Synthesis and inhibitory activity of alkyl(hydroxyaryl)amines

The reaction of ω-(4-hydroxyaryl)haloalkanes with various nitrogen-containing agents afforded primary, secondary, and tertiary amino derivatives of 2,6-dialkylphenols. For the compounds synthesized, the reaction rate constants with peroxide radicals were measured for cumene and methyl oleate oxidation. The total inhibitory activity in the model reactions of thermal autooxidation of lard and hexadecane was studied. The rate constants of alkyl(hydroxylaryl)amines are the same as those of the corresponding alkylphenols, whereas the total inhibitory activity of some alkyl(hydroxylaryl)amines exceeds substantially that for alkylphenols. Dedicated to the memory of Academician N. N. Vorozhtsov on the 100th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1107–1112, June, 2007.     

GIF S-亚硝基化的一些见解

Neural growth inhibitory factor （GIF）, a member of metallothionein family （metallothionein-3, MT3）, was well known by its distinct neural growth inhibitory activity, which is not shown by other MT isoforms. However, till now, people still did not know clearly how GIF exerts its biological functions. Since it has been reported that GIF might serve as NO scavenger and was related to the release of zinc, our study was focused on the interaction of GIF and NO. By studying the reactions of human GIF and human MTlg with SNOC-a type of NO donor, it was found that GIF was more reactive than MT-lg toward SNOC. In order to further figure out if the high reactivity of GIF in this reaction resulted from the acid-base catalysis, several mutants were constructed： E23K, E41G/E43A, E23K/E41G/E43A. By studying their basic properties and the reactions toward SNOC, it was found that the S-nitrosylation of GIF was not only related to the acid-base catalysis, but also to the accessibility of metal-thiolate clusters.     

Essential of Proline and Valine Residues in the Peptide Derived from Lactoferrin for Angiotensin Converting Enzyme Inhibition

We synthesized Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu, the peptide contained in lactoferrin (Lf), to identify the angiotensin converting enzyme (ACE) inhibition. In an attempt to know the structure‐activity relationship of this peptide, we replaced Pro (the third amino acid residues from N‐terminal) or Val (the fourth amino acid residues from N‐terminal) with Ala (neutral amino acid), Glu (acidic amino acid) or Lys (basic amino acid) to produce six peptides. From the in vitro ACE inhibition (IC₅₀) of these synthesized peptides, the original peptide (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu) showed higher ACE inhibition than the replaced six peptides. Thus, replacement of Pro at the third amino acid residues or Val at the fourth position with Ala, Glu or Lys revealed the ACE inhibition to be lower than the original form of Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu. Otherwise, we added one peptide at the C‐terminal of Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu and found both products with an addition of Val (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu‐Val) or Ile (Leu‐Arg‐Pro‐Val‐Ala‐Ala‐Glu‐Ile) showing a lower ACE inhibition than the original one. The ACE inhibitions produced by both replaced peptides were without significance. Also, deletion of the last peptide at the C‐terminal (Leu‐Arg‐Pro‐Val‐Ala‐Ala) failed to produce a marked change of ACE inhibition as compared to the original one. These results suggest that Pro and Val are essential in the peptide for inhibition of ACE activity.     

Influence of extractions on physicochemical characterization and bioactivity of Piper nigrum oils: Study on the non-isothermal decomposition kinetic

Black pepper oils have been investigated frequently in the recent years. However, there is a significant variation in physicochemical properties and bioactivity of oils depended on extraction techniques. In this study, the systemic investigation of four various extraction methods was performed to evaluate the physicochemical characterizations, antioxidant and antibacterial activity. The investigation of ¹H NMR, FTIR and UV–Vis spectra confirmed presence of non-volatile components in oils extracted through supercritical CO₂ and hexane-soaking extractions which induced their typical thermal properties. The isothermal behaviour of extracted oils related to evaporation was within range of 3.2–7.3% (w/w) at 27 °C. The SEM images of the black pepper confirmed different operation manners of mechanism between extractions using the solvents and heating process. The lowest MIC for both essential oils from conventional hidrodistillation and microwave-assisted hidrodistillation against two bacteria including E. coli and B. subtilis were found to be 137 µg mL⁻¹. The non-isothermal decomposition kinetics were investigated on the essential oil of microwave-assisted hydrodistillation extraction. The activation energies and pre-exponent factors of non-isothermal decomposition were found to be in range of 36.5–73.7 KJ mol⁻¹ and 4.98 × 10³–1.97 × 10⁸ s⁻¹, respectively, dependent on conversional fractions of the oil. The results revealed that chemical components, physicochemical properties and bioactivity of black pepper essential oils depended on the extraction techniques.     

