A novel antimicrobial triterpenic acid from the leaves of Ficus benjamina (var. comosa)

The chloroform extract of the leaves of Ficus benjamina (var. comosa) (Moraceae) afforded a new triterpenic acid named as (9,11), (18,19)-disecoolean-12-en-28-oic acid (1) along with β-amyrin (2). Their structures were established on the basis of chemical and physical evidences (IR, ¹H NMR, and MS data). The compound 1 exhibited significant antimicrobial activity against Salmonella typhimurium (MTCC-98), Candida albicans (IAO-109), Staphylococcus aureus (IAO-SA-22), Escherichia coli (K-12) and low activity against Aspergillus niger (lab isolate ICAR) and Aspergillus brassicola.     

Determination of the formation constant for the inclusion complex between Lanthanide ions and Dansyl chloride derivative by fluorescence spectroscopy: Theoretical and experimental investigation

In this paper, a sensitive, easy, efficient, and suitable method for the calculation of K_f values of complexation between one derivative of Dansyl chloride [5-(dimethylamino) naphthalene-1-sulfonyl 4-phenylsemicarbazide] (DMNP) and Lanthanide(III) (Ln) ions is proposed, using both spectrofluorometric and spectrophotometric methods. Determination of K_f showed that DMNP was mostly selective towards the erbium (III) ion. The validity of the method was also confirmed calculating the Stern–Volmer fluorescence quenching constants (K_sv) that resulted in the same consequence, obtained by calculating the K_f of complexation values. In addition, the UV–vis spectroscopy was applied for the determination of K_f only for the Ln ions that had interactions with DMNP. Finally, the DFT studies were done on Er³⁺ and the DMNP complex for distinguishing the active sites and estimating the pair wise interaction energy. It can be concluded that this derivative of Dansyl chloride with inherent high fluorescence intensity is a suitable reagent for the selective determination of the Er³⁺ ion which can be used in constructing selective Er³⁺ sensors.     

Confocal microscopy study of uptake kinetics of α‐lactalbumin and β‐lactoglobulin onto the cation‐exchanger SP Sepharose FF

Confocal laser scanning microscopy (CLSM) was used to study single‐ and two‐component protein uptake for α‐lactalbumin (ALA) and β‐lactoglobulin (BLG), as models for whey proteins, to SP Sepharose FF at pH 3.7 during batch experiments in a finite bath. By coupling a fluorescent dye with the protein molecule, the penetration into individual adsorbent particles at different times during batch uptake was visualised. In a single‐component system, BLG penetrated fast into the adsorbent beads and gradually filled them in a shell‐wise fashion, while adsorption of ALA was mostly confined to the outer shells of the adsorbent. For the two‐component studies, the results showed that ALA was able to displace BLG despite its lower affinity to the adsorbent under the employed conditions. CLSM results were then compared both qualitatively and quantitatively to their counterparts obtained in traditional experiments by indirect measurements of the protein concentration in the fluid phase. A novel quantitative approach was undertaken by modifying the simple kinetic rate model traditionally used to determine the kinetic rate constant, k₁, for batch uptake experiments, in order to describe batch uptake kinetics based on CLSM data. Although BLG results were in good agreement, there was a discrepancy in ALA results.     

Resolution of 1,1′-Binaphthyl-2,2′-Dicarboxylic Acid with Quinine: Structure of the Intermediate (<Emphasis Type="Italic">S</Emphasis>)-1,1′-Binaphthyl-2,2′-Dicarboxylate Dihydrate Diastereomeric Salt

Abstract  

Racemic 1,1′-binaphthyl-2,2′-dicarboxylic acid (BNDA) was resolved using quinine as the resolving agent. The structure of the resultant quininium (S)-1,1′-binaphthyl-2,2′-dicarboxylate dihydrate salt (1) was elucidated. The asymmetric unit contained one 1,1′-binaphthyl-2,2′-dicarboxylate anion, two quininium cations and two water molecules. The structure was solved successfully in the orthorhombic space group P2₁2₁2₁ with unit cell dimensions: a = 11.100(2) ?, b = 16.572(3) ?, c = 28.726(6) ?.     

Synthesis,Crystal Structure,Ab Initio Studies and Fingerprint Plots of 2-Chloro-1,3-dioxo-2,3-dihydro-1H-inden-2-yl acetate

Abstract  

2-Chloro-1,3-dioxo-2,3-dihydro-1H-inden-2-yl acetate, C₁₁H₇ClO₄ (Fig. 1), has been synthesized and the structure has been solved by IR and X-ray diffraction studies. The crystals are triclinic, space group P [`1] \bar{1} , with a = 7.62060(10) ?, b = 11.5944(2) ?, c = 13.0753(3) ?, α = 97.2820(10)°, β = 101.5740(10)°, γ = 101.7930(10)°, Mr = 238.62, V = 1090.82(3) ?³, Z = 4 and R = 0.0557. In the title compound there are two molecules in the asymmetric unit. The molecules are linked via weak C–H···O hydrogen bonds forming R₄⁴(28) rings. The intermolecular interactions were analysed by means of the fingerprint plots derived from the Hirshfeld surfaces. The fingerprint plots evidenced subtle differences in the intermolecular contacts for the two independent molecules.      

