Unique Ring Research Articles

Crystal structures of N2,N3,N5,N6-tetra-kis-(pyridin-2-ylmeth-yl)pyrazine-2,3,5,6-tetra-carboxamide and N2,N3,N5,N6-tetra-kis-(pyridin-4-ylmeth-yl)pyrazine-2,3,5,6-tetra-carboxamide.

The title compounds, C32H28N10O4· unknown solvent, (I), and C32H28N10O4, (II), are pyrazine-2,3,5,6-tetra-carboxamide derivatives. In (I), the substituents are (pyridin-2-ylmeth-yl)carboxamide, while in (II), the substituents are (pyridin-4-ylmeth-yl)carboxamide. Both compounds crystallize in the monoclinic space group P21/n, with Z' = 1 for (I), and Z' = 0.5 for (II). The whole mol-ecule of (II) is generated by inversion symmetry, the pyrazine ring being situated about a center of inversion. In (I), the four pyridine rings are inclined to the pyrazine ring by 83.9 (2), 82.16 (18), 82.73 (19) and 17.65 (19)°. This last dihedral angle involves a pyridine ring that is linked to the adjacent carboxamide O atom by an intra-molecular C-H⋯O hydrogen bond. In compound (II), the unique pyridine rings are inclined to the pyrazine ring by 33.3 (3) and 81.71 (10)°. There are two symmetrical intra-molecular C-H⋯O hydrogen bonds present in (II). In the crystal of (I), mol-ecules are linked by N-H⋯O and N-H⋯N hydrogen bonds, forming layers parallel to (10-1). The layers are linked by C-H⋯O and C-H⋯N hydrogen bonds, forming a three-dimensional framework. In the crystal of (II), mol-ecules are linked by N-H⋯N hydrogen bonds, forming chains propagating along the [010] direction. The chains are linked by a weaker N-H⋯N hydrogen bond, forming layers parallel to the (101) plane, which are in turn linked by C-H⋯O hydrogen bonds, forming a three-dimensional structure. In the crystal of compound (I), a region of disordered electron density was treated with the SQUEEZE routine in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18]. Their contribution was not taken into account during refinement. In compound (II), one of the pyridine rings is positionally disordered, and the refined occupancy ratio for the disordered Car-Car-Npy atoms is 0.58 (3):0.42 (3).

複雑な炭素骨格の構築法

Ryanodine is a ryanodane diterpene isolated from Ryania speciosa in 1948. This compound has an agonist activity for ryanodine receptor (RyR) as the calcium channel. Moreover, ryanodol is known as the hydrolysis analogue of ryanodine. The structural features of these compounds are a unique complex ring system with highly oxygenated carbon skeleton. Thus, it is important to construct pentacyclic rings and introduce oxygen functions efficiently for the synthesis. In this review, the total syntheses of ryanodol reported by three groups are described.

Glioblastoma multiforme presenting with an open ring pattern of enhancement on MR imaging

Background:Intracerebral ring enhancing lesions can be the presentation of a variety of pathologies, including neoplasia, inflammation, and autoimmune demyelination. Use of a precise diagnostic algorithm is imperative in correctly treating these lesions and minimizing potential adverse treatment effects.Case Description:A 55-year-old patient presented to the hospital with complaints of a post-concussive syndrome and a non-focal neurologic exam. Imaging revealed a lesion with an open ring enhancement pattern, minimal surrounding vasogenic edema, and minimal mass effect. Given the minimal mass effect, small size of the lesion, and nonfocal neurological exam, we elected to pursue a comprehensive noninvasive neurologic workup because our differential ranged from inflammatory/infectious to neoplasm. Over the next 8 weeks, the patient's condition worsened, and repeat imaging showed marked enlargement of the lesion with a now closed ring pattern of enhancement with satellite lesions and a magnetic resonance (MR) spectroscopy and perfusion signature suggestive of neoplasm. The patient was taken to surgery for biopsy and debulking of the lesion. Surgical neuropathology examination revealed glioblastoma multiforme.Conclusion:The unique open ring enhancement pattern of this lesion on initial imaging is highly specific for a demyelinating process, however, high-grade glial neoplasms can also present with complex and irregular ring enhancement including an open ring sign. Therefore, other imaging modalities should be used, and close follow-up is warranted when the open ring sign is encountered.

Radical-Mediated C-H Functionalization: A Strategy for Access to Modified Cyclodextrins.