Effect of Cationic Surfactant on the Inhibition of Ligninase by Hydrogen Peroxide

The inhibition of lingninase by hydrogen peroxide in the presence of cationic surfactant CTAB was studied by kinetic speetrophotometdc technique. Results showed that addition of CTAB enhanced the inhibition by H202, but it did not alter the inhibition pattern and the inhibition constant changed little with theco-ncentration of CTAB. Modification of the enzymic protein by the surfactant monomer may be responsible for the above mentioned results.     

A new dimeric alkylresorcinol from the stem barks of Swintonia floribunda (Anacardiaceae)

From an EtOAc-soluble fraction of the stem barks of Swintonia floribunda (Anacardiaceae), one new dimeric alkylresorcinol named integracin E (1), together with 4 known compounds (2–5) were isolated. Their chemical structures were elucidated based on the spectroscopic data interpretation. The absolute configuration of 1 was determined by the specific rotation analysis of its acid-catalyzed hydrolysis product. Compound 1 showed potent tyrosinase inhibitory activity with an IC₅₀ value of 48.2?μM.     

Dayaolingzhiols A−E,AchE inhibitory meroterpenoids from Ganoderma lucidum

Ganoderma mushrooms are widely used as effective medicines for treating and preventing chronic diseases. In this study, five new meroterpenoids, dayaolingzhiols A (1) and B (2) featuring a 6/6/6 ring system, dayaolingzhiols C?E (3–5) harboring a γ-lactone motif, along with eight known ones (6–13), were purified from G. lucidum. To clarify their chemical structures, spectroscopic and ECD and OR computational methods were used. In addition, the inhibition of all the new meroterpenoids against AChE was evaluated, disclosing that (+)-4 and (±)-5 possess potent AChE inhibitory activities with respective IC₅₀ values of 8.52?±?1.90?μM and 7.37?±?0.52?μM.     

Some issues associated with the intermediate space in single-crystal plasticity

In this study we show that some discussions of finite-deformation single-crystal plasticity are conceptually flawed in their focus on a set referred to as the intermediate configuration. Specifically, we prove that what is usually referred to as the intermediate configuration is not a configuration but instead a vector space that we term the intermediate space. We argue that when applied to single crystals this intermediate space represents the lattice.     

Strain gradient plasticity analysis of elasto-plastic contact between rough surfaces

From a microscopic point of view, the real contact area between two rough surfaces is the sum of the areas of contact between facing asperities. Since the real contact area is a fraction of the nominal contact area, the real contact pressure is much higher than the nominal contact pressure, which results in plastic deformation of asperities. As plasticity is size dependent at size scales below tens of micrometers, with the general trend of smaller being harder, macroscopic plasticity is not suitable to describe plastic deformation of small asperities and thus fails to capture the real contact area and pressure accurately. Here we adopt conventional mechanism-based strain gradient plasticity (CMSGP) to analyze the contact between a rigid platen and an elasto-plastic solid with a rough surface. Flattening of a single sinusoidal asperity is analyzed first to highlight the difference between CMSGP and J₂ isotropic plasticity. For the rough surface contact, besides CMSGP, pure elastic and J₂ isotropic plasticity analysis is also carried out for comparison. In all cases, the contact area A rises linearly with the applied load, but with a different slope which implies that the mean contact pressures are different. CMSGP produces qualitative changes in the distributions of local contact pressures compared with pure elastic and J₂ isotropic plasticity analysis, furthermore, bounded by the two.