Separation of bioactive chamazulene from chamomile extract using metal-organic framework.

Isolation of bioactive compounds from extracts of pharmaceutical plant is very important. In this work, copper benzene-1,3,5-tricarboxylate metal organic framework (Cu-BTC MOF) has been synthesized. It is used in separating of chamazulene from chamomile extract. The Cu-BTC MOF not only shows good chamazulene adsorption but also maintains good desorption properties. However, the research on this field is still new and the maturation of novel MOFs or the enhancements of known ones are required.The chamomile extract obtained after each stage of the treatments was carefully characterized by thin-layer chromatography (TLC), Fourier-transform infrared spectroscopy (FTIR), UV-vis spectrometry and gas chromatography-mass spectrometry (GC-MS). The morphology and the crystallinity of Cu-BTC MOF were investigated using scanning electron microscopy (SEM) and powder X-ray diffraction (PXRD), respectively. Breakthrough experiments in a column was investigated and the data was fitted with Bohart-Adams model. Monte Carlo simulation was conducted to investigate the preferential adsorption sites of Cu-BTC for chamazulene molecules.

SILAC-based proteomic analysis reveals that salidroside antagonizes cobalt chloride-induced hypoxic effects by restoring the tricarboxylic acid cycle in cardiomyocytes.

Hypoxic status alters the energy metabolism and induces cell injury in cardiomyocytes, and it further triggers the occurrence and development of cardiovascular diseases. Our previous studies have shown that salidroside (SAL) exhibits anti-hypoxic activity. However, the mechanisms remain obscure. In the present study, we successfully screened 92 different expression proteins in CoCl2-induced hypoxic conditions, 106 different expression proteins in the SAL-mediated anti-hypoxic group were compared with the hypoxic group using quantitative proteomics strategy, respectively. We confirmed that SAL showed a positive protective function involving the acetyl-CoA metabolic, tricarboxylic acid (TCA) cycle using bioinformatics analysis. We also demonstrated that SAL plays a critical role in restoring the TCA cycle and in protecting cardiomyocytes from oxidative injury via up-regulation expressions of PDHE1-B, ACO2, SUCLG1, SUCLG2 and down-regulation of MDH2. SAL also inhibited H9c2 cell apoptosis by inhibiting the activation of pro-apoptotic molecules caspase 3 and caspase 9 as well as activation of the anti-apoptotic molecular Bcl-2. Additionally, SAL also improved mitochondrial membrane potential (ΔΨm), reduced reactive oxygen species (ROS) and intercellular Ca(2+) concentration ([Ca(2+)]i) accumulation and inhibited the excessive consumption of ATP in H9c2 cells.

[Studies on chemical constituents from fruits of Morus alba L].

Chemical investigation of fruits of Mours alba L. lead to the isolation of fifteen compounds by various chromatographies such as silica gel, Sephadex LH-20, RP-C18 column chromatography. Their structures were determined to be: 1-[5-(2-formlfuryl) methyl] dihydrogen 2-hydroxypropane-1, 2, 3-tricarboxylate 2, 3-diethyl ester (1), 1-[2-(furan-2-yl)-2-oxoethyl] pyrrolidin-2-one (2), divaricataester A (3), methyl 1-[2-(furan-2-yl)-2-oxoethyl]-5-oxopyrrolidine-2-carboxylate (4), 1-[2-(furan-2-yl)-2-oxoethyl]-5-oxopyrrolidine-2-carboxylic acid (5), L-pyroglutamic acid (6), L-pyroglutamic acid ethyl ester (7), 3-O-caffeoylquinic acid methyl ester (8), 3-O-caffeoylquinic acid ethyl ester (9), 5-O-caffeoylquinic acid methyl ester (10), 5-O-caffeoylquinic acid ethyl ester (11), 4-O-caffeoylquinic acid methyl ester (12), 4-O-caffeoylquinic acid methyl ester (13), 4-O-caffeoylquinic acid (14), 3-O-caffeoylquinic acid (15), respectively, based on the spectral analysis such as NMR, MS etc. Compounds 1-14 were isolated from this genus for the first time, among which 1 was a new compound.