A simple and efficient radical C-H functionalization to access modified cyclodextrins (CDs) has been developed. The well-defined conformation of glycosidic and aglyconic bonds in α-, β-, and γ-CDs favors the intramolecular 1,8-hydrogen atom transfer (HAT) promoted by the 6I-O-yl radical, which abstracts regioselectively the hydrogen at C5II of the contiguous pyranose. The C5II-radical evolves by a polar crossover mechanism to a stable 1,3,5-trioxocane ring between two adjacent glucoses or alternatively triggers the inversion of one α-d-glucose into a 5-C-acetoxy-β-l-idose unit possessing a 1C4 conformation. The 6I,IV- and 6I,III-diols of α- and β-CDs behave similarly to the monoalcohols, forming mostly compounds originating from two 1,8-HAT consecutive processes. In the case of 6I,II-diols the proximity of the two 6-O-yl radicals in adjacent sugar units allows the formation of unique lactone rings within the CD framework via a 1,8-HAT-β-scission tandem mechanism. X-ray diffraction carried out on the crystalline 1,4-bis(trioxocane)-α-CD derivative shows a severe distortion toward a narrower elliptical shape for the primary face.

Factorizations in self-idealizations of PIRs and UFRs

The self-idealization of a commutative ring R is isomorphic to the ring \(R[x]/(x^2)\) or, equivalently, the ring of upper-triangular Toeplitz matrices \({{\mathrm{\mathcal {T}}}}(R)=\left\{ \left( \begin{matrix} a &{} b \\ 0 &{} a \end{matrix}\right) :a,b\in R\right\} \). Recently, Chang and Smertnig characterized the sets of lengths of factorizations in \({{\mathrm{\mathcal {T}}}}(D)\) where D is a principal ideal domain. In this work, in addition to correcting an error in their paper, we extend the study to \({{\mathrm{\mathcal {T}}}}(R)\) when R is either a principal ideal ring or a unique factorization ring.

Unique maximal rings of functions

ABSTRACTFor several classes of groups G, we characterize when the near-ring M0(G) of 0-preserving selfmaps on G contains a unique maximal ring. Definitive results are obtained for finite Abelian, finite nilpotent, and finite permutation groups. As an application, we determine those finite groups G such that all rings in M0(G) are commutative.

Asymmetric Total Synthesis of (−)-Lycospidine A

The first asymmetric total synthesis of the structurally unique Lycopodium alkaloid (-)-lycospidine A, containing an unprecedented five-membered ring, has been accomplished in only 10 steps with 21.6% overall yield from the known conveniently available sulfoxide. This protecting-group-free short synthesis relied on the use of a key amidation/aza-Prins domino cyclization reaction to rapidly construct the tricyclic skeleton and two continuous stereocenters (one of which is a bridged quaternary stereocenter). An intramolecular aldol condensation was successfully utilized to establish the unique five-membered ring, and a late-stage oxidation inspired by biosynthesis pathway was adopted to synthesize the diosphenol ring of (-)-lycospidine A.

Personalized Ring Design and Rapid Manufacturing Based on Reverse Engineering and 3D Printing

Ring as a souvenir and decorations for common people. Due to the design of the market a lot of repetition, people often wish have a unique custom ring , which often have personal logo. This paper Introduces a method of through the fingers to do a CT scan, reverse engineering software and 3 d printing to manufacture custom unique ring for people, This method has high practical value.

ChemInform Abstract: Two‐Carbon Ring Expansion of Isatin: A Convenient Construction of a Dibenzo[b,d]azepinone Scaffold.

A unique two-carbon ring expansion of isatin has been achieved to conveniently construct the functionalized dibenzo[b,d]azepin-6-one scaffold in moderate to high yields, and the two carbon sources are different: one carbon is from the N-substituent of pyridinium bromide and the other is from indene-1,3-dione.

Nilradicals of the unique product monoid rings

Armendariz rings are generalization of reduced rings, and therefore, the set of nilpotent elements plays an important role in this class of rings. There are many examples of rings with nonzero nilpotent elements which are Armendariz. Observing structure of the set of all nilpotent elements in the class of Armendariz rings, Antoine introduced the notion of nil-Armendariz rings as a generalization, which are connected to the famous question of Amitsur of whether or not a polynomial ring over a nil coefficient ring is nil. Given an associative ring [Formula: see text] and a monoid [Formula: see text], we introduce and study a class of Armendariz-like rings defined by using the properties of upper and lower nilradicals of the monoid ring [Formula: see text]. The logical relationship between these and other significant classes of Armendariz-like rings are explicated with several examples. These new classes of rings provide the appropriate setting for obtaining results on radicals of the monoid rings of unique product monoids and also can be used to construct new classes of nil-Armendariz rings. We also classify, which of the standard nilpotence properties on polynomial rings pass to monoid rings. As a consequence, we extend and unify several known results.

