Whole‐Cell Photoenzymatic Cascades to Synthesize Long‐Chain Aliphatic Amines and Esters from Renewable Fatty Acids

Long‐chain aliphatic amines such as (S,Z)‐heptadec‐9‐en‐7‐amine and 9‐aminoheptadecane were synthesized from ricinoleic acid and oleic acid, respectively, by whole‐cell cascade reactions using the combination of an alcohol dehydrogenase (ADH) from Micrococcus luteus, an engineered amine transaminase from Vibrio fluvialis (Vf‐ATA), and a photoactivated decarboxylase from Chlorella variabilis NC64A (Cv‐FAP) in a one‐pot process. In addition, long chain aliphatic esters such as 10‐(heptanoyloxy)dec‐8‐ene and octylnonanoate were prepared from ricinoleic acid and oleic acid, respectively, by using the combination of the ADH, a Baeyer–Villiger monooxygenase variant from Pseudomonas putida KT2440, and the Cv‐FAP. The target compounds were produced at rates of up to 37 U g^?1 dry cells with conversions up to 90 %. Therefore, this study contributes to the preparation of industrially relevant long‐chain aliphatic chiral amines and esters from renewable fatty acid resources.     

ChemInform Abstract: Synthesis and Structural Characterization of an Antiinflammatory Principle Purified from Lindera aggregata.

Linderaggrine A (I) exhibits significant inhibitory effects against the superoxide anion generation.     

β1-integrin-dependent migration of microglia in response to neuron-released α-synuclein

Chronic neuroinflammation is an integral pathological feature of major neurodegenerative diseases. The recruitment of microglia to affected brain regions and the activation of these cells are the major events leading to disease-associated neuroinflammation. In a previous study, we showed that neuron-released α-synuclein can activate microglia through activating the Toll-like receptor 2 (TLR2) pathway, resulting in proinflammatory responses. However, it is not clear whether other signaling pathways are involved in the migration and activation of microglia in response to neuron-released α-synuclein. In the current study, we demonstrated that TLR2 activation is not sufficient for all of the changes manifested by microglia in response to neuron-released α-synuclein. Specifically, the migration of and morphological changes in microglia, triggered by neuron-released α-synuclein, did not require the activation of TLR2, whereas increased proliferation and production of cytokines were strictly under the control of TLR2. Construction of a hypothetical signaling network using computational tools and experimental validation with various peptide inhibitors showed that β1-integrin was necessary for both the morphological changes and the migration. However, neither proliferation nor cytokine production by microglia was dependent on the activation of β1-integrin. These results suggest that β1-integrin signaling is specifically responsible for the recruitment of microglia to the disease-affected brain regions, where neurons most likely release relatively high levels of α-synuclein.     

Cobalt Complexes with Pyrazole Ligands as Catalyst Precursors for the Peroxidative Oxidation of Cyclohexane: X‐ray Absorption Spectroscopy Studies and Biological Applications

[CoCl(μ‐Cl)(Hpz^Ph)₃]₂ ( 1 ) and [CoCl₂(Hpz^Ph)₄] ( 2 ) were obtained by reaction of CoCl₂ with HC(pz^Ph)₃ and Hpz^Ph, respectively (Hpz^Ph=3‐phenylpyrazole). The compounds were isolated as air‐stable solids and fully characterized by IR and far‐IR spectroscopy, MS(ESI+/?), elemental analysis, cyclic voltammetry (CV), controlled potential electrolysis, and single‐crystal X‐ray diffraction. Electrochemical studies showed that 1 and 2 undergo single‐electron irreversible Co^II→Co^III oxidations and Co^II→Co^I reductions at potentials measured by CV, which also allowed, in the case of dinuclear complex 1 , the detection of electronic communication between the Co centers through the chloride bridging ligands. The electrochemical behavior of models of 1 and 2 were also investigated by density functional theory (DFT) methods, which indicated that the vertical oxidation of 1 and 2 (that before structural relaxation) affects mostly the chloride and pyrazolyl ligands, whereas adiabatic oxidation (that after the geometry relaxation) and reduction are mostly metal centered. Compounds 1 and 2 and, for comparative purposes, other related scorpionate and pyrazole cobalt complexes, exhibit catalytic activity for the peroxidative oxidation of cyclohexane to cyclohexanol and cyclohexanone under mild conditions (room temperature, aqueous H₂O₂). In situ X‐ray absorption spectroscopy studies indicated that the species derived from complexes 1 and 2 during the oxidation of cyclohexane (i.e., Ox‐ 1 and Ox‐ 2 , respectively) are analogous and contain a Co^III site. Complex 2 showed low in vitro cytotoxicity toward the HCT116 colorectal carcinoma and MCF7 breast adenocarcinoma cell lines.     

