Plane Of Ring Research Articles

The X-ray Structures of 2- and 3-Sulfolene and Two Halogenated Derivatives

The structures of the isomeric 2,5-dihydrothiophene 1,1-dioxide [orthorhombic, a = 11.340(2), b = 7.0887(15), c = 6.2811(13) Å, space group Pnma] and 2,3-dihydrothiophene 1,1-dioxide [orthorhombic, a = 6.3903(13), b = 7.2783(16), c = 11.075(2) Å, space group Pnma] have been determined and show perfectly planar rings with the expected bond lengths and angles. In contrast, the halogenated derivatives 3,3,4,4-tetrachlorotetrahydrothiophene 1,1-dioxide [monoclinic, a = 11.8716(8), b = 6.5579(4), c = 11.4802(8) Å, β = 97.705(17), space group P21/c] and 2,3-dibromotetrahydrothiophene 1,1-dioxide [orthorhombic, a = 5.2502(3), b = 11.3561(6), c = 24.9802(17) Å, space group Pbca] both show twisted conformations. The degree of planarity is compared with that in the structures of comparable 5-membered ring cyclic sulfones and C–H…O hydrogen bonding patterns are discussed for all four structures.Graphical The two isomeric sulfolenes are perfectly planar while tetrachloro- and dibromo-derivatives adopt twisted structures.

Uncovering the mechanisms of cyclic peptide self-assembly in membranes with the chirality-aware MA(R/S)TINI forcefield

Cyclic peptides (CPs) formed by alternation of D- and L-amino acids (D,L-CPs) can self-assemble into nanotubes (SCPNs) by parallel or/and antiparallel stacking. Different applications have been attributed to these nanotubes, including the disruption of lipid bilayers of specific compositions and the selective transport of ions throughout membranes. Molecular dynamics (MD) simulations have significantly contributed to understand the interaction between CPs, including the structural, dynamic and transport properties of their supramolecular aggregates. The high computational cost of atomic resolution forcefields makes them impractical for simulating the self-assembly of macromolecules, so coarse-grained (CG) models might represent a more feasible solution for this purpose. However, general CG models used for the simulation of biomolecules such as the MARTINI forcefield do not explicitly consider the non-covalent interactions leading to the formation of secondary structure patterns in proteins. This becomes particularly important in the case of CPs due to the D- and L-chirality alternation in their sequence, leading to opposite orientations of the backbone polar groups on both sides of the cyclic ring plane. In order to overcome this limitation, we have extended the MARTINI forcefield to introduce chirality in each residue of the CPs. The new parametrization, which we have called MA(R/S)TINI, reproduces the expected self-assembly patterns for several CP sequences in the presence of different membrane models, explicitly considering the chirality of the CPs and with no significant extra computational cost. Our simulations provide new mechanistic information of how these systems self-assemble in presence of different lipid scenarios, showing that the CP-CP and CP-membrane interactions are sensitive to the peptide sequence chirality. This opens the door to design new bioactive CPs based on CG-MD simulations. A web-based tool for the automatic parameterization of new CP sequences using MA(R/S)TINI, among other functionalities, is under construction (see http://cyclopep.com).

Vulnerability of the ventricular conduction axis during transcatheter aortic valvar implantation: A translational pathologic study.

The ventricular components of the conduction axis remain vulnerable following transcatheter aortic valvar replacement. We aimed to describe features which may be used accurately by interventionalists to predict the precise location of the conduction axis, hoping better to avoid conduction disturbances. We scanned eight normal adult heart specimens by 3T magnetic resonance, using the images to simulate histological sections in order accurately to place the conduction axis back within the heart. We then used histology, tested in two pediatric hearts, to prepare sections, validated by the magnetic resonance images, to reveal the key relationships between the conduction axis and the aortic root. The axis was shown to have a close relationship to the nadir of the right coronary leaflet, in particular when the aortic root was rotated in counterclockwise fashion. The axis was more vulnerable in the setting of a narrow inferoseptal recess, when the inferior margin of the membranous septum was above the plane of the virtual basal ring, and when minimal myocardium was supporting the right coronary sinus. The features identified in our study are in keeping with the original description provided by Tawara, but at variance with more recent accounts. They suggest that the vulnerability of the axis during transcatheter valvar replacement can potentially be inferred on the basis of knowledge of the position of the aortic root within the ventricular base. If validated by clinical studies, our findings may better permit avoidance of new-onset left bundle branch block following transcatheter aortic valvar replacement.

