A concise and stereospecific synthesis of some cyclitols containing eight-membered rings: cyclooctane-1,2,3,4-tetraoles

A concise and efficient synthesis of cyclooctane-1,2,3,4-tetraoles, new polyhydroxylated eight-membered carbocycles, is described starting from cis,cis-1,3-cyclooctadiene. Cyclooctene endoperoxide obtained by photooxygenation of cis,cis-1,3-cyclooctadiene was the key compound in the synthesis. Reduction of the endoperoxide with zinc or thiourea followed by acetylation of the hydroxyl group and OsO₄/NMO oxidation of the double bond gave (1R(S),2S(R),3R(S),4S(R))-cyclooctane-1,2,3,4-tetraol. Interestingly, epoxidation of cyclooctene-1,4-diol with m-CPBA also afforded trans-epoxy-diol 17. (1R(S),2R(S),3R(S),4S(R))-cyclooctane-1,2,3,4-tetraol was easily obtained by hydrolysis of epoxy-diol 17.     

Facilitated Transfer of Alkali and Alkaline‐Earth Metal Ions by a Calix[4]arene Derivative Across Water/1,2‐Dichloroethane Microinterface: Amperometric Detection of Ca2+

The host–guest complexation reactions between 5,11,17,23‐tetra‐tert‐butyl‐25,27‐diethoxycarbonylmethoxy‐26,28‐dimethoxy calix[4]arene (BDDC4) and alkali and alkaline‐earth metal ions were investigated by facilitated ion transfer processes across water/1,2‐dichloroethane microinterface by using steady‐state cyclic voltammetry and differential pulse voltammetry. The obtained facilitated transfers for Li⁺, Na⁺, K⁺, Rb⁺ and Ca²⁺ were evaluated under the different experimental conditions, at the excess concentrations of metal ions with respect to BDDC4 and vice versa. The association constants having 1 : 1 stoichiometry for Li⁺, Na⁺, K⁺ and Rb⁺ in 1,2‐DCE were determined. Also, we demonstrated that BDDC4 can play an important role for the development of highly selective chemical sensor for Ca²⁺ among alkaline‐metal ions in the concentration range of 0.1–1.0 mM in aqueous solution.     

Preparation of a series of Ru(II) complexes with N-heterocyclic carbene ligands for the catalytic transfer hydrogenation of aromatic ketones

The reaction of [RuCl(2)(p-cymene](2) with Ag-N-heterocyclic carbene (NHC) complexes yields a series of [(p-cymene)Ru(NHC)] complexes (2a-f). All synthesised compounds were characterized by elemental analysis, NMR spectroscopy and the molecular structure of 2a was determined by X-ray crystallography. All complexes have been tested as catalysts for the transfer hydrogenation of aromatic ketones, showing excellent activity in this reaction.     

Energy and Momentum of Higher Dimensional Black Holes

In this paper, we devote to investigate the energy-momentum problem of higher dimensional black holes in the general theory of relativity. The energy and momentum complex of M?ller has been used for the calculations. Also, total energy and total momentum of some special cases for higher dimensional black holes such as Schwarzschild-like black holes, Reissner-Nordstr?m-like charged black holes, AdS-like black holes, topological black holes, BTZ-like and charged BTZ-like black holes were obtained. It is invented that the momentum of black holes vanishes everywhere while the energy of black holes are not equal to zero in higher dimension. Also the results agree with Yang and Radinschi or Vagenas results in three and four dimensional black holes, respectively (Jang and Radinschi in AIP Conf. Proc. 895, 325, 2007; Vagenas in Mod. Phys. Lett. A 21, 1947, 2006).     

Epibatidine alkaloid chemistry: 5. Domino-Heck reactions of azabicyclic and tricyclic systems

Palladium-catalyzed hydroarylations and additional domino reactions of aza-bicyclic and tricyclic norbornene derivatives were investigated and a series of new epibatidine analogues were synthesized.     

Assessment of the orbital‐optimized coupled‐electron pair theory for thermochemistry and kinetics: Improving on CCSD and CEPA(1)

An assessment of the orbital‐optimized coupled‐electron pair theory [or simply “optimized CEPA(0),” OCEPA(0)] [Bozkaya and Sherrill, J. Chem. Phys. 2013, 139, 054104] for thermochemistry and kinetics is presented. The OCEPA(0) method is applied to closed‐ and open‐shell reaction energies, barrier heights, and radical stabilization energies (RSEs). The performance of OCEPA(0) is compared with those of the MP2, CEPA(0), OCEPA(0), CEPA(1), coupled‐cluster singles and doubles (CCSD), and CCSD(T) methods [at complete basis set limits employing cc‐pVTZ and cc‐pVQZ basis sets]. For the most of the test sets, the OCEPA(0) method performs better than CEPA(0), CEPA(1), and CCSD, and provides accurate results. Especially, for open‐shell reaction energies and barrier heights, the OCEPA(0)–CEPA(1) and OCEPA(0)–CCSD differences become obvious. Similarly, for barrier heights and RSEs, the OCEPA(0) method improves on CEPA(0) by 1.6 and 2.3 kcal mol^?1. Our results demonstrate that the CEPA(0) method dramatically fails when the reference wave function suffers from the spin‐contamination problem. Conversely, the OCEPA(0) method can annihilate spin‐contamination in the unrestricted‐Hartree–Fock initial guess orbitals and can yield stable solutions. For overall evaluation, we conclude that the OCEPA(0) method is quite helpful not only for problematic open‐shell systems and transition‐states but also for closed‐shell molecules. Hence, one may prefer OCEPA(0) over CEPA(0), CEPA(1), and CCSD as an method, where N is the number of basis functions, for thermochemistry and kinetics. As discussed previously, the cost of the OCEPA(0) method is as much as of CCSD and CEPA(1) for energy computations. However, for analytic gradient computations, the OCEPA(0) method is two times less expensive than CCSD and CEPA(1). Further, the stationary properties of the OCEPA(0) method making it promising for excited state properties via linear response theory. © 2014 Wiley Periodicals, Inc.     

