Biosynthesis of (+)-,(-)- and (±)-tetrahydropalmatines

Specific incorporation of didehydroreticuline and reticuline into (±)- (+)-, and (-)-tetrahydropalmatines in Cocculus laurifolius and of (R)- and (S)-reticulines into (R)- and (S)-tetrahydropalmatines respectively has been demonstrated. Feeding of[l-³H, 4'-methoxy-¹⁴C]reticuline suggested that reticuline was not converted in the plants into didehydroreticuline and racemisation of optically active forms of tetrahydropalmatine did not take place via dehydrotetrahydropalmatine     

Biosynthesis of tetrahydropalmatine and palmatine

The incorporation of (±)-norlaudanosoline, norprotosinomenine, nororientaline, norlaudanidine, reticuline and laudanosine into tetrahydropalmatine and palmatine has been studied, and specific utilization of reticuline demonstrated. Feeding of (±)-[N-methyl-¹⁴C] reticuline showed that C atom 8 of tetrahydropalmatine and palmatine are formed by oxidative cyclisation of the N-Me group of reticuline. Parallel experiments with (R)-; and (S)-, reticulines demonstrated specific incorporation of (R)- isomer into these bases. Feeding experiments also revealed that the plants can convert tetrahydropalmatine into palmatine with high efficiency.     

Inequalities for a polynomial and its derivative

Let , 1?μ?n, be a polynomial of degree n such that p(z)≠0 in |z|<k, k>0, then for 0<r?R?k, Dewan, Yadav and Pukhta [K.K. Dewan, R.S. Yadav, M.S. Pukhta, Inequalities for a polynomial and its derivative, Math. Inequal. Appl. 2 (2) (1999) 203-205] proved

     

Unambiguous Stereochemical Assignment of Cyclo(Phe-Pro), Cyclo(Leu-Pro), and Cyclo(Val-Pro) by Electronic Circular Dichroic Spectroscopy

2,5-diketopiperazines (DKPs) are cyclic dipeptides ubiquitously found in nature. In particular, cyclo(Phe-Pro), cyclo(Leu-Pro), and cyclo(Val-Pro) are frequently detected in many microbial cultures. Each of these DKPs has four possible stereoisomers due to the presence of two chirality centers. However, absolute configurations of natural DKPs are often ambiguous due to the lack of a simple, sensitive, and reproducible method for stereochemical assignment. This is an important problem because stereochemistry is a key determinant of biological activity. Here, we report a synthetic DKP library containing all stereoisomers of cyclo(Phe-Pro), cyclo(Leu-Pro), and cyclo(Val-Pro). The library was subjected to spectroscopic characterization using mass spectrometry, NMR, and electronic circular dichroism (ECD). It turned out that ECD can clearly differentiate DKP stereoisomers. Thus, our ECD dataset can serve as a reference for unambiguous stereochemical assignment of cyclo(Phe-Pro), cyclo(Leu-Pro), and cyclo(Val-Pro) samples from natural sources. The DKP library was also subjected to a biological screening using assays for E. coli growth and biofilm formation, which revealed distinct biological effects of cyclo(D-Phe-L-Pro).     

Synthesis of zinc oxide porous structures by anodization with water as an electrolyte

We report a simple, reliable and one-step method of synthesizing ZnO porous structures at room temperature by anodization of zinc (Zn) sheet with water as an electrolyte and graphite as a counter electrode. We observed that the de-ionized (DI) water used in the experiment is slightly acidic (pH=5.8), which is due to the dissolution of carbon dioxide from the atmosphere forming carbonic acid. Porous ZnO is characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy and photoluminescence (PL) studies. The current-transient measurement is carried out using a Gamry Instruments Reference 3000 and the thickness of the deposited films is measured using a Dektak surface profilometer. The PL, Raman and X-ray photoelectron spectroscopy are used to confirm the presence of ZnO phase. We have demonstrated that the hybrid structures of ZnO and poly (3,4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS) exhibit good rectifying characteristics. The evaluated barrier height and the ideality factor are 0.45 eV and 3.6, respectively.     