Actin-Microtubule Crosstalk Imparts Stiffness to the Contractile Ring in Fission Yeast.

Actin-microtubule interactions are critical for cell division, yet how these networks of polymers mutually influence their mechanical properties and functions in live cells remains unknown. In fission yeast, the post-anaphase array (PAA) of microtubules assembles in the plane of the contractile ring, and its assembly relies on the Myp2p-dependent recruitment of Mto1p, a component of equatorial microtubule organizing centers (eMTOCs). The general organization of this array of microtubules and the impact on their physical attachment to the contractile ring remain unclear. We found that Myp2p facilitates the recruitment of Mto1p to the inner face of the contractile ring, where the eMTOCs polymerize microtubules without their direct interaction. The PAA microtubules form a dynamic polygon of Ase1p crosslinked microtubules inside the contractile ring. The specific loss of PAA microtubules affects the mechanical properties of the contractile ring of actin by lowering its stiffness. This change in the mechanical properties of the ring has no measurable impact on cytokinesis or on the anchoring of the ring. Our work proposes that the PAA microtubules exploit the contractile ring for their assembly and function during cell division, while the contractile ring may receive no benefit from these interactions.

Crystal structure of tert-butyl 3,6-di-iodo-carbazole-9-carboxyl-ate.

The mol-ecular structure of tert-butyl 3,6-di-iodo-carbazole-9-carboxyl-ate, C17H15I2NO2, features a nearly planar 13-membered carbazole ring with C-I bond lengths of 2.092 (4) and 2.104 (4) Å. The carbamate group has key bond lengths of 1.404 (6) Å (N-C), 1.330 (5) Å (O-C), and 1.201 (6) Å (C=O). The crystal contains inter-molecular π-π inter-actions, as well as both type I and type II inter-molecular I⋯I inter-actions.

A study of the anisotropy of dimensional change in the compaction plane during sintering of low alloyed cold compacted steels

ABSTRACT The anisotropy of dimensional change in compaction plane of rings made of three low alloyed steels was investigated as a function of green density and geometry. Increasing green density and (D ext–D int)/H ratio, the anisotropy of both shrinkage and swelling increases. A correlation with springback during ejection of the rings from die cavity after cold compaction was found. The ratio between the dimensional changes of diameters, as a function of the ratio between springback of diameters, describes a linear correlation intersecting point (1,1), representative of isotropic behaviour. This correlation confirms the hypothesis of an effect of micropores, generated in the green parts during ejection from die cavity, on dimensional change anisotropy. An analytical correlation was determined for the anisotropy of dimensional change in the compaction plane as a function of green density and geometrical parameter, which can be implemented in the design methodology accounting for the anisotropic dimensional change previously proposed.

Trapping of Small Molecules within Single or Double Cyclo[18]carbon Rings.

The encapsulation of a set of small molecules, H2, CO, CO2, SO2, and SO3, by a circular C18 ring is investigated by quantum calculations. These ligands lie near the center of the ring but, with the exception of H2, are disposed roughly perpendicular to the ring plane. Their binding energies with the C18 vary from 1.5 kcal/mol for H2 up to 5.7 kcal/mol for SO2, and the bonding is dominated by dispersive interactions spread over the entire ring. The binding of these ligands on the outside of the ring is weaker but allows the opportunity for each to bond covalently with the ring. A pair of C18 units lie parallel to one another. This pair can bind each of these ligands in the area between them with only small perturbations of the double ring geometry. The binding energies of these ligands to this double ring configuration are amplified by some 50% compared to the single ring systems. The presented data concerning the trapping of small molecules may have larger implications regarding hydrogen storage or air pollution reduction.