MOF-76: from a luminescent probe to highly efficient U(VI) sorption material.

MOF-76 exhibits not only high sensitivity for the detection of U(vi), but also high adsorption capacity of 298 mg g(-1) at a low pH value of ∼3.0. Furthermore, the high selectivity for uranium adsorption over a series of competing metal ions is also illustrated.

Effect of self-adhesive resin cement and tribochemical treatment on bond strength to zirconia.

AIM: To evaluate the interactive effects of different self-adhesive resin cements and tribochemical treatment on bond strength to zirconia. METHODOLOGY: The following self-adhesive resin cements for bonding two zirconia blocks were evaluated: Maxcem (MA), Smartcem (SM), Rely X Unicem Aplicap (UN), Breeze (BR), Biscem (BI), Set (SE), and Clearfil SA luting (CL). The specimens were grouped according to conditioning as follows: Group 1, polishing with 600 grit polishing paper; Group 2, silica coating with 110 microm Al2O3 particles which modified with silica; and, Group 3, tribochemical treatment--silica coating + silanization. Specimens were stored in distilled water at 37 degrees C for 24 hours before testing shear bond strength. RESULTS: Silica coating and tribochemical treatment significantly increased the bond strength of the MA, UN, BR, BI, SE and CL to zirconia compared to #600 polishing. For both #600 polished and silica coating treatments, MDP-containing self-adhesive resin cement CL had the highest bond strengths to zirconia. CONCLUSION: Applying silica coating and tribochemical treatment improved the bond strength of self-adhesive resin cement to zirconia, especially for CL.

Porous coordination polymer with flexibility imparted by coordinatively changeable lithium ions on the pore surface.

Solvothermal reactions of equimolar zinc acetate, lithium acetate, and 1,3,5-benzenetricarboxylic acid (H(3)btc) in different mixed solvents yielded isostructural three-dimensional frameworks [LiZn(btc)(cG)].lG [cG and lG denote coordinated and lattice guests, respectively; cG = (nmp)(0.5)(H(2)O)(0.5), lG = (EtOH)(0.5) (1a); cG = H(2)O, lG = EtOH (1b); nmp = N-methyl-2-pyrrolidone] with one-dimensional channels occupied by guest molecules and solvent-coordinated, extrusive Li(+) ions. Thermogravimetry analyses and powder X-ray diffraction measurements revealed that both 1a and 1b can lose all lattice and coordinated guests to form a desolvated phase [LiZn(btc)] (MCF-27, 1) and almost retains the original framework structure. Gas adsorption measurements on 1 confirmed its permanent porosity but suggested a structural transformation from 1a/1b to 1. It is noteworthy that only 1a can undergo a single-crystal to single-crystal (SCSC) transformation into 1 upon desolvation. The crystal structure of 1 revealed that the Li(+) ions were retracted into the channel walls via complementary coordination to the carboxylate oxygen atoms in the framework rather than being exposed on the pore surface. Single-crystal X-ray diffraction analyses were also performed for N(2)- and CO(2)-loaded samples of 1, revealing that the framework remained unchanged when the gases were adsorbed. Although the gas molecules could not be modeled, the residue electrons inside the channels demonstrated that the retracted Li(+) ions still behave as the primary interacting site for CO(2) molecules. Nevertheless, solvent molecules such as H(2)O can readily compete with the framework oxygen atom to retrieve the extrusive Li(+) ions, accompanying the reverse structural transformation, i.e., from 1 to 1a/1b.

Molecular structures of citrate and tricarballylate adsorbed on alpha-FeOOH particles in aqueous suspensions.

