LC-ESI-MS/MS profiling of alkaloids and antiproliferative activity of Pachypoduim lamerei drake leaves

Abstract

In the present study, evaluation of the antiproliferative activity of Pachypodium lamerei Drake leaves (family Apocyaceae) against human breast cancer cell lines MDA-MB-231 was done for the total methanolic extract, crude alkaloidal mixture and ursolic acid using the MTT colorimetric assay. The methanolic extract showed the strongest antiproliferative activity followed by ursolic acid and crude alkaloidal fraction with an IC₅₀ equal to 6.2, 14.55 and 56.3?µg/ml respectively compared to oleocanthal. It is the first record for the LC/ESI-MS/MS alkaloidal profiling of the leaves of P. lamerei. Seven alkaloids were tentatively identified according to their fragmentation patterns. Four alkaloids were related to the parent indole class and two alkaloids belong to the quinoline class in addition to one steroidal alkaloid with a pregnan nucleus. Phytochemical investigation of the methanolic extract led to the isolation of three triterpenoidal compounds including ursolic acid, 11,12-didehydroursolic acid lactone and ursolic acid lactone.     

A Deadly Organometallic Luminescent Probe: Anticancer Activity of a ReI Bisquinoline Complex

The photophysical properties of [Re(CO)₃(L ‐N₃)]Br (L ‐N₃=2‐azido‐N,N‐bis[(quinolin‐2‐yl)methyl]ethanamine), which could not be localized in cancer cells by fluorescence microscopy, have been revisited in order to evaluate its use as a luminescent probe in a biological environment. The Re^I complex displays concentration‐dependent residual fluorescence besides the expected phosphorescence, and the nature of the emitting excited states have been evaluated by DFT and time‐dependent (TD) DFT methods. The results show that fluorescence occurs from a ¹LC/MLCT state, whereas phosphorescence mainly stems from a ³LC state, in contrast to previous assignments. We found that our luminescent probe, [Re(CO)₃(L ‐N₃)]Br, exhibits an interesting cytotoxic activity in the low micromolar range in various cancer cell lines. Several biochemical assays were performed to unveil the cytotoxic mechanism of the organometallic Re^I bisquinoline complex. [Re(CO)₃(L ‐N₃)]Br was found to be stable in human plasma indicating that [Re(CO)₃(L ‐N₃)]Br itself and not a decomposition product is responsible for the observed cytotoxicity. Addition of [Re(CO)₃(L ‐N₃)]Br to MCF‐7 breast cancer cells grown on a biosensor chip micro‐bioreactor immediately led to reduced cellular respiration and increased glycolysis, indicating a large shift in cellular metabolism and inhibition of mitochondrial activity. Further analysis of respiration of isolated mitochondria clearly showed that mitochondrial respiratory activity was a direct target of [Re(CO)₃(L ‐N₃)]Br and involved two modes of action, namely increased respiration at lower concentrations, potentially through increased proton transport through the inner mitochondrial membrane, and efficient blocking of respiration at higher concentrations. Thus, we believe that the direct targeting of mitochondria in cells by [Re(CO)₃(L ‐N₃)]Br is responsible for the anticancer activity.     

Performance of delay‐sensitive traffic in multi‐layered satellite IP networks with on‐board processing capability

In this article, performance of delay‐sensitive traffic in multi‐layered satellite Internet Protocol (IP) networks with on‐board processing (OBP) capability is investigated. With OBP, a satellite can process the received data, and according to the nature of application, it can decide on the transmission properties. First, we present a concise overview of relevant aspects of satellite networks to delay‐sensitive traffic and routing. Then, in order to improve the system performance for delay‐sensitive traffic, specifically Voice over Internet Protocol (VoIP), a novel adaptive routing mechanism in two‐layered satellite network considering the network's real‐time information is introduced and evaluated. Adaptive Routing Protocol for Quality of Service (ARPQ) utilizes OBP and avoids congestion by distributing traffic load between medium‐Earth orbit and low‐Earth orbit layers. We utilize a prioritized queueing policy to satisfy quality‐of‐service (QoS) requirements of delay‐sensitive applications while evading non‐real‐time traffic suffer low performance level. The simulation results verify that multi‐layered satellite networks with OBP capabilities and QoS mechanisms are essential for feasibility of packet‐based high‐quality delay‐sensitive services which are expected to be the vital components of next‐generation communications networks. Copyright © 2007 John Wiley & Sons, Ltd.     

