-linked products due to reaction of NAMI-A with DNA bases – a DFT study

Structural Chemistry - It is reported that NAMI-A and other Ru-anticancer complexes preferably bind with the N7 site of guanine and can also form DNA inter-strand cross-links. Therefore, in order...     

Easy and Efficient Microwave-Assisted Synthesis of 1,2,3-Triazolyl-Tethered 2-Pyridinylbenzimidiazoles and Their Antimicrobial Activity

Russian Journal of Organic Chemistry - A series of novel 1,2,3-triazole-tethered 2-pyridinylbenzimidazole derivatives have been synthesized form 2-(pyridine-3-yl)benzimidazole under microwave...     

HPLC–PDA identification and resolution of rufinamide forced degradation impurities: A congregated chemometric expedite optimization coupled with factorials and desirability

Rufinamide is used presently to treat Lenaux–Gastaut syndrome. A full factorial design and desirability approach was investigated for the optimization of hydrolytic stress via response surface curves (RSCs). The degradation impurities were identified and resolved using reversed-phase high-performance liquid chromatography (RP-HPLC) on the Qualisil® BDS C₈ column. Acetonitrile–water (29:71, v/v) was optimized for the mobile phase and used at a flow rate of 1.0 ml/min with detection at a wavelength of 230 nm. Rufinamide showed appreciable susceptibility to hydrolysis under acidic and alkaline stress, and substantial degradation in the neutral condition. It degraded much less under oxidative stress. Exposure towards thermal and photolytic stress conditions indicated appreciable stability. The developed method was subjected to validation as per the recommendations of the International Conference on Harmonization. The proposed method showed no influence from the excipients and the degradation products. As well as good precision and accuracy in determination, the method showed a linear response between 2 and 12 μg ml⁻¹. The method was extended for determination in a human plasma sample, which resulted in excellent recovery without interference from matrix effects. The combined use of desirability and design for the optimization of acidic and alkaline hydrolytic stress led to simple and rapid analysis.     

Hetero-Polar Sextuple Bond: A Relativistic Quantum Chemical Study**

Number of bonds formed by sharing an electron pair between two atoms is not restricted to one, it can go beyond four and six is the maximum. While homopolar sextuple bond in Mo₂ and W₂ has been reported, such a high bond order in heteropolar diatomics has remained elusive. In the pursuit of the sextuple bond in polar diatomics, the present study depicts the existence of such multiple bonds in Rhodium-Scandium hetero-diatom based on relativistic quantum chemical calculations. The bonding comprises of three normal electron sharing covalent bonds and three dative covalent bonds.