Ab Initio Determination of Molecular Geometry and Vibrational Frequencies of Benzotrifluoride

Using Gaussian 05 Revision C.02 version of the quantum chemical program ab initio computations has been carried out to compute optimized geometry, harmonic vibrational frequencies along with intensities in IR and Raman spectra and atomic charges at rhf / 6–31+g*, b3lyp / 6–31++g** and b3lyp / 6–311++g** levels. The optimized molecular structure is found to possess Cs point group symmetry with the plane of symmetry passing through the C atom, to which the CF3 group is attached, the centrally opposite C atom and the C atom of the CF3 group and perpendicular to the phenyl ring plane. One of the three F atoms of the CF3 group is found to be on one side of the ring plane and is situated on the plane of the symmetry while the other two F atoms are found to be on the other side of the ring plane placed symmetrically on either side of the symmetry plane. Vibrational assignments for the normal modes have been reviewed. To make vibrational assignments for the normal modes of vibration the Gauss View software was used. The CF3 group has the characteristic frequencies in the 340, 768, 1072, 1152 and 1318 cm-1 which are due to the modes δs (CF3), Vs (CF3 ), Vas(CF3) (a’), Vas(CF3) (a”) and V(C–CF3 ) respectively. The torsional frequency of the CF3 group is found to be 16 cm-1 which would lead to barrier height of ~ 0.5 kJ / mol for the torsional motion of the CF3 group.

1,4-Phenyl-ene diallyl bis-(carbonate).

The title mol-ecule, C14H14O6, is based on a benzene core di-substituted by allyl carbonate groups in the para positions. The mol-ecule is placed on an inversion centre, and the substituents are twisted with respect to the central benzene ring plane. The crystal structure does not include significant inter-molecular inter-actions other than weak C-H⋯O contacts between CH groups in the benzene ring and carbonate O atoms.

Enhanced electron density of the π-conjugated structure and in-plane charge transport to boost photocatalytic H2 evolution of g-C3N4

Graphite carbon nitride (g-C3N4) has become an emerging metal-free photocatalyst and attracted the attention of researchers. However, pure g-C3N4 (PCN) prepared by traditional thermal condensation polymerization has a low polymerization of heptazine ring chains and a large number of charge recombination centers, which hinder in-plane charge transport, leading to undesirable photocatalytic performance. Herein, PCN fabrication by thermal treatment with ammonium oxalate monohydrate was performed to produce highly dispersed porous g-C3N4 nanosheets, and the integrity of their in-plane heptazine ring chains was successfully improved without introducing heteroatoms. Electron paramagnetic resonance and 13C nuclear magnetic resonance analyses revealed significantly increased electron density and delocalization of the π-conjugated structure. The obtained samples exhibited acceptable stability and photocatalytic activity, and the hydrogen reduction rates without and with the Pt co-catalyst were 11.2 and 5.3 times that of PCN.

Magneto-Structural Correlations in a Mixed Porphyrin(Cu2+ )/Trityl Spin System: Magnitude, Sign, and Distribution of the Exchange Coupling Constant.

