Synthesis of (r)- and (s)-1-formyl-6,7,8,9-tetrahydro- N,N-(dipropyl)-3H-benz[e]indol-8-amines: Potent and orally active 5-ht1a receptor agonists

An efficient synthesis of the potent and orally active 5-HT_1A agonists, (R)-(+)- and (S)-(-)-1-formyl-6,7,8,9-tetrahydro-N,N-dipropyl-3H-benz[e]indol-8-amines 1a and 1b , is described. This synthesis was accomplished in twelve steps from commercially available 1,5,6,7-tetrahydro-4H-indol-4-one ( 5 ). The key step involved a regio-controlled Friedel-Crafts acylation of 1-(p-toluenesulfonyl)indol-4-acetyl chloride with ethylene to yield a versatile synthon, 3-(p-toluenesulfonyl)-6,7,8,9-tetrahydro-3H-benz[e]indol-8-one ( 10 ). Subsequent coupling of this ketone with chiral α-methylbenzylamine under reductive amination conditions yielded a mixture of diastereomers. These diastereomers were efficiently separated by either chromatography or fractional recrystallization of the derived hydrochloride salts. Debenzylation of the pure diastereomers was followed by alkylation and formylation to yield (R)-(+)- and (S)-(-)-enantiomers 1a and 1b with >99% purity.     

Predictive control of uncertain nonlinear parabolic PDE systems using a Galerkin/neural-network-based model

In this paper, a model predictive control (MPC) scheme for a class of parabolic partial differential equation (PDE) systems with unknown nonlinearities, arising in the context of transport-reaction processes, is proposed. A spatial operator of a parabolic PDE system is characterized by a spectrum that can be partitioned into a finite slow and an infinite fast complement. In this view, first, Galerkin method is used to derive a set of finite dimensional slow ordinary differential equation (ODE) system that captures the dominant dynamics of the initial PDE system. Then, a Multilayer Neural Network (MNN) is employed to parameterize the unknown nonlinearities in the resulting finite dimensional ODE model. Finally, a Galerkin/neural-network-based ODE model is used to predict future states in the MPC algorithm. The proposed controller is applied to stabilize an unstable steady-state of the temperature profile of a catalytic rod subject to input and state constraints.     

Heck coupling reaction using monomeric ortho‐palladated complex of 4‐methoxy‐ benzoylmethylenetriphenylphosphorane under microwave irradiation

The activity of [Pd(C₆H₄CH₂ NH₂‐κ²‐C‐N)PPh₃MOBPPY]OTf complex, A (MOBPPY = 4‐methoxybenzoylmethylenetriphenyl‐ phosphoraneylide), was investigated in the Heck–Mizoroki C? C cross‐coupling reaction under conventional heating and microwave irradiation conditions. The complex is an active and efficient catalyst for the Heck reaction of aryl halides. The yields were excellent using a catalytic amount of [Pd(C₆H₄CH₂ NH₂‐κ²‐C‐N)PPh₃MOBPPY]OTf complex in N‐methyl‐2‐pyrrolidinone (NMP) at 130 °C and 600 W. In comparison to conventional heating conditions, the reactions under microwave irradiation gave higher yields in shorter reaction times. Copyright © 2010 European Peptide Society and John Wiley & Sons, Ltd.     

Periodogram analysis with missing observations

Estimation of the spectral measure, covariance and spectral density functions of a strictly stationaryr- vector valued time series is considered, under the assumption that some of the observations are missed. The modified periodograms are calculated using data window. The asymptotic normality is studied.     

Study of ultrafast dynamics of 2-picoline by time-resolved photoelectron imaging

The dynamics of electronically excited states in 2-picoline is studied using femtosecond time-resolved photoelectron imaging spectroscopy. The internal conversion from the S(2) state to the vibrationally excited S(1) state is observed in real time. The secondarily populated high vibronic S(1) state deactivates further to the S(0) state. Photoelectron energy and angular distributions reveal the feature of ionization from the singlet 3p Rydberg states. In addition, variation of time-dependent anisotropy parameters indicates the rotational coherence of the molecule.     

Density functional investigation of the interaction of acetone with small gold clusters

The structural evolution of Au(n) (n=2, 3, 5, 7, 9, and 13) clusters and the adsorption of organic molecules such as acetone, acetaldehyde, and diethyl ketone on these clusters are studied using a density functional method. The detailed study of the adsorption of acetone on the Au(n) clusters reveals two main points. (1) The acetone molecule interacts with one gold atom of the gold clusters via the carbonyl oxygen. (2) This interaction is mediated through back donation mainly from the spd-hybridized orbitals of the interacting gold atom to the oxygen atom of the acetone molecule. In addition, a hydrogen bond is observed between a hydrogen atom of the methyl group and another gold atom (not involved in the bonding with carbonyl oxygen). Interestingly, the authors notice that the geometries of Au(9) and Au(13) undergo a significant flattening due to the adsorption of an acetone molecule. They have also investigated the role of the alkyl chain attached to the carbonyl group in the adsorption process by analyzing the interaction of Au(13) with acetaldehyde and diethyl ketone.     