Functional Limit Theorems for d-dimensional FBM in HSlder Norm

In this paper, we obtain functional limit theorems for d-dimensional FBM in HSlder norm via estimating large deviation probabilities for d-dimensional FBM in HSlder norm.     

Modeling and large sample estimation for multi-casting autoregression

Multi-casting autoregression (MCAR, for short) is suggested as a natural extension of the bifurcating autoregressive (BAR) model (cf. [Cowan, R., Staudte, R.G., 1986. The bifurcating autoregression model in cell lineage studies. Biometrics 42, 769–783]) in order to analyze multi-splitting tree-structured data. Pathwise stationarity of the MCAR model is discussed. Least squares estimation for the autoregressive parameter is considered and relevant limiting distribution is derived, in particular, for the pathwise explosive case. These results can be regarded as generalizations of those for standard stationary and explosive AR(1) time series. A simulation study is conducted to illustrate our results.     

A smeared / layered reinforced concrete model for finite element analysis

A new reinforced concrete model, in which the reinforcement steel is assumed as smeared / layered in concrete, is established and installed into a currently used finite element code for nonlinear analysis. It performs the nonlinear behaviors of both concrete and the reinforcement steel. The results of examples are in good agreement with the experimental data.     

Construction of BIB designs with various support sizes—with special emphasis for v = 8 and k = 4

This paper deals with methods of constructing new BIB designs from known designs. First, we provide a method of finding trades on a given BIB design so that new designs with the same parameters ν, b, k can be constructed. Second, we point out that the method of combining designs mentioned in [9] is particularly useful for constructing designs based on ν = 2k, k even, when designs based on ν = 2k ? 1 are available. By utilizing the above methods with the aid of Table I in [4], we have constructed a table of 53 BIB designs based on V = 8 and k = 4 with support sizes $\text{14 ? b 1 (}\text{8}\text{4}\text{)=70}$ except for $\text{b}{}^1\text{= 15, 16, 17, 19}$. BIB designs with ν = 8, k = 4 and $\text{b}{}^1\text{< 14}$ are shown to be nonexistent.     

The Mean-Partition Problem

In mean-partition problems the goal is to partition a finite set of elements, each associated with a d-vector, into p disjoint parts so as to optimize an objective, which depends on the averages of the vectors that are assigned to each of the parts. Each partition is then associated with a d × p matrix whose columns are the corresponding averages and a useful approach in studying the problem is to explore the mean-partition polytope, defined as the convex hull of the set of matrices associated with feasible partitions.     

Antiferromagnet IrMn thickness dependence in exchange-biased perpendicular magnetic anisotropy based on CoFe/Pt/CoFe/[IrMn(tIrMn)] multilayers

The effect of the antiferromagnetic IrMn thickness upon the magnetic properties of CoFe/Pt/CoFe/[IrMn(t_IrMn)] multilayers is studied. An oscillatory interlayer coupling (IEC) has been shown in pinned CoFe/Pt(t_Pt)/CoFe/IrMn multilayers with perpendicular anisotropy. The period of oscillation corresponds to about 2 monolayers of Pt. The oscillatory behavior of IEC depends on the nonmagnetic metallic Pt thickness and is thought to be related to the antiferromagnetic ordering induced by the IrMn layer. From the extraordinary Hall voltage amplitude (EHA) curves as function of IrMn thickness, we report that the oscillation dependence of IEC for the [CoFe/Pt/CoFe] multilayer system induced by IrMn with spacer-layer thickness is a important features of perpendicular exchange biased system.