3‐Methyl 5‐isopropyl 2‐methoxy­imino­methyl‐6‐methyl‐4‐(3‐nitro­phenyl)‐1,4‐di­hydro­pyridine‐3,5‐di­carboxyl­ate

The crystal structure of the title compound, C₂₀H₂₃N₃O₇, consists of relatively isolated mol­ecules. The substituted 1,4‐di­hydro­pyridine ring adopts a flattened boat conformation. Both ester groups, at positions 3 and 5, have cis,cis geometry. The phenyl ring is nearly planar and is approximately perpendicular to the 1,4‐di­hydro­pyridine ring (dihedral angle 87.70°).     

Application of a novel linear/exponential hybrid force field scaling scheme to the longitudinal Raman active mode of polyyne

The properties of an infinite carbon chain (polyyne), an allotropic form of elemental carbon, are of importance in materials science as well as astronomy. The Raman active longitudinal optical (LO) frequencies are calculated with first-principles methods for oligoynes and polyyne and compared with experiments. Since traditional force constant scaling schemes fail in this case, we introduced a linear/exponential scaling scheme based on the exponential behavior of the carbon-carbon bond stretching force constant couplings in quasi-one-dimensional conjugated chains. The LO Raman active frequency is predicted at 1870-1877 cm-1. Our results provides further evidence for the assignment of the characteristic Raman peaks near 1850 cm-1 of the recently discovered long linear carbon chains encapsulated inside multiwalled or double-walled carbon nanotubes.     

Synthesis of readily cleavable immobilized 1,10-phenanthroline resins

1,10-Phenanthroline is derivatized and ultimately immobilized on two different polystyrene/divinylbenzene solid supports using convenient methodology. All syntheses are amenable to semiautomatic processing and are scalable for high-throughput screening. A domino copper-catalyzed coupling-cyclization reaction is used to illustrate applicability in catalytic studies.     

Extraction products from <Emphasis Type="Italic">Miscanthus</Emphasis> var. ‘Soranovskii’

The chemical structures of Miscanthus var. ‘Soranovskii’ lignin fractions released via extraction of lignin from the lignocellulosic feedstock using moderately heated acetone under atmospheric pressure, without acidic and alkaline catalysts, were studied. A blend of Miscanthus stems and leaves was pretreated with water under thermobaric conditions. The acetone organosolv process subsequently afforded a substance related to a lignin-like matter-acetone organosolv Miscanthus lignin (AOML). Non-destructive analytical techniques such as FTIR spectroscopy, gas chromatography-mass spectrometry, size-exclusion chromatography, and 2D NMR were used. The IR and NMR spectroscopies revealed the AOML structure to comprise all the three major types of phenylpropane units: guaiacyl (G), syringyl (S), and p-hydroxyphenyl (H). The resultant acetone-organosolv lignin exhibits good solubility in polar solvents, moderate solubility in aromatic chemicals, and is insoluble in non-polar solvents, exhibiting the physicochemical properties of a thermoplastic polymer with a softening point of 67.0°C (onset 33.0°C, endset 81.5°C).     

Synthesis of Nature‐Inspired Medium‐Sized Fused Heterocycles from Amino Acids

Herein, we describe the synthesis of molecular scaffolds consisting of medium‐sized fused heterocycles using amino acids, which are some of the most useful building blocks used by nature as well as chemists to create structural diversity. The acyclic precursors were assembled by using traditional Merrifield solid‐phase peptide synthesis, and cyclization was carried out through acid‐mediated tandem endocyclic N‐acyliminium ion formation, followed by nucleophilic addition with internal nucleophiles. The synthesis of molecular scaffolds consisting of seven‐, eight‐, and nine‐membered rings proceeded with full stereocontrol of the newly generated stereogenic center in most cases.     