Biotransformation of Resveratrol: New Prenylated trans-Resveratrol Synthesized by Aspergillus sp. SCSIOW2

Arahypin-16 (1), a new prenylated resveratrol with a unique dihydrobenzofuran ring, has been isolated as a microbial metabolite of resveratrol (2) from whole-cell fermentation of Aspergillus sp. SCSIOW2. The stereochemistry of 1 was determined by ECD calculations. 1 showed about half of the extracellular radical scavenging effect (IC50 = 161.4 μM) compared with resveratrol (IC50 = 80.5 μM), while on biomembranes it exhibited the same range of protection effects against free radicals generated from AAPH (IC50 = 78.6 μM and 87.9 μM).

A non-destructive internal nuclear forensic investigation at Argonne: discovery of a Pu planchet from 1948

A plutonium alpha standard dating from 1948 was discovered at Argonne National Laboratory and characterized using a number of non-destructive analytical techniques. The principle radioactive isotope was found to be 239Pu and unique ring structures were found across the surface of the deposition area. Due to chronological constraints on possible sources and its high isotopic purity, the plutonium in the sample was likely produced by the Oak Ridge National Lab X-10 Reactor. It is proposed that the rings are resultant through a combination of polishing and electrodeposition, though the hypothesis fails to address a few key features of the ring structures.

Novel archaeal tetraether lipids with a cyclohexyl ring identified in Fayetteville Green Lake, NY, and other sulfidic lacustrine settings.

The meromictic Fayetteville Green Lake (FGL) is of significant geobiological interest because of microbial cycling of sulfur within and below the permanent chemocline and in the euxinic deep waters. Studies of glycerol dibiphytanyl glycerol tetraethers (GDGTs) may help shed light on understanding the activity of archaeal communities in these habitats. Normal-phase and reversed-phase liquid chromatography/mass spectrometry (LC/MS) analysis on total lipid extracts of environmental samples revealed series of GDGTs with different biphytane structures. Comparison of the mass spectrum of biphytane obtained from separated novel GDGTs with that of a synthetic C40 biphytane confirms our structural assignments. A unique cyclohexyl ring configured in the middle of a C40 biphytane chain was identified in these novel GDGTs. We suggest the trivial name S-GDGTs for these compounds, where 'S' stands for 'sulfidic' and 'six-membered ring'. S-GDGT derivatives composed of biphytanes modified with double bonds and cyclopentane rings were also detected in the samples we analyzed. Intact polar lipid precursors of S-GDGT include compounds with mono- and diglycosyl head groups. The carbon isotopic composition of S-GDGTs and their occurrence in FGL, Messel Shale as well as Salt Pond and salt marshes on Cape Cod suggest that S-GDGTs may be produced by chemoautotrophic archaea that prefer sulfidic conditions. Copyright © 2016 John Wiley & Sons, Ltd.

Noncyanogenic Cyanoglucoside Cyclooxygenase Inhibitors from Simmondsia chinensis.

Two new noncyanogenic cyanoglucoside dimers, simmonosides A and B (1 and 2), were identified from the aqueous extract of jojoba (Simmondsia chinensis) leaves. Compounds 1 and 2 are the first examples of noncyanogenic cyanoglucoside dimers containing a unique four-membered ring, representing novel dimerization patterns at α,β-unsaturated carbons of a nitrile group in 1 and γ,δ-unsaturated carbons in 2. Their structures were elucidated based on spectroscopic evidence and electronic circular dichroism (ECD) calculations. Compounds 1 and 2 exhibit promising COX-2 inhibition activity, with IC50 values of 13.5 and 11.4 μM, respectively.

A Multifunctional Monooxygenase XanO4 Catalyzes Xanthone Formation in Xantholipin Biosynthesis via a Cryptic Demethoxylation

Xantholipin and several related polycyclic xanthone antibiotics feature a unique xanthone ring nucleus within a highly oxygenated, angular, fused hexacyclic system. In this study, we demonstrated that a flavin-dependent monooxygenase (FMO) XanO4 catalyzes the oxidative transformation of an anthraquinone to a xanthone system during the biosynthesis of xantholipin. Invitro isotopic labeling experiments showed that the reaction involves sequential insertion of two oxygen atoms, accompanied by an unexpected cryptic demethoxylation reaction. Moreover, characterizations of homologous FMOs of XanO4 suggested the generality of the XanO4-like-mediated reaction for the assembly of a xanthone ring in the biosynthesis of polycyclic xanthone antibiotics. These findings not only expand the repertoire of FMO activities but also reveal a novel mechanism for xanthone ring formation.