In this work, the adsorption of citric (2-hydroxypropane-1,2,3-tricarboxylic acid) and tricarballylic (propane-1,2,3-tricarboxylic acid) acids onto alpha-FeOOH (goethite) in aqueous suspensions was studied as a function of pH and total ligand concentration in 0.1 M NaCl at 25.0 degrees C, and the molecular structures of the surface complexes formed were analyzed by means of ATR-FTIR spectroscopy. The adsorption experiments were carried out as a series of batch experiments, and a newly developed simultaneous infrared and potentiometric titration technique was used to collect in situ infrared spectra with high signal-to-noise ratios. The high quality of the infrared spectra allowed analysis by means of two-dimensional correlation spectroscopy formalism that aided the resolution of pH-dependent spectral features. This has enabled the detection of two previously unidentified citrate-goethite surface complexes: one protonated species at low pH, and one inner sphere complex prevailing at high pH and coordinated via a combination of hydroxyl and carboxylate groups. In addition, an inner sphere complex involving only carboxylate coordination predominating at low pH and an outer sphere complex existing in the circumneutral pH region were identified. The behavior of tricarballylate parallels that of citrate, except no inner sphere surface complex is formed at high pH values, which is in accordance with the lack of an alpha-hydroxyl group. The comparison between citrate and tricarballylate reinforces previous observations showing that inner sphere surface complexes of pure carboxylates at water-iron oxide interfaces are suppressed at high pH values, where outer sphere species are relatively more predominant. It also shows that significant amounts of inner sphere surface complexes of carboxylates only seem to form in the basic pH region when the ligands contain complementary functional groups, such as the hydroxyl or amine groups.

Adhesive bonding of resin composite to various Ni-Cr alloy surfaces using different metal conditioners and a surface modification system.

PURPOSE: This study evaluated the effect of three metal conditioners [Metal Photo Primer (MPP), Cesead II Opaque Primer (OP), Targis Link (TL)], and one surface modification system [Siloc (S)] on the shear bond strength (SBS) of a prosthetic composite material to Ni-Cr alloy. MATERIALS AND METHODS: Rivet-shaped specimens were cast, and three surface treatments were evaluated: Polishing (P); sandblasting with either 50 microm (50SB) or 250 microm (250SB) Al(2)O(3). All products were applied to half of the specimens, while the other half remained without the materials. Veneering resin composite (8-mm diameter, 2-mm thick) was applied and light-exposed for 90 seconds in a laboratory light-curing unit. The specimens were stored in water at 37 degrees C for 24 hours, and half were subjected to 500 thermal cycles consisting of water baths at 4 degrees C and 60 degrees C. All specimens were submitted to SBS test (0.5 mm/min) until failure. Failure patterns were determined using optical and scanning electron microscope (SEM) analysis. Data were analyzed by ANOVA and post hoc Tukey's test (preset alpha of 5%). RESULTS: The SBS values of OP and TL groups were higher than those of MPP and S within the 50SB treatment (p < 0.05). No significant difference in SBS was noted between OP and TL as well as between MPP and S. On the other hand, no significant differences were found among conditioners within the 250SB group (p > 0.05). The SBS values of MPP, OP, and S from the 250SB group were higher than those from 50SB (p < 0.05). No significant difference in SBS was noted among most groups with conditioners after thermocycling. The only exception was observed for MPP, which showed an increase in SBS after thermocycling (p < 0.05). Differences in SBS were noted among the groups with conditioners (p < 0.05), and no significant difference in SBS was noted between TL and OP groups, which showed the highest values among all within the P group. No significant difference was noted between MPP and S. Debonded surfaces showed adhesive failures predominantly located between metal surface and opaque resin. CONCLUSIONS: The OP and TL conditioners and surface sandblasting with 250 microm Al(2)O(3) promoted the highest SBS between resin and the Ni-Cr metal surface.

Manganese-based nanoscale metal-organic frameworks for magnetic resonance imaging.