Effect of UV irradiation on detection of cocaine hydrochloride and crack vapors by IMIS and API-MS methods

Detection of drug vapors and volatile products of their decomposition is an important, and sometimes the only way to determine the presence of illegal drug traces at the surface of mail items, documents, hands and banknotes. This paper gives the results of experimental studies on the effect of UV irradiation on the sensitivity of a vapor phase detection of cocaine of different origin by a technology of ion mobility increment spectrometry (IMIS). It is shown that the influence of UV irradiation on the surface of cocaine hydrochloride and crack increases the amplitude of IMIS signals by about eight times. We analyzed ions emerged by photolysis of tested cocaine samples using mass-spectrometry with atmospheric pressure ionization (API-MS). The assumption is made about structural formula of volatile products of photolysis of crack and cocaine hydrochloride. By the results of API-MS and IMIS studies on photolysis of cocaine samples it is assumed that compound C₁₀H₁₅NO₃ with a molecular weight of 197 amu and ecgonidine methyl ester with a molecular weight of 181 amu are responsible for the increase of an amplitude of IMIS signals upon UV irradiation of samples of crack and cocaine hydrochloride.     

Design, preparation, X-ray crystal structure, and reactivity of o-alkoxyphenyliodonium bis(methoxycarbonyl)methanide, a highly soluble carbene precursor

The preparation, X-ray structure, and reactivity of new, highly soluble, and reactive iodonium ylides derived from malonate methyl ester and bearing an ortho substituent on the phenyl ring are reported. These new reagents show higher reactivity than common phenyliodonium ylides in the Rh-catalyzed cyclopropanation, C-H insertion, and transylidation reactions under homogeneous conditions.     

Efficient Access to Deuterated and Tritiated Nucleobase Pharmaceuticals and Oligonucleotides using Hydrogen‐Isotope Exchange

A general approach for the efficient hydrogen‐isotope exchange of nucleobase derivatives is described. Catalyzed by ruthenium nanoparticles, using mild reaction conditions, and involving either D₂ or T₂ as isotopic sources, this reaction possesses a wide substrate scope and a high solvent tolerability. This novel method facilitates the access to essential diagnostic tools in drug discovery and development: tritiated pharmaceuticals with high specific activities and deuterated oligonucleotides suitable for use as internal standards during LC‐MS quantification.     

DNA Interaction with 17α‐Ethinylestradiol Studied Using Electrochemical Biosensors and Biosensing in Solution

The synthetic estrogen 17α‐ethinylestradiol (EE2) is an active component of oral contraceptives. It is considered as an endocrine disrupting compound that, once incorporated into an organism, affects the hormonal balance of animals and humans. In this study we characterized the DNA‐EE2 interaction using an electrochemical biosensor and biosensing in solution phase with the double stranded DNA from salmon sperm and deoxyguanosine monophosphate (dGMP). Differential pulse voltammetry method has been applied based on voltammetric anodic responses of the deoxyguanine (dGuo) and deoxyadenine (dAdo) as well as EE2 in the medium of phosphate buffer solution pH 7.0. Binding of EE2 to the nucleobases leads to a decrease of their anodic signals. Association constant for DNA‐EE2 interaction has been estimated to be about 1.1 ? 10³ L mol^?1 and 1.4 ? 10³ L mol^?1 for dGuo and dAdo responses, respectively. The association is reversible as indicated by decrease of the EE2 response in pure buffer solution due to leaching of EE2 from the surface attached DNA. The DNA‐EE2 association has been confirmed also by UV‐vis spectrometric experiments.     

Nonequilibrium molecular transport photoinduced by potential energy fluctuations

The mechanism of directed substrate-parallel motion of molecules caused by photoinduced potential energy fluctuations is investigated. Unlike simplistic models (e.g., an on-off ratchet), the approach suggested implies that the necessary asymmetry of the potential energy can arise not only from the asymmetry of the substrate potential but also from an asymmetric distribution of the fluctuating charge density in the molecule. The thus induced asymmetry of the potential energy governs the direction motion and enables, under certain conditions, its reversal at some frequencies of resonant laser pulses or temperature. These inferences are exemplified by the model charge distributions in the molecule and substrate, and the charge density fluctuations which are obtained by quantum chemical calculations for the realistic molecule of a substituted phenylpyrene compound on a model substrate.