Tetrathiatriarylmethyl radicals (TAM or trityl) are receiving increasing attention in various fields of magnetic resonance such as imaging, dynamic nuclear polarization, spin labeling, and, more recently, molecular magnetism and quantum information technology. Here, a trityl radical attached via a phenyl bridge to a copper(II)tetraphenylporphyrin was synthesized, and its magnetic properties studied by multi-frequency continuous-wave electron paramagnetic resonance (EPR) spectroscopy and magnetic measurements. EPR revealed that the electron spin-spin coupling constant J between the trityl and Cu2+ spin centers is ferromagnetic with a magnitude of -2.3 GHz (-0.077 cm-1 , convention) and a distribution width of 1.2 GHz (0.040 cm-1 ). With the help of density functional theory (DFT) calculations, the obtained ferromagnetic exchange coupling, which is unusual for para-substituted phenyl-bridged biradicals, could be related to the almost perpendicular orientation of the phenyl linker with respect to the porphyrin and trityl ring planes in the energy minimum, while the J distribution was rationalized by the temperature weighted rotation of the phenyl bridge about the molecular axis connecting both spin centers. This study exemplifies the importance of molecular dynamics for the homogeneity (or heterogeneity) of the magnetic properties of trityl-based systems.

An in-plane flexible ring model for the analysis of the free and forced response of a rolling tyre

The increased demand for vibroacoustic comfort as well as regulations on noise and vibration levels have made the NVH (Noise, Vibration, Harshness) performances of a vehicle to become one of the fundamental design criteria. Therefore, predictive models for the analysis of noise and vibration transmission mechanisms represent interesting tools to support the R&D department of the automotive companies. Focusing the attention on passenger's comfort, the vibrations induced by the tyre/road interaction propagate from the contact area to the hub and finally inside the cockpit through structure-borne transmission paths. This can be regarded as one of the major contributors to the car cabin interior noise at low frequencies (between 20 and 500 Hz). Simplified models able to interpret the waves propagating inside the tyre structure and influenced by the angular speed may support the studies in this research field. To this end, an analytical model based on the theory of the flexible ring on elastic foundation has been developed. It allows analysing the tyre dynamics in both static and rolling conditions. Model parameters have been calibrated based on an Experimental Modal Analysis of the static tyre. The free response of the tyre shows the bifurcation effect at different rolling speeds, while a cleat test simulation has been carried out to investigate the forced response of the tyre.

Probing Colossal Carbon Rings.

Carbon aggregates containing between 10 and 30 atoms preferentially arrange themselves as planar rings. To learn more about this exotic allotrope of carbon, electronic spectra are measured for even cyclo[n]carbon radical cations (-) using two-color photodissociation action spectroscopy. To eliminate spectral contributions from other isomers, the target cyclo[n]carbon radical cations are isomer-selected using a drift tube ion mobility spectrometer prior to spectroscopic interrogation. The electronic spectra exhibit sharp transitions spanning the visible and near-infrared spectral regions with the main absorption band shifting progressively to longer wavelength by ≈100 nm for every additional two carbon atoms. This behavior is rationalized with a Hückel theory model describing the energies of the in-plane and out-of-plane π orbitals. Photoexcitation of smaller carbon rings leads preferentially to neutral C3 and C5 loss, whereas rings larger than tend to also decompose into two smaller rings, which, when possible, have aromatic stability. Generally, the observed charged photofragments correspond to low energy fragment pairs, as predicted by density functional theory calculations (CAM-B3LYP-D3(BJ)/cc-pVDZ). Using action spectroscopy it is confirmed that and photofragments from rings have cyclic structures.

Design, synthesis, and evaluation of substituted alkylindoles that activate G protein-coupled receptors distinct from the cannabinoid CB1 and CB2 receptors