Manganese-containing nanoscale metal-organic frameworks (NMOFs) with controllable morphologies were synthesized using reverse-phase microemulsion techniques at room temperature and a surfactant-assisted procedure at 120 degrees C with microwave heating. The nanoparticles were characterized using a variety of methods including SEM, TEM, TGA, PXRD, and ICP-MS. Although the nanoparticles gave a modest longitudinal relaxivity (r1) on a per Mn basis, they provided an efficient vehicle for the delivery of large doses of Mn2+ ions which exhibited very high in vitro and in vivo r1 values and afforded excellent MR contrast enhancement. The particle surface was also modified with a silica shell to allow covalent attachment of a cyclic RGD peptide and an organic fluorophore. The cell-targeting molecules on the Mn NMOFs enhanced their delivery to cancer cells to allow for target-specific MR imaging in vitro. The MR contrast enhancement was also demonstrated in vivo using a mouse model. Such core-shell hybrid nanostructures provide an ideal platform for targeted delivery of other imaging and therapeutic agents to diseased tissues.

A comparative metal ion adsorption study by trimesic acid coated alumina: a potent adsorbent.

Benzene-1,3,5-tri-carboxylic acid (trimesic acid, TMA) coated on basic alumina has been shown to be an effective adsorbent for Fe(III) and Fe(II) from aqueous solution. A comparative study on the adsorption of Fe(III) and Fe(II) revealed that TMA coated alumina is more selective towards Fe(III) than Fe(II). The maximum adsorptions of Fe(III) and Fe(II) were 26.6 mg/g and 8.4 mg/g, respectively. Fe(III)/Fe(II) adsorption was also compared in some cases with adsorption of Co(II) and Ni(II). Maximum uptakes (Qm) for Co(II) and Ni(II) were found much lower (approximately 1 mg/g) than Fe(III)/Fe(II). pH dependent studies have revealed that Fe(III) was adsorbed efficiently at high acidic condition (pH approximately 1.5) compared to Fe(II), Co(II) and Ni(II), while temperature did not have significant effect on the adsorption processes. Adsorption of Fe(III) and Fe(II) was quite rapid and thermodynamically favourable. Adsorption processes fitted well in Langmuir isotherm model and followed second order rate kinetics in all cases.

Trimesic acid coated alumina: an efficient multi-cyclic adsorbent for toxic Cu(II).

Biodegradable and eco-friendly organic acid, benzene-1,3,5-tri-carboxylic acid (trimesic acid), coated on commercial basic alumina, was used as adsorbent to remove toxic Cu(II) ion from aqueous solution. Adsorbent preparation was optimized and was characterized by SEM, EDX, FT-IR, and powder XRD pattern. Effect of various regulating parameters like reaction pH, adsorbent dose and initial Cu(II) concentration was studied in detail. Adsorption isotherms followed the Langmuir isotherm model and adsorption was thermodynamically favourable. Maximum adsorption capacity (Qm) for Cu(II) ion has been achieved as 10.80 mg/g. Detail kinetic study revealed that it followed second-order rate. Desorption of Cu(II) ion and re-usability of the adsorbent was also studied.

Influence of L-isoleucine and pantothenate auxotrophy for L-valine formation in Corynebacterium glutamicum revisited by metabolome analyses.

The effect of different amounts of supplemented L-isoleucine and pantothenate has been analysed with the auxotrophic strain Corynebacterium glutamicum DeltailvA DeltapanB, showing that the final biomass concentration of this preliminary L-valine production strain can be controlled by the amount of added L-isoleucine. One gramme cell dry weight is formed from 48 micromol L-isoleucine. Different amounts of available pantothenate affect the intracellular pyruvate concentration. By limiting pantothenate supplementation from 0.8 to 0.1 microM, a 35-fold increase of cytoplasmic pyruvate up to 14.2 mM can be observed, resulting in the increased formation of L-valine, L-alanine and organic acids in the presence of low pantothenate concentrations. These findings can be used to redirect the carbon flux from glycolysis via pyruvate to the TCA cycle towards the desired product L-valine.

