Noncovalent Intermolecular Interaction in Cofacially Stacked 24π Antiaromatic Hexaphyrin Dimer

π–π Stacking is omnipresent not only in nature but in a wide variety of practical fields applied to our lives. Because of its importance in a performance of natural and artificial systems, such as light harvesting system and working layer in device, many researchers have put intensive effort into identifying its underlying nature. However, for the case of π–π stacked systems composed of antiaromatic units, the understanding of the fundamental mechanisms is still unclear. Herein, we synthesized a new type of planar β,β’-phenylene-bridged hexaphyrin (1.0.1.0.1.0), referred as naphthorosarin which possesses the 24π-electron conjugated pathway. Especially, the corresponding antiaromatic porphyrinoid shows the unique property to form dimeric species adopting the face-to-face geometry which is unprecedented in cases of known annulated naphthorosarins. In order to elucidate the intriguing properties derived from the stacked dimer, the current study focuses on the experimental support to rationalize the observed π–π interactions between the two subunits.     

Biological Removal of Phosphate at Low Concentrations Using Recombinant Escherichia coli Expressing Phosphate-Binding Protein in Periplasmic Space

During wastewater treatment, phosphate removal is an important and challenging process; thus, diverse technologies, including those derived from biological means, have been devised for efficient phosphate removal. Although conventional biological methods are effective in decreasing wastewater phosphate levels to ~1 mg/L, long periods of microbial adaptation are required for effective phosphate removal, and the removal efficiency of these methods is relatively poor at lower phosphate concentrations. In the present work, we constructed a recombinant Escherichia coli with periplasmic-expressed phosphate-binding protein (PBP) and investigated its biological removal ability for low phosphate levels. We found that the PBP-expressing recombinant E. coli cells showed efficient (> 94 %) removal of phosphate at low concentrations (0.2–1.0 mg/L) in a treated cell mass-dependent manner. Collectively, we propose that our PBP-expressing recombinant whole-cell system could be successfully used during wastewater treatment for the biological removal of low concentrations of phosphate.     

Aromatic CC Bonds as Dipolarophiles: Facile Reactions of Uncomplexed Electron‐Deficient Benzene Derivatives and Other Aromatic Rings with a Non‐Stabilized Azomethine Ylide

Non‐stabilized azomethine ylide 4 a reacts smoothly at room temperature with a variety of uncomplexed aromatic heterocycles and carbocycles on the condition that the ring contains at least one or two electron‐withdrawing substituents, respectively. Aromatic substrates, including pyridine and benzene derivatives, participate as 2 π components in [3+2] cycloaddition reactions and interact with one, two, or three equivalent(s) of the ylide, depending on their structure and substitution pattern. Thus, this process affords highly functionalized polycyclic structures that contain between one and three pyrrolidinyl ring(s) in useful yields. These results indicate that the site selectivity of the cycloaddition reactions strongly depends on both the nature and the positions of the substituents. In most cases, the second 1,3‐dipolar reaction occurs on the opposite face to the one that contains the first pyrrolidinyl ring. DFT calculations on model compounds indicate that a concerted mechanism features a low activation barrier.     

Deformations of Charged Axially Symmetric Initial Data and the Mass–Angular Momentum–Charge Inequality

We show how to reduce the general formulation of the mass–angular momentum–charge inequality, for axisymmetric initial data of the Einstein–Maxwell equations, to the known maximal case whenever a geometrically motivated system of equations admits a solution. It is also shown that the same reduction argument applies to the basic inequality yielding a lower bound for the area of black holes in terms of mass, angular momentum, and charge. This extends previous work by the authors (Cha and Khuri, Ann Henri Poincaré, doi: 10.1007/s00023-014-0332-6, arXiv:1401.3384, 2014), in which the role of charge was omitted. Lastly, we improve upon the hypotheses required for the mass–angular momentum–charge inequality in the maximal case.     

4,5-Dicyanoimidazole-promoted synthesis of dinucleoside polyphosphates and their analogs

A general and efficient P(V)–N activation method for the preparation of symmetrical and asymmetrical dinucleoside polyphosphates (Np_nN′s, n=2–4) and P²,P³-CX₂-dinucleoside tetraphosphates (X=H, F, and Cl) has been established. Twenty-two dinucleoside polyphosphates and their phosphonate analogs were synthesized from nucleoside 5′-phosphoropiperidates with 4,5-dicyanoimidazole as the activator in good to high yields.     