HPLC Separation of Different Groups of Small Polar Compounds on a Novel Amide-Embedded Stationary Phase

Retention behaviors of an amide-embedded silica base stationary phase, which was recently developed by our group, were studied by using six different groups of small polar compounds including phenolic compounds, substituted anilines, chlorinated herbicides, Sudan dyes and some nucleotides and nucleosides in HPLC. The chromatographic behaviors of the prepared stationary phase for these analytes were compared with those of a commercially available reversed-phase column ACE C18 under same conditions. Among the six groups of analytes studied, the amide-silica stationary phase showed enhanced selectivity towards phenolic compounds, substituted anilines, Sudan dyes and herbicides under reversed-phase conditions and satisfactory selectivity towards nucleosides and nucleotides which could not be separated with ACE C18 column under HILIC conditions. Experimental data provided some evidence that functional groups on the stationary phases might have certain degrees of influence on selectivity possibly through secondary interactions with the model compounds. The retentions of the moderately polar compounds such as phenolic acids, anilines and herbicides on the stationary phase are higher than highly polar compounds such as nucleotides and nucleosides due to both the hydrophobic and hydrophilic interactions between the stationary phase and analytes. The quantitative determination of Sudan dyes (I, II, III, and IV) in red chilli peppers was performed. Many red chilli peppers were screened and three of them contained Sudans dyes.     

A Novel Synthesis of DL-proto-, and DL-vibo-Quercitol via 1, 4-Cyclohexadiene

Photooxygenation of 1, 4-cyclohexadiene 3 followed by reduction with LiAlH₄ or thiourea gave (25/1)-cyclohex-3-ene-triol 7a. trans-Hydroxylation of triol 7a with three different methods afforded both of proto-quercitol la and vibo-quercitol 2a.     

Synthesis,Characterization, and Biological Evaluation of Some Novel Thiosemicarbazones as Possible Antibacterial and Antioxidant Agents

Abstract

The synthesis and characterization of 18 novel thiosemicarbazones have been investigated as part of a research program on development of compounds with antibacterial and antioxidant activities. Among the tested compounds, 2-(4-hydroxybenzylidene)-N-[4-(trifluoromethoxy)phenyl]hydrazine carbothioamide (3g) and 2-(thiophen-2-ylmethylidene)-N-[4-(morpholin-4-yl)phenyl]hydrazine carbothioamide (4b) showed excellent inhibition potency at low concentration (0.5 μg/mL) against Gram-positive pathogens (Enterococcus faecalis and Staphylococcus aureus). All tested compounds were also found to possess antioxidant activity against 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical and 2,2’-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical cation.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional text, tables, and figures.]     

Additive manufacturing and biomechanical validation of a patient‐specific diabetic insole

Centers for Disease Control and Prevention (CDC) has reported that lower extremity amputation (LEA) rate of per 1000 diabetic patients is 18.4 because of the complications that first appeared in the foot. A second amputation is also required for 9% to 17% of these patients within the same year although LEA may be preventable. Most of the diabetic foot conditions may be prevented and treated by a therapeutic footwear or a medical device such as an insole or an orthotic shoe. Traditional insole manufacturing is a laborious work that requires specific skills. Moreover, traditional approaches contain harmful material particles that may cause respiratory failure. Unfortunately, manufactured insoles may not be suitable for any mass‐produced footwear in all cases. Therefore, patient requires to get insole‐specific footwear. In this study, a diabetic insole was manufactured by means of a fused deposition modeling‐(FDM) based system and a thermoplastic polymer. Biomechanical functionality was determined according to the applied polymer analysis on each produced sample and foam material. Subsequently, finite element analysis (FEA) was performed to target insole geometry to ensure the quality of the final medical product. Additive and traditional manufactured insoles are compared according to the cost and function. As a result, fabrication of an insole, based on the FDM method, was improved down to 8 h and 9 m. The weight of an insole prototype was 74.74 g, and the material cost was $3.44 while total cost of the traditional foam casting was determined as $35.37 and weight of the insole was 72.6 g for this study. Consequently, benefits of the applied method are evaluated.