1-Aminocyclopentane-1,2,4-tricarboxylic acids screening on glutamatergic and serotonergic systems.

Enantiopure constrained 1-aminocyclopentane-1,2,4-tricarboxylic acids containing the glutamic acid skeleton were prepared as two diastereomers characterized by having the carboxylic groups in position two and four cis-oriented to each other and trans with respect to 1-carboxylic group and all cis-oriented carboxylic groups, respectively. A biochemical screening of activity of the above amino acids was investigated on glutamate and 5-HT receptors to find a possible metabotropic agonist, acting on the serotoninergic system.

Analysis of chemical interaction of 4-MET with hydroxyapatite using XPS.

Each dental adhesive contains a specific functional monomer that determines its actual adhesive performance to tooth tissue. 4-methacryloxyethyl trimellitic acid (4-MET) is well-known as one of the functional monomers mostly available and consequently widely used in commercial adhesives. We therefore characterized the chemical interaction of 4-MET with hydroxyapatite (HAp) using X-ray Photoelectron Spectroscopy (XPS). XPS revealed that the peak representing -COO- of 4-MET shifted to a lower binding energy, when 4-MET was adsorbed onto HAp. Deconvolution of this shifted peak disclosed two components with a peak representing unreacted carboxyl groups and ester groups, and a peak suggesting chemical bonding of other carboxyl groups to Ca of HAp. XPS spectra of HAp treated with 4-MET also disclosed the surface to be enriched in calcium and decreased in phosphorus, indicating that phosphorus was extracted at a relatively higher rate than calcium. It can thus be concluded that true chemical bonding of 4-MET with calcium present in HAp occurred, as it was proven using XPS.

Structural elucidation of natural 2-hydroxy di- and tricarboxylic acids and esters, phenylpropanoid esters and a flavonoid from Autonoë madeirensis using gas chromatographic/electron ionization, electrospray ionization and tandem mass spectrometric techniques.

The chemical composition of Autonoë madeirensis bulbs was characterized as part of a systematic phytochemical study of this species. The compounds reported were mainly identified on the basis of gas chromatography/electron ionization, electrospray ionization and tandem mass spectrometry. The structures of the pure compounds were also characterized by means of other physical and spectroscopic data (m.p., IR, UV, NMR). The compounds identified were 2-hydroxy di- and tricarboxylic acids and esters (malic acid, citric acid and their methyl and ethyl esters), cis- and trans-hydroxycinnamic esters (methyl and ethyl p-coumarate and methyl ferulate) and a new flavone diglucoside, 7-O-[beta-glucosyl-(1-->2)-O-beta-glucosyl]apigenin, the interglucosidic linkage (1-->2) of which is, to the best of our knowledge, reported for the first time in a diglucoside of apigenin. The results may contribute to the chemotaxonomy of the Autonoë genus and lead to a rapid tool for the systematic characterization of these compounds in plant extracts.

Discovery, biosynthesis, and mechanism of action of the zaragozic acids: potent inhibitors of squalene synthase.

The zaragozic acids (ZAs), a family of fungal metabolites containing a novel 4,6,7-trihydroxy-2,8-dioxobicyclo[3.2.1]octane-3,4,5-tricarboxylic acid core, were discovered independently by two separate groups screening natural product sources to discover inhibitors of squalene synthase. This family of compounds all contain the same core but differ in their 1-alkyl and their 6-acyl side chains. Production of the ZAs is distributed over an extensive taxonomic range of Ascomycotina or their anamorphic states. The zaragozic acids are very potent inhibitors of squalene synthase that inhibit cholesterol synthesis and lower plasma cholesterol levels in primates. They also inhibit fungal ergosterol synthesis and are potent fungicidal compounds. The biosynthesis of the zaragozic acids appears to proceed through alkyl citrate intermediates and new members of the family have been produced through directed biosynthesis. These potent natural product based inhibitors of squalene synthase have potential to be developed either as cholesterol lowering agents and/or as antifungal agents.