The alkylindole (AI), WIN55212-2, modulates the activity of several proteins, including cannabinoid receptors 1 and 2 (CB1R, CB2R), and at least additional G protein-coupled receptor (GPCR) that remains uncharacterized with respect to its molecular identity and pharmacological profile. Evidence suggests that such AI-sensitive GPCRs are expressed by the human kidney cell line HEK293. We synthesized fourteen novel AI analogues and evaluated their activities at AI-sensitive GPCRs using [35S]GTPγS and [3H]WIN55212-2 binding in HEK293 cell membranes, and performed in silico pharmacophore modeling to identify characteristics that favor binding to AI-sensitive GPCRs versus CB1R/CB2R. Compounds 10 and 12 stimulated [35S]GTPγS binding (EC50s = 3.5 and 1.1 nM, respectively), and this response was pertussis toxin-sensitive, indicating that AI-sensitive GPCRs couple to Gi/o proteins. Five AI analogues reliably distinguished two binding sites that correspond to the high and low affinity state of AI-sensitive GPCRs coupled or not to G proteins. In silico pharmacophore modeling suggest 3 characteristics that favor binding to AI-sensitive GPCRs versus CB1R/CB2R: 1) an s-cis orientation of the two aromatic rings in AI analogues, 2) a narrow dihedral angle between the carbonyl group and the indole ring plane [i.e., O-C(carbonyl)-C3-C2] and 3) the presence of a carbonyl oxygen. The substituted alkylindoles reported here represent novel chemical tools to study AI-sensitive GPCRs.

Inquiring into geometric structures and electronic properties of sodium doped boron clusters: DFT study of NaB n (n = 1–12) clusters

The systems of alkali metal atom doped boron have been investigative topics over the years because of their diverse configurations and unique properties. Based on this, with the assistance of the CALYPSO software facilitates the structure prediction process, our group went into the geometric structures and bonding characteristics of the NaB n (n = 1–12) clusters. From the structural analysis, the participation of the Na atom does not dramatically change the configurations of the clusters, and the NaB n (n = 1–12) clusters maintain the parallel planar configuration evolution model with the pure boron clusters. The local most stable structures emerge at n = 3, 5, 8, the NEC result shows electrons transfer from Na-3s and B-2s orbitals to B-2p orbitals, indicating the s-p hybridisation exists between Na-B, B-B atoms, and the DOS analysis also prove this point. In the subsequent bonding analysis of the NaB3 and NaB8 clusters, the high proportions of B-2s, B-2p, or Na-3s orbitals at HOMO, LUMO, demonstrate the formation of strong B-B, Na-B covalent bonds, which is the benefit to forming high stability. Last, the calculations of ICSS show, perpendicular to the boron ring plane direction, the NaB3 exhibits strong aromaticity while the NaB8 shows anti-aromaticity.

A numerical algorithm for ground reaction curves of circular openings in strain-softening rock masses satisfying the generalized Hoek-Brown criterion

Based on the self-similarity method, a numerical algorithm for constructing ground reaction curves (GRC) of circular openings in elastic-strain softening rock mass that satisfies the generalized Hoek-Brown failure criterion is proposed. The algorithm is derived from the analysis of the axisymmetric plane strain model, where the far-field and excavation boundary are both axisymmetric stresses. Using the self-similar transformation, the plastic zone of the model was transformed into unit plane ring, which has unit radius at the boundary between the plastic zone and the elastic zone. The unit plane ring was dispersed into multiple concentric rings, for which the Runge-Kutta discrete equations of the stress and deformation were established based on corresponding self-similar governing equations. The equations were solved ring by ring in a successive manner, starting from the outer boundary to the excavation boundary. The comparison with the verified algorithm in literature shows that the results of the different algorithms are in good agreement and the relative errors of the plastic zone radius under various softening parameters are only 1.7%–2.0%. These results verified the correctness and reliability of the proposed new algorithm. Finally, the new algorithm is used to investigate the influence of the Hoek-Brown parameter a on GRC. A discussion of the potential capability of practical applications of this algorithm is also provided.