Photodissociation of iodocyclohexane at 266 and 277 nm: Energy partitioning and curve crossing analysis

The photodissociation dynamics of iodocyclohexane (C₆H₁₁I) at 266 and 277 nm has been investigated by ion velocity imaging technique. The velocity distributions, angular distributions and relative quantum yields are obtained for I (²P_3/2) (denoted I) and I (²P_1/2) (denoted I*) fragments. The energy partitioning shows that about 70% of the available energy goes into the internal excitation of the photofragments for both dissociation channels. From the angular distributions, we found the value of the anisotropy parameter β for I* at the corresponding excitation wavelength was less than that for I. Based on the measured angular distributions and relative quantum yields, the relative fractions of each excited state to the products are determined. The curve crossing probabilities between the ³Q₀ and ¹Q₁ states are determined 0.503 at 266 nm and 0.443 at 277 nm.     

Chemoenzymatic Hydrogen Production from Methanol through the Interplay of Metal Complexes and Biocatalysts

Microbial methylotrophic organisms can serve as great inspiration in the development of biomimetic strategies for the dehydrogenative conversion of C₁ molecules under ambient conditions. In this Concept article, a concise personal perspective on the recent advancements in the field of biomimetic catalytic models for methanol and formaldehyde conversion, in the presence and absence of enzymes and co-factors, towards the formation of hydrogen under ambient conditions is given. In particular, formaldehyde dehydrogenase mimics have been introduced in stand-alone C₁-interconversion networks. Recently, coupled systems with alcohol oxidase and dehydrogenase enzymes have been also developed for in situ formation and decomposition of formaldehyde and/or reduced/oxidized nicotinamide adenine dinucleotide (NADH/ NAD⁺). Although C₁ molecules are already used in many industries for hydrogen production, these conceptual bioinspired low-temperature energy conversion processes may lead one day to more efficient energy storage systems enabling renewable and sustainable hydrogen generation for hydrogen fuel cells under ambient conditions using C₁ molecules as fuels for mobile and miniaturized energy storage solutions in which harsh conditions like those in industrial plants are not applicable.     

Purple subphthalocyanine-phthalocyanine dyad: Synthesis,photophysicochemical properties and DFT study

A new phthalocyanine-subphthalocyanine heterodyad ( 5 ) was prepared by Pd(0)-catalyzed Sonogashira coupling reaction between an asymmetrical phthalocyanine ( 3 ) bearing monoiodo and multiple triazolide moieties on its backbone and a subphthalocyanine ( 4 ) bearing axially propargyl group. The structure of this heterodyad ( 5 ) was subsequently confirmed by the conventional spectroscopic techniques. The photophysical and photochemical properties including; fluorescence and singlet oxygen generation of ( 5 ) along with its building chromophores ( 3 ) and ( 4 ) were also investigated. Interestingly, a purple colored solution was observed by this novel dyad which was significantly different from those colors (green or blue) obtained by phthalocyanine-subphthalocyanine conjugates. Based on steady state absorption spectroscopic data and transient absorption results, the synthesized dyad 5 was free of aggregation and there is good energy transfer occurs between Pc and subPc moieties. This result was confirmed using density functional theory (DFT) and time-dependent DFT (TDDFT) analyses: B3LYP exchange-correlation functional and the 6–31 + G(d) basis set.     

A comparative homocoupling reaction of aryl halides using monomeric orthopalladated complex of 4‐methoxybenzoylmethylenetri‐ phenylphosphorane under conventional and microwave irradiation conditions

The activity of [Pd(C₆H₄CH₂NH₂‐κ²‐C‐N)PPh₃MOBPPY]OTf complex, A (MOBPPY = 4‐methoxybenzoylmethylenetriphenylphosphoraneylide) was investigated in the homocoupling reaction of a vast range of aryl halides under both conventional and microwave irradiation conditions and their results were compared. The complex was active and showed high efficiency in the formation of new C‐C bonds. The yields were excellent using a catalytic amount of [Pd(C₆H₄CH₂NH₂‐κ²‐C‐N)PPh₃MOBPPY]OTf complex in N, N‐dimethylformamide at 120 °C. In comparison to conventional heating conditions, the reactions under microwave irradiation gave higher yields in shorter reaction times. Copyright © 2011 John Wiley & Sons, Ltd.