On the two classes of high‐order convergent methods of approximate inverse preconditioners for solving linear systems

Two classes of methods for approximate matrix inversion with convergence orders p =3?2^k +1 (Class 1) and p =5?2^k ?1 (Class 2), k ≥1 an integer, are given based on matrix multiplication and matrix addition. These methods perform less number of matrix multiplications compared to the known hyperpower method or p th‐order method for the same orders and can be used to construct approximate inverse preconditioners for solving linear systems. Convergence, error, and stability analyses of the proposed classes of methods are provided. Theoretical results are justified with numerical results obtained by using the proposed methods of orders p =7,13 from Class 1 and the methods with orders p =9,19 from Class 2 to obtain polynomial preconditioners for preconditioning the biconjugate gradient (BICG) method for solving well‐ and ill‐posed problems. From the literature, methods with orders p =8,16 belonging to a family developed by the effective representation of the p th‐order method for orders p =2^k , k is integer k ≥1, and other recently given high‐order convergent methods of orders p =6,7,8,12 for approximate matrix inversion are also used to construct polynomial preconditioners for preconditioning the BICG method to solve the considered problems. Numerical comparisons are given to show the applicability, stability, and computational complexity of the proposed methods by paying attention to the asymptotic convergence rates. It is shown that the BICG method converges very quickly when applied to solve the preconditioned system. Therefore, the cost of constructing these preconditioners is amortized if the preconditioner is to be reused over several systems of same coefficient matrix with different right sides.     

Enantiomeric Thin-Layer Chromatographic Assay of Escitalopram in Presence of “In-Process Impurities”

JPC – Journal of Planar Chromatography – Modern TLC - A simple, rapid and precise thin-layer chromatographic (TLC) method for analysis of escitalopram oxalate (ESC-OX) (S-enantiomer) in...     

Measurement and comparison of complex impedance of silicon <Emphasis Type="Italic">p-i-n</Emphasis> photodiodes at different temperatures

The dark alternating current (ac) parameters of BPW34 and BPW41 (Vishay-Telefunken) silicon p-i-n photodiodes are measured and compared at different temperatures using the impedance spectroscopy technique. The impedance plots are nearly semicircular and typically distorted on the high frequency side. For BPW41, the distortion apparently arises from one of the two interfaces as expected for a typical p-i-n device. However, for BPW34, the presence of the distortion is attributed to the variation of photodiode capacitance and resistance with measurement frequency. The text was submitted by the authors in English.     

Measurement and comparison of silicon <Emphasis Type="Italic">p-i-n</Emphasis>-photodiodes with ac impedance at different voltages

The dark alternating current (ac) parameters of commercially available silicon p-i-n-photodiodes are measured and compared at room temperature both in forward and reverse bias using the impedance spectroscopy technique. The ac behavior of the photodiodes is found to be almost the same. For bias voltages in the range from −0.8 to 0.0 V, the typical photodiode behaves like a pure capacitor. For higher voltages (V >-0.2 V) the impedance spectra are nearly semicircular and typically distorted on the high frequency side. At 0.2 V the distortion apparently arises from one of the two interfaces. However, at high bias voltages the nature of the distortion is attributed to the variation of photodiode capacitance and resistance with measurement frequency. The text was submitted by the authors in English.     

Palladium(II)‐N‐heterocyclic carbene complexes: synthesis,characterization and catalytic application

N‐Heterocyclic carbenes (NHCs) are of great importance and are powerful ligands for transition metals. A new series of sterically hindered benzimidazole‐based NHC ligands (LHX) ( 2a , 2b , 2c , 2d , 2e , 2f ), silver–NHC complexes ( 3a , 3b , 3c , 3d , 3e , 3f ) and palladium–NHC complexes ( 4a , 4b , 4c , 4d , 4e , 4f ) have been synthesized and characterized using appropriate spectroscopic techniques. Studies have focused on the development of a more efficient catalytic system for the Suzuki coupling reaction of aryl chlorides. Catalytic performance of Pd–NHC complexes and in situ prepared Pd(OAc)₂/LHX catalysts has been investigated for the Suzuki cross‐coupling reaction under mild reaction conditions in aqueous N,N‐dimethylformamide (DMF). These complexes smoothly catalyzed the Suzuki–Miyaura reactions of electron‐rich and electron‐poor aryl chlorides. Copyright © 2014 John Wiley & Sons, Ltd.     

Direct Introduction of an Alkylsulfonamido Group on C-sites of Isomeric Dicarba-closo-dodecaboranes: The Influence of Stereochemistry on Inhibitory Activity against the Cancer-Associated Carbonic Anhydrase IX Isoenzyme

Carbonic anhydrase IX (CA IX), a tumor-associated metalloenzyme, represents a validated target for cancer therapy and diagnostics. Herein, we report the inhibition properties of isomeric families of sulfonamidopropyl-dicarba-closo-dodecaboranes group(s) prepared using a new direct five-step synthesis from the corresponding parent cages. The protocol offers a reliable solution for synthesis of singly and doubly substituted dicarba-closo-dodecaboranes with a different geometric position of carbon atoms. The closo-compounds from the ortho- and meta-series were then degraded to corresponding 11-vertex dicarba-nido-undecaborate(1−) anions. All compounds show in vitro enzymatic activity against CA IX in the low nanomolar or subnanomolar range. This is accompanied by clear isomer dependence of the inhibition constant (K_i) and selectivity towards CA IX. Decreasing trends in K_i and selectivity index (S_I) values are observed with increasing separation of the cage carbon atoms. Interactions of compounds with the active sites of CA IX were explored with X-ray crystallography, and eight high-resolution crystal structures uncovered the structural basis of inhibition potency and selectivity.