Ethanol oxidation by imidorhenium(V) complexes: formation of amidorhenium(III) complexes

The reaction of Re(NC6H4R)Cl3(PPh3)2 (R = H, 4-Cl, 4-OMe) with 1,2-bis(diphenylphosphino)ethane (dppe) is investigated in refluxing ethanol. The reaction produces two major products, Re(NC6H4R)Cl(dppe)(2)2+ (R = H, 1-H; R = Cl, 1-Cl; R = OMe, 1-OMe) and the rhenium(III) species Re(NHC6H4R)Cl(dppe)2+ (R = H, 2-H; R = Cl, 2-Cl). Complexes 1-H (orthorhombic, Pcab, a = 22.3075(10) A, b = 23.1271(10) A, c = 23.3584(10) A, Z = 8), 1-Cl (triclinic, P1, a = 11.9403(6) A, b = 14.6673(8) A, c = 17.2664(9) A, alpha = 92.019(1) degrees, beta = 97.379(1) degrees, gamma = 90.134(1) degrees, Z = 2), and 1-OMe (triclinic, P1, a = 11.340(3) A, b = 13.134(4) A, c = 13.3796(25) A, alpha = 102.370(20) degrees, beta = 107.688(17) degrees, gamma = 114.408(20) degrees, Z = 1) are crystallographically characterized and show an average Re-N bond length (1.71 A) typical of imidorhenium(V) complexes. There is a small systematic decrease in the Re-N bond length on going from Cl to H to OMe. Complex 2-Cl (monoclinic, Cc, a = 24.2381(11) A, b = 13.4504(6) A, c = 17.466(8) A, beta = 97.06900(0) degrees, Z = 4) is also crystallographically characterized and shows a Re-N bond length (1.98 A) suggestive of amidorhenium(III). The rhenium(III) complexes exhibit unusual proton NMR spectra where all of the resonances are found at expected locations except those for the amido protons, which are at 37.8 ppm for 2-Cl and 37.3 ppm for 1-H. The phosphorus resonances are also unremarkable, but the 13C spectrum of 2-Cl shows a significantly shifted resonance at 177.3 ppm, which is assigned to the ipso carbon of the phenylamido ligand. The extraordinary shifts of the amido hydrogen and ipso carbon are attributed to second-order magnetism that is strongly focused along the axially compressed amido axis. The reducing equivalents for the formation of the Re(III) product are provided by oxidation of the ethanol solvent, which produces acetal and acetaldehyde in amounts as much as 30 equiv based on the quantity of rhenium starting material. Equal amounts of hydrogen gas are produced, suggesting that the catalyzed reaction is the dehydrogenation of ethanol to produce acetaldehyde and hydrogen gas. Metal hydrides are detected in the reaction solution, suggesting a mechanism involving beta-elimination of ethanol at the metal center. Formation of the amidorhenium(III) product possibly arises from migration of a metal hydride in the imidorhenium(V) complex.     

Simulation of non-Newtonian ink transfer between two separating plates for gravure-offset printing

The inks used in gravure-offset printing are non-Newtonian fluids with higher viscosities and lower surface tensions compared to Newtonian fluids. This paper examines the transfer of a non-Newtonian ink between two parallel plates when the top plate is moved upward with a constant velocity while the bottom plate is held fixed. Numerical simulations were carried out using the Carreau model to explore the behavior of a non-Newtonian ink in gravure-offset printing. The volume of fluid (VOF) model was adopted to demonstrate the stretching and break-up behaviors of the ink. The results indicate that the ink transfer ratio is greatly influenced by the contact angle, especially the contact angle at the upper plate (α). For lower values of α, oscillatory or unstable behavior of the position of minimum thickness of the ink between the two parallel plates during the stretching period is observed. This oscillation gradually diminishes as the contact angle at the upper plate is increased. Moreover, the number of satellite droplets increases as the velocity of the upper plate is increased. The surface tension of the conductive ink shows a positive impact on the ink transfer ratio to the upper plate. Indeed, the velocity of the upper plate has a significant influence on the ink transfer in gravure-offset printing when the Capillary number (Ca) is greater than 1 and the surface tension dominates over the ink transfer process when Ca is less than 1.