A New Varactor-Tuned 5.8 GHz Dielectric Resonator Band-Stop Filter for ITS and C-V2X Coexistence with Vehicular DSRC

In this paper, we introduce an electronically tuneable band-stop filter based on a dielectric resonator, along with its design principles and equivalent circuit model aimed at the coexistence of intelligent transport systems (ITS) and cellular vehicle-to-everything (C-V2X) communications operating at 5.9 GHz, with the widely spread vehicular dedicated short range communications (DSRC) at 5.8 GHz. The proposed architecture involves a dielectric resonator coupled via a microstrip transmission line to a planar ring resonator. The resonance is electronically tuned by varying the bias voltage of a varactor diode placed in the ring. This design is analyzed theoretically and experimentally. For validation, a filter operating at 5.8 GHz was designed. The prototype is capable of enhancing coexistence exhibiting to features. First, when inserted into the ITS transmitter chain, it reduces unwanted transmitter emissions in the out-of-band spectrum occupied by the DSRC carriers in the 5.8 GHz frequency band of at least 25 dB, with a minimal insertion loss at 5. 9 GHz of 1.6 dB; secondly, when inserted in the ITS receiver chain, it exhibits high linearity that prevents the generation of intermodulation products falling into the filter pass band. The prototype features more than 21 dBm of third-order input intercept points, and a tuning range of 26 MHz while maintaining a minimal loaded Q factor of 93. The prototype is discussed regarding the detailed equivalent circuit parameter extraction and their dependency upon the control voltage.

Propagation and focusing characteristics of the Bessel–Gaussian beam with the spiral phase term of new power-exponent-phase

A new type of beam called the NPEP-BG (a Bessel–Gaussian (BG) beam with a spiral phase term of a new power-exponent-phase (NPEP)) is theoretically studied in this paper. The results show that the number of singularities of the phase and side lobes of the intensity of this beam were equal to the topological charges (TCs) and the beam has the characteristics of self-healing during propagation. The NPEP-BG beam combined the partial characteristics of the new power-exponent-phase vortex (NPEPV) and the Bessel–Gaussian beam. At the focus of the beam, the characteristic like a perfect vortex beam was present, in which the focal radius is stable and independent of the topological charge. There are multi-focal spots around a ring in the focal plane, meaning that the NPEP-BG beam has a potential for application in multi-particle manipulation.

Planar index and outerplanar index of zero-divisor graphs of commutative rings without identity

Let $R$ be a commutative ring without identity. The zero-divisor graph of $R,$ denoted by $\Gamma(R)$ is a graph with vertex set $Z(R)\setminus \{0\}$ which is the set of all nonzero zero-divisor elements of $R,$ and two distinct vertices $x$ and $y$ are adjacent if and only if $xy=0.$ In this paper, we characterize the rings whose zero-divisor graphs are ring graphs and outerplanar graphs. Further, we establish the planar index, ring index and outerplanar index of the zero-divisor graphs of finite commutative rings without identity.

Room Temperature Intermolecular Dearomatization of Arenes by an Acyclic Iminosilylene.

A novel nontransient acyclic iminosilylene (1), bearing a bulky super silyl group (-SitBu3) and N-heterocyclic imine ligand with a methylated backbone, was prepared and isolated. The methylated backbone is the feature of 1 that distinguishes it from the previously reported nonisolable iminosilylenes, as it prevents the intramolecular silylene center insertion into an aromatic C-C bond of an aryl substituent. Instead, 1 exhibits an intermolecular Büchner-ring-expansion-type reactivity; the silylene is capable of dearomatization of benzene and its derivatives, giving the corresponding silicon analogs of cycloheptatrienes, i.e. silepins, featuring seven-membered SiC6 rings with nearly planar geometry. The ring expansion reactions of 1 with benzene and 1,4-bis(trifluoromethyl)benzene are reversible. Similar reactions of 1 with N-heteroarenes (pyridine and DMAP) proceed more rapidly and irreversibly forming the corresponding azasilepins, also with nearly planar seven-membered SiNC5 rings. DFT calculations reveal an ambiphilic nature of 1 that allows the intermolecular aromatic C-C bond insertion to occur. Additional computational studies, which elucidate the inherent reactivity of 1, the role of the substituent effect, and reaction mechanisms behind the ring expansion transformations, are presented.