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1.
Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark.  相似文献   
2.
Chiral cyclic [n]spirobifluorenylenes consisting of helically arranged quaterphenyl rods, illustrating partial units of woven patterns, were designed and synthesized as a new family of carbon nanorings. The synthesis was accomplished by the Ni(0)-mediated Yamamoto-coupling of chiral spirobifluorene building blocks. The structures of the cyclic 3-, 4-, and 5-mers were determined by X-ray crystallographic analysis. These carbon nanorings exhibited a strong violet colored emission with high quantum yields in solution (95%, 93%, and 94% for 3-, 4-, and 5-mer, respectively). Other spectroscopic properties, including their chiroptical properties, were also investigated. The g-values for circularly polarized luminescence were found to be in the order of 10−3. Characteristic spiroconjugation induced by multiple (≧3) bifluorenyl units, for example the even-odd effect of the number of units in the matching of the signs of the orbitals, was also indicated by DFT calculations.

Chiral cyclic [n]spirobifluorenylenes consisting of helically arranged quaterphenyl rods, illustrating partial units of woven patterns, were designed and synthesized as a new family of carbon nanorings.  相似文献   
3.
The reductive cleavage of the C–O bonds of aryl ethers has great potential in organic synthesis. Although several catalysts that can promote the reductive cleavage of aryl ethers have been reported, all such systems require the use of an external reductant, e.g., hydrosilane or hydrogen. Here, we report the development of a new nickel-based catalytic system that can cleave the C–O bonds of ethers in the absence of an external reductant. The hydrogen atom required in this new reductive cleavage reaction is provided by the alkoxy group of the substrate, which serves as an internal reductant. The absence of an external reductant enables the unique chemoselectivity, i.e., the selective reduction of an alkoxy group over alkenes and ketones.  相似文献   
4.
4‐Substituted tryptophan derivatives and the total synthesis of cis‐clavicipitic acid were achieved in reactions in which Ir‐catalyzed C?H bond activation was a key step. The starting material for these reactions is asparagine, which is a cheap natural amino acid. The reductive amination step from the 4‐substituted tryptophan derivative gave cis‐clavicipitic acid with perfect diastereoselectivity.  相似文献   
5.
Appropriate experimental platforms are required to clarify the structure–function relationships of membrane protein assemblies. In photosynthetic bacteria, light-harvesting complex 2 and light-harvesting/reaction center core complex play key roles in capturing and transferring light energy and facilitating subsequent charge separation. These photosynthetic apparatuses form a supramolecular assembly in the photosynthetic membrane. However, the mechanism through which this assembly influences the efficiency of energy conversion remains to be clarified. We review our recent studies that were conducted to evaluate the structure–function relationship of the supramolecular assembly of photosynthetic antenna complexes in various lipid bilayer systems, as well as the construction of novel systems of planar lipid membranes for use as experimental platforms.  相似文献   
6.

Purpose

To evaluate the use of the intravoxel incoherent motion (IVIM) technique in half-Fourier single-shot turbo spin-echo (HASTE) diffusion-weighted imaging (DWI), and to compare its accuracy to that of apparent diffusion coefficient (ADC) to predict malignancy in head and neck tumors.

Patients and methods

HASTE DW images of 33 patients with head and neck tumors (10 benign and 23 malignant) were evaluated. Using the IVIM technique, parameters (D, true diffusion coefficient; f, perfusion fraction; D*, pseudodiffusion coefficient) were calculated for each tumor. ADC values were measured over a range of b values from 0 to 1000 s/mm2. IVIM parameters and ADC values in benign and malignant tumors were compared using Student's t test, receiver operating characteristics (ROC) analysis, and multivariate logistic regression modeling.

Results

Mean ADC and D values of malignant tumors were significantly lower than those of benign tumors (P < 0.05). Mean D* values of malignant tumors were significantly higher than those of benign tumors (P < 0.05). There was no significant difference in mean f values between malignant and benign tumors (P > 0.05). The technique of combining D and D* was the best for predicting malignancy; accuracy for this model was higher than that for ADC.

Conclusions

The IVIM technique may be applied in HASTE DWI as a diagnostic tool to predict malignancy in head and neck masses. The use of D and D* in combination increases the diagnostic accuracy in comparison with ADC.  相似文献   
7.
ZnO deposited on nanoporous Au showed photocatalytic decomposition toward methyl orange under visible light, unlike ZnO sputtered on flat Au without a nanoporous structure. First-principles calculations suggested that the surface lattice disorder in nanoporous Au induced a band gap narrowing and a large built-in electric field in the adjacent ZnO, resulting in the visible-light photocatalytic response.  相似文献   
8.
9.
A liquid chromatography/electrospray ionization–tandem mass spectrometry‐based method was developed for the identification of the conjugation positions of the monoglucuronides of 25‐hydroxyvitamin D3 [25(OH)D3] and 24,25‐dihydroxyvitamin D3 [24,25(OH)2D3] in human urine. The method employed derivatization with 4‐(4‐dimethylaminophenyl)‐1,2,4‐triazoline‐3,5‐dione to convert the glucuronides into fragmentable derivatives, which provided useful product ions for identifying the conjugation positions during the MS/MS. The derivatization also enhanced the assay sensitivity and specificity for urine sample analysis. The positional isomeric monoglucuronides, 25(OH)D3‐3‐ and ‐25‐glucuronides, or 24,25(OH)2D3‐3‐, ‐24‐ and ‐25‐glucuronides, were completely separated from each other under the optimized LC conditions. Using this method, the conjugation positions were successfully determined to be the C3 and C24 positions for the glucuronidated 25(OH)D3 and 24,25(OH)2D3, respectively. The 3‐glucuronide was not present for 24,25(OH)2D3, unlike 25(OH)D3, thus we found that selective glucuronidation occurs at the C24‐hydroxy group for 24,25(OH)2D3.  相似文献   
10.
Concerted nucleophilic aromatic substitution (CSNAr) has emerged as a powerful mechanistic manifold, in which nucleophilic aromatic substitution can proceed in one step without the need to form a Meisenheimer intermediate. However, all of the CSNAr reactions reported thus far require a stoichiometric strong base or activating reagent, and no catalytic variants have yet been reported. Herein, we report an N‐heterocyclic carbene (NHC)‐catalyzed intramolecular cyclization of acrylamides that contain a 2‐fluorophenyl group on the nitrogen through a CSNAr reaction. By using this catalytic method, it is possible to synthesize an array of quinolin‐2‐one derivatives, which are common structural motifs in pharmaceuticals and organic materials. DFT calculations unambiguously revealed that this reaction proceeds through the concerted nucleophilic aromatic substitution of aryl fluorides, in which a stereoelectronic σ (Cipso‐Cβ)→ σ*(Cipso‐F) interaction critically contributes to the stabilization of the transition state for the cyclization.  相似文献   
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