Multiscale Modeling of Nanocrystalline Materials: A Variational Approach

This paper presents a variational multi-scale constitutive model in the finite deformation regime capable of capturing the mechanical behavior of nanocrystalline (nc) fcc metals. The nc-material is modeled as a two-phase material consisting of a grain interior (GI) phase and a grain boundary (GB) phase. A rate-independent isotropic porous plasticity model is employed to describe the GB phase, whereas a crystal-plasticity model which accounts for the transition from partial dislocation to full dislocation mediated plasticity is employed for the GI phase. Assuming the rule of mixtures, the overall behavior of a given grain is obtained via volume averaging. The scale transition from a single grain to a polycrystal is achieved by Taylor-type homogenization. It is shown that the proposed model is able to capture the inverse Hall-Petch effect. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Anticancer and anti-inflammatory sulfur-containing semisynthetic derivatives of sarcophine

Sarcophine (1), a cembranoid diterpene is known to inhibit the process of tumorigenesis. Sarcophine can be isolated in large amounts from the Red Sea soft coral Sarcophyton glaucum and hence is an ideal target for semisynthetic or biocatalytic modifications. Hydroxylated derivatives of 1 were reported to improve its anticancer activity. Despite the promising results and ready availability, there are limited attempts towards further diversifying the library of sarcophine derivatives. Hence, the current study targets the epoxide ring to generate sulfur-containing derivatives of sarcophine by reacting it with ammonium thiocyanate and Lawesson's reagent. Structure elucidation of the products was based on extensive 1D and 2D NMR and high resolution mass spectrometry, in addition to mechanistic considerations. The effect of these derivatives on highly malignant +SA mammary epithialial cell proliferation is reported. Anti-inflammatory potential of sarcophine and its derivatives is also demonstrated.     

Design of a fast convergent backpropagation algorithm based on optimal control theory

The main contribution of this paper is using optimal control theory for improving the convergence rate of backpropagation algorithm. In the proposed approach, the learning algorithm of backpropagation is modeled as a minimum time control problem in which the step-size of its learning factor is considered as the input of this model. In contrast to the traditional backpropagation, learning algorithms which select the step-size by trial and error, it is selected adaptively based on optimal control criterion. The effectiveness of the proposed algorithm is evaluated in two simulations: XOR and 3-bit parity. In both simulation examples, the proposed algorithm outperforms well in speed and the ability to escape from local minima.     

Chiral Monolithic Silica-Based HPLC Columns for Enantiomeric Separation and Determination: Functionalization of Chiral Selector and Recognition of Selector-Selectand Interaction

This review draws attention to the use of chiral monolithic silica HPLC columns for the enantiomeric separation and determination of chiral compounds. Properties and advantages of monolithic silica HPLC columns are also highlighted in comparison to conventional particle-packed, fused-core, and sub-2-µm HPLC columns. Nano-LC capillary monolithic silica columns as well as polymeric-based and hybrid-based monolithic columns are also demonstrated to show good enantioresolution abilities. Methods for introducing the chiral selector into the monolithic silica column in the form of mobile phase additive, by encapsulation and surface coating, or by covalent functionalization are described. The application of molecular modeling methods to elucidate the selector–selectand interaction is discussed. An application for enantiomeric impurity determination is also considered.     

Thermal Stability of Modified i‐Motif Oligonucleotides with Naphthalimide Intercalating Nucleic Acids

In continuation of our investigation of characteristics and thermodynamic properties of the i‐motif 5′‐d[(CCCTAA)₃CCCT)] upon insertion of intercalating nucleotides into the cytosine‐rich oligonucleotide, this article evaluates the stabilities of i‐motif oligonucleotides upon insertion of naphthalimide (1H‐benzo[de]isoquinoline‐1,3(2H)‐dione) as the intercalating nucleic acid. The stabilities of i‐motif structures with inserted naphthalimide intercalating nucleotides were studied using UV melting temperatures (T_m) and circular dichroism spectra at different pH values and conditions (crowding and non‐crowding). This study indicated a positive effect of the naphthalimide intercalating nucleotides on the stabilities of the i‐motif structures compared to the wild‐type structure which is in contrast to a previous observation for a pyrene‐intercalating nucleotide showing a decrease in T_m values.