Sea surface salinity variability in the Agulhas Current region inferred from SMOS and Aquarius

Abstract Understanding of the Agulhas Current's unique retroflection and ring shedding has been greatly improved by satellite altimetry data over the last several decades, but salinity remote sensing technology has not been available to conduct similar studies with respect to regional sea surface salinity (SSS) variability. ESA's Soil Moisture and Ocean Salinity (SMOS) and NASA's Aquarius/SAC-D salinity missions can provide such data, but it remains unclear if the accuracy of these sensors is high enough to properly study this dynamic region. To address this issue, this study validates both SMOS and Aquarius against monthly in situ data from Argo floats. All available, corresponding data points over a three year period have root mean square differences less than 0.2 pss and correlation coefficients greater than 0.9. Additionally, over 80% of differences between the products fall between ± 0.5 pss. Surface salt transports were calculated to see how well the satellite products estimate SSS advection in the Agulhas region. Zonal and meridional surface salt transports have annual maxima in austral winter and minima in austral summer, although the seasonal range is small. Using Argo, SMOS, and Aquarius SSS for this calculation produces statistically identical results, suggesting the utility of using the satellites to monitor regional salinity advection at higher frequencies and horizontal resolutions than previously possible using only sparse in situ data. SSS gradients along the subtropical front reveal that SMOS and Aquarius are much more effective tools for observing small-scale structure prevalent in the meandering of the Agulhas Return Current. Finally, we conclude that when compared to Argo floats in situ observations SMOS and Aquarius are statistically accurate and may yet prove powerful tools for observing Agulhas salinity processes on smaller time and spatial scales.

Two-carbon ring expansion of isatin: a convenient construction of a dibenzo[b,d]azepinone scaffold.

A unique two-carbon ring expansion of isatin has been achieved to conveniently construct the functionalized dibenzo[b,d]azepin-6-one scaffold in moderate to high yields, and the two carbon sources are different: one carbon is from the N-substituent of pyridinium bromide and the other is from indene-1,3-dione.

Expeditious synthesis of the fused hexacycle of puberuline C via a radical-based cyclization/translocation/cyclization process.

The fused 6/7/5/6/6/6-hexacyclic ring system of puberuline C was assembled in 18 steps from 2-(ethoxycarbonyl)cyclohexanone. After the azabicyclo[3.3.1]nonane derivative was sequentially coupled with propargyl magnesium bromide, 2-iodo cyclopentenone and allyl bromide, the pentacycle was constructed in a single step via a radical-based cyclization/translocation/cyclization process. The C11-bridgehead radical generated via C-Br homolysis participated in a 7-endo cyclization, and the 1,5-hydrogen translocation of the resultant radical was followed by transannular 6-exo cyclization to simultaneously realize the construction of the two rings and the introduction of the five contiguous stereocenters. The last 6-exo cyclization was induced by the Mukaiyama aldol reaction, and the C16-ketone was stereoselectively reduced by the action of SmI2/t-BuOH, leading for the first time to the synthesis of the entire hexacycle of puberuline C.

ChemInform Abstract: Substrate‐Controlled Product‐Selectivity in the Reaction of the Bestmann—Ohira Reagent with N‐Unprotected Isatin‐Derived Olefins.

AbstractThe title reaction features a substrate‐controlled product‐selectivity to afford either spiro‐pyrazoline‐oxindoles (III) or pyrazoloquinazolinones (V) depending on the electronic nature of the substituent at the isatylidene moiety.

Torsion-free modules with UA-rings of endomorphisms

An associative ring R is called a unique addition ring (UA-ring) if its multiplicative semigroup (R, · ) can be equipped with a unique binary operation+ transforming the triple (R, ·, +) to a ring. An R-module A is said to be an End-UA-module if the endomorphism ring EndR(A) of A is a UA-ring. In the paper, the torsion-free End-UA-modules over commutative Dedekind domains are studied. In some classes of Abelian torsion-free groups, the Abelian groups having UA-endomorphism rings are found.