Assessment of the various ionization methods in the analysis of metal salen complexes by mass spectrometry

Metal salen complexes are one of the most frequently used catalysts in enantioselective organic synthesis. In the present work, we compare a series of ionization methods that can be used for the mass spectral analysis of two types of metalosalens: ionic complexes (abbreviated as Com⁺X^?) and neutral complexes (NCom). These methods include electron ionization and field desorption (FD) which can be applied to pure samples and atmospheric pressure ionization techniques: electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI) which are suitable for solutions. We found that FD is a method of choice for recording molecular ions of the complexes containing even loosely bonded ligands. The results obtained using atmospheric pressure ionization methods show that the results depend mainly on the structure of metal salen complex and the ionization method. In ESI spectra, Com⁺ ions were observed, while in APCI and APPI spectra both Com⁺ and [Com + H]⁺ ions are observed in the ratio depending on the structure of the metal salen complex and the solvent used in the analysis. For complexes with tetrafluoroborate counterion, an elimination of BF₃ took place, and ions corresponding to complexes with fluoride counterion were observed. Experiments comparing the relative sensitivity of ESI, APCI and APPI (with and without a dopant) methods showed that for the majority of the studied complexes ESI is the most sensitive one; however, the sensitivity of APCI is usually less than two times lower and for some compounds is even higher than the sensitivity of ESI. Both methods show very high linearity of the calibration curve in a range of about 3 orders of magnitude of the sample concentration. Copyright © 2014 John Wiley & Sons, Ltd.     

Therapeutic effect of hepatocyte growth factor-secreting mesenchymal stem cells in a rat model of liver fibrosis

Bone marrow-derived mesenchymal stromal cells (MSCs) have been reported to be beneficial for the treatment of liver fibrosis. Here, we investigated the use of genetically engineered MSCs that overexpress hepatocyte growth factor (HGF) as a means to improve their therapeutic effect in liver fibrosis. Liver fibrosis was induced by intraperitoneal injection of dimethylnitrosamine. HGF-secreting MSCs (MSCs/HGF) were prepared by transducing MSCs with an adenovirus carrying HGF-encoding cDNA. MSCs or MSCs/HGF were injected directly into the spleen of fibrotic rats. Tissue fibrosis was assessed by histological analysis 12 days after stem cell injection. Although treatment with MSCs reduced fibrosis, treatment with MSCs/HGF produced a more significant reduction and was associated with elevated HGF levels in the portal vein. Collagen levels in the liver extract were decreased after MSC/HGF therapy, suggesting recovery from fibrosis. Furthermore, liver function was improved in animals receiving MSCs/HGF, indicating that MSC/HGF therapy resulted not only in reduction of liver fibrosis but also in improvement of hepatocyte function. Assessment of cell and biochemical parameters revealed that mRNA levels of the fibrogenic cytokines PDGF-bb and TGF-β1 were significantly decreased after MSC/HGF therapy. Subsequent to the decrease in collagen, expression of matrix metalloprotease-9 (MMP-9), MMP-13, MMP-14 and urokinase-type plasminogen activator was augmented following MSC/HGF, whereas tissue inhibitor of metalloprotease-1 (TIMP-1) expression was reduced. In conclusion, therapy with MSCs/HGF resulted in an improved therapeutic effect compared with MSCs alone, probably because of the anti-fibrotic activity of HGF. Thus, MSC/HGF represents a promising approach toward a cell therapy for liver fibrosis.     

Preparation of thermal-enhanced epoxy resin adhesive with organic PCM for applying wood flooring

Epoxy resins are well-known materials that show beneficial properties, such as high tensile strength and modulus, good adhesive properties, low cost, and ease of processing and environmental advantages. However, epoxy resin adhesive has no characteristic of thermal storage. Latent heat storage is one of the favorable kinds of thermal energy storage methods considered for energy saving and thermal efficiency in various fields, such as solar air conditioning systems and buildings. So we prepared thermal-enhanced epoxy resin adhesive by using PCM. This paper addresses the effects of n-hexadecane and sodium lauryl sulfate on the thermal properties and chemical properties of epoxy resin adhesive and HEAC, using differential scanning calorimetry, thermal gravimetric analysis, and Fourier transform-infrared spectroscopy. Also, we evaluated the applicability of composite epoxy resin adhesive to wood-based flooring using n-hexadecane, through measurement of bonding strength from universal testing machine analysis.