Neomacrophorin I,II, and III,novel drimenyl cyclohexanes with hydroxylated butanoates from Trichoderma sp. 1212-03

Neomacrophorins I (1), II (2), and III (3) were isolated from the culture broth of Trichoderma sp. 1212-03, which was collected at Shirakami Mountainous area in Japan. Structural analyses disclosed that these resemble known macrophorins but possess axial-hydroxy group at C3 as well as different side chains at C7′. These are diastereomeric forms of macrophorins for 5′,6′-epoxide functionality. The NMR analyses suggested their relative configurational relationship between the C1–C15 drimene and C1′–C7′ epoxyquinone moieties. ECD spectral discussions verified them particularly for C5′,C6′-epoxyquinone (1), C5′,C6′-epoxysemiquinone (2 and 3), and 2″,3″-dihydroxybutanoate moiety in 1 and 2. The configuration of C3″-stereocenter of 3 was determined by chiral GC–MS after converting into methyl (S)-3″-hydroxybutanoate by basic of 3 methanolysis. Biological assays disclosed that 1 induces hyphal branching of Cochliobolus miyabeanus as well as cytotoxicity against human colorectal cancer COLO 201.     

Chemical Profiling,Toxicity and Anti-Inflammatory Activities of Essential Oils from Three Grapefruit Cultivars from KwaZulu-Natal in South Africa

The medicinal potential and volatile composition of different parts of three cultivars of grapefruit (Citrus paradisi) were evaluated for their toxicity and anti-inflammatory activities. Fresh leaf and fruit peel were separately isolated by hydrodistillation for 4 h. The essential oils were subjected to GC/GC-MS analysis for chemical profile. Toxicity of the essential oils in mice were evaluated using Lorke’s method, while an anti-inflammatory assay was performed in a rat model using egg albumin-induced oedema. The oils obtained were light yellow in colour, and odour varied from strong citrus smell to mild. Percentage yield of fresh peel oil (0.34–0.57%) was greater than the fresh leaf oil yield (0.21–0.34%). D-limonene (86.70–89.90%) was the major compound identified in the leaf oil, while β-phellandrene (90.00–91.01%) dominated the peel oil. At a dosage level of 5000 mg/kg, none of the oils showed mortality in mice. An anti-inflammatory bioassay revealed that all the oils caused a significant (p < 0.05–0.01) reduction in oedema size when compared to the negative control group throughout the 5 h post induction assessment period. The study reveals that the oils are non-toxic and demonstrate significant anti-inflammatory activity. Our findings suggest that the leaf and peel oils obtained from waste parts of grapefruit plants can be useful as flavouring agents, as well as anti-inflammatory agents.     

Cross‐sectional structural characterization of the surface of exfoliated HOPG using HRTEM‐EELS

We analyzed the surface atomic structure of highly oriented pyrolytic graphite (HOPG) substrate exfoliated with adhesive tape, using high‐resolution transmission electron microscopy and scanning transmission electron microscopy‐electron energy‐loss spectroscopy (STEM‐EELS). The surface step height of the exfoliated HOPG substrate was determined using high‐angle annular dark‐field‐scanning transmission electron microscopy (HAADF‐STEM) images and the depth profiles of the EELS spectra of a cross‐sectioned thin foil specimen prepared via focused ion beam milling. The exfoliated surface of the HOPG substrate presented disordered and curved graphene layers. The STEM‐EELS measurements indicated that upon exfoliation, the surface of the HOPG substrate reacted with atmospheric water and oxygen molecules.     

Direct Asymmetric Mannich‐Type Reaction of α‐Isocyanoacetates with Ketimines using Cinchona Alkaloid/Copper(II) Catalysts

The enantioselective direct Mannich‐type reaction of ketimines with α‐isocyanoacetates has been developed. Excellent yields and enantioselectivity were observed for the reaction of various ketimines and α‐isocyanoacetates using cinchona alkaloid/Cu(OTf)₂ and a base. Both enantiomers of the products could be obtained by using pseudoenantiomeric chiral catalysts. This process offers an efficient route for the synthesis of α,β‐diamino acids.     

Ultrafast Encapsulation of Metal Nanoclusters into MFI Zeolite in the Course of Its Crystallization: Catalytic Application for Propane Dehydrogenation

Encapsulating metal nanoclusters into zeolites combines the superior catalytic activity of the nanoclusters with high stability and unique shape selectivity of the crystalline microporous materials. The preparation of such bifunctional catalysts, however, is often restricted by the mismatching in time scale between the fast formation of nanoclusters and the slow crystallization of zeolites. We herein demonstrate a novel strategy to overcome the mismatching issue, in which the crystallization of zeolites is expedited so as to synchronize it with the rapid formation of nanoclusters. The concept was demonstrated by confining Pt and Sn nanoclusters into a ZSM-5 (MFI) zeolite in the course of its crystallization, leading to an ultrafast, in situ encapsulation within just 5 min. The Pt/Sn-ZSM-5 exhibited exceptional activity and selectivity with stability in the dehydrogenation of propane to propene. This method of ultrafast encapsulation opens up a new avenue for designing and synthesizing composite zeolitic materials with structural and compositional complexity.     

A new application of statistical moment theory to evaluate the swelling behavior of thermo-responsive gels

The loosely cross-linked poly(acryloyl-L -proline methyl ester) gel, which is known as one of the typical thermo-responsive gels, shows a volume transition around approximately 14°C in pure water. This volume transition is shifted to higher temperature by treatment in aqueous sodium dodecyl sulfate (SDS). The analysis of the swelling-temperature curve (frequency distribution) was performed according to a moment analysis, in which the area under the swelling-temperature curve (AUC), mean swelling transition temperature (MSTT) and variance of swelling transition temperature (VSTT) were calculated. It is shown that the apparent volume transition temperature can be estimated from MSTT and that VSTT can be used to characterize the shape of the corresponding curves.