Paecilomycines A and B,Novel Diterpenoids,Isolated from Insect‐Pathogenic Fungi Paecilomyces sp. ACCC 37762

Two new diterpenoids, named paecilomycine A ( 1 ) and paecilomycine B ( 2 ), including a novel skeleton with a five‐membered lactone ring, together with three known labdane diterpenoids, rel‐(1R,3S,4aS,5R,8aS)‐5‐[(3E)‐4‐carboxy‐3‐methylbut‐3‐en‐1‐yl]decahydro‐3‐hydroxy‐1,4a‐dimethyl‐6‐methylidenenaphthalene‐1‐carboxylic acid ( 3 ), botryosphaerin E ( 4 ), and agathic acid ( 5 ), were isolated from solid culture of the insect pathogenic fungi strain Paecilomyces sp. The structures of all compounds were established on the basis of comprehensive spectroscopic studies. The relative configurations of 1 and 2 were determined by single‐crystal X‐ray diffraction analyses.     

Direct Conversion of Bulk Metals to Size‐Tailored,Monodisperse Spherical Non‐Coinage‐Metal Nanocrystals

Monodisperse non‐noble metal nanocrystals (NCs) that are highly uniform in shapes and particle size are much desired in various advanced applications, and are commonly prepared by either thermal decomposition or reduction, where reactive organometallic precursors or/and strong reducing agents are mandatory; however, these are usually toxic, costly, or suffer a lack of availability. Bulk Group 12 metals can now be converted into ligand‐protected, highly crystalline, monodisperse spherical metal NCs with precisely controlled sizes without using any precursors and reducers. The method is based on low‐power NIR‐laser‐induced size‐selective layer‐by‐layer surface vaporization. The monodisperse Cd NCs show pronounced deep‐UV (DUV) localized surface plasmon resonance making them highly competitive DUV‐plasmonic materials. This approach will promote appreciably the emergence of a wide range of monodisperse technically important non‐coinage metal NCs with compelling functionalities.     

Thermo-sensitive poly(DEGMMA-co-MEA) microgels: Synthesis,characterization and interfacial interaction with adsorbed protein layer

The novel microgels, poly[di(ethylene glycol) methyl ether methacrylate-co-2-methoxyethyl acrylate] poly(DEGMMA-co-MEA) microgels, were synthesized. The poly(DEGMMA-co-MEA) microgels were thermo-sensitive and exhibited a volume phase transitive temperature(VPTT) of 14–22 ?C. The incorporation of hydrophobic comonomer MEA shifted the VPTT of poly(DEGMMA-co-MEA) microgels to lower temperatures. The interfacial interaction of poly(DEGMMA-co-MEA) microgels and three model proteins, namely fibrinogen, bovine serum albumin and lysozyme, was investigated by quartz crystal microbalance(QCM). An injection sequence of "microgel-after-protein" was then established for the real-time study of the interaction of proteins and the microgels at their swollen and collapsed states by using QCM technique. The results indicated that the interfacial interaction of poly(DEGMMA-co-MEA) microgels and adsorbed protein layers was mainly determined by the electrostatic interaction. Because poly(DEGMMA-co-MEA) microgels were negatively charged in Tris-HCl buffer solution(p H = 7.4), the microgels did not adsorb on negatively charged fibrinogen and bovine serum albumin layers but strongly adsorbed on positively charged lysozyme layer. Stronger interaction between lysozyme and the microgels at collapsed state(i.e. at 37 ?C) was observed. Furthermore, the incorporation of MEA might weaken the interaction between poly(DEGMMA-co-MEA) microgels and proteins.     

Flame-retardant Wrapped Ramie Fibers towards Suppressing “Candlewick Effect” of Polypropylene/Ramie Fiber Composites

In this work, a flame-retardant polypropylene(PP)/ramie fiber(RF) composite was prepared. The ramie fibers were wrapped chemically by a phosphorus- and nitrogen-containing flame retardant(FR) produced via in situ condensation reaction so as to suppress their candlewick effect. Fourier transform infrared spectroscopy(FTIR), X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy(SEM) demonstrated that the ramie fibers wrapped chemically by FR(FR-RF) were obtained successfully. Thermogravimatric test showed that the PP/FR-RF composite had more residue and better thermal stability at high temperatures than the PP/RF composite. Cone calorimeter(CC) results indicated that the peak of heat release rate(PHRR) and total heat release(THR) correspondingly decreased by 23.4% and 12.5% compared with the values of neat PP/RF. The PP/FR-RF composite created a continuous and compact char layer after the combustion. Combining FTIR analysis of char residue after CC test with heat conduction coefficient results, it could be concluded that the charring of FR on RF greatly weakened the candlewick effect of RF, and more char residue in the RF domain facilitated the formation of more continuous and compact char layer in the whole combustion zone, consequently protected PP composites during combustion, resulting in the better flame retardancy of PP/FR-RF composite than that of PP/RF composite.     

Formation of a vanillic Mannich base — theoretical study

One-pot anti-Mannich reaction of vanillin, aniline and cyclohexanone was successfully catalyzed by ionic liquid triethanolammonium chloroacetate, at room temperature. Yield of the obtained Mannich base was very good and excellent diastereoselectivity was achieved. Mechanism of the reaction was investigated using the density functional theory. The reaction started with a nucleophilic attack of aniline nitrogen at the carbonyl group of vanillin. The intermediate α-amino alcohol formed in this way was further subjected to protonation by the triethanolammonium ion yielding the imminium ion. Theoretically, the obtained imminium ion and the enol form of cyclohexanone can build the protonated Mannich base via the anti and syn pathways. The chloroacetic anion spontaneously abstracts the proton yielding the final product of the reaction anti 2-[1-(N-phenylamino)-1-(4-hydroxy-3-methoxyphenyl)]methylcyclohexanone (MB-H). The syn pathway requires lower activation energy but the anti pathway yields a thermodynamically more stable product, which implies that the examined Mannich reaction is thermodynamically controlled.     

Single‐Crystal‐to‐Single‐Crystal Transition in an Enantiopure [7]Helquat Salt: The First Observation of a Reversible Phase Transition in a Helicene‐Like Compound

Here it is reported that crystals of an enantiopure [7]helquat salt undergo reversible thermal solid–solid phase transition at 404 K. Differential scanning calorimetry (DSC), capillary electrophoresis (CE), and X‐ray diffraction analysis were used to unravel the mechanistic details of this process. The single‐crystal‐to‐single‐crystal course enabled direct monitoring of the structural changes by in situ variable‐temperature X‐ray diffraction, thus providing the first direct evidence of a solid phase transition in a helicene‐like compound.