Orientation Of Ring Research Articles

Comprehensive Analysis of Methyl-β-D-ribofuranoside: A Multifaceted Spectroscopic and Theoretical Approach.

This study presents a comprehensive analysis of the vibrational spectra of methyl-β-D-ribofuranoside. Employing a combination of inelastic neutron scattering, Raman, and infrared spectroscopy allows for the observation of all modes regardless of the selection rules. The experimental techniques were complemented by density functional theory computational methods using both gas-phase (Gaussian) and solid-state (CRYSTAL, CASTEP) approaches to provide an unambiguous assignment of the defining vibrational features. Two distinct structures of the molecule were identified in the unit cell, differentiated mainly by the orientation of the furanose ring O-H bonds. The low-energy region of the spectrum (<400 cm-1) is dominated by lattice vibrations and functional group rotation, while the midenergy region is dominated by out-of-plane bending motions of the furanose ring (400-900 cm-1) and by C-H bending in the methyl and methylene groups (1400-1600 cm-1). The high-energy region (>2800 cm-1) encompasses the C-H and O-H stretching modes and offers convincing evidence of at least one H-bonding interaction between the two structures of methyl-β-D-ribofuranoside.

Hydrophilicity of Organically Modified Montmorillonite and Effect on Benzene Adsorption by the Molecular Dynamics Method.

Interlayer modification of layered materials with organocations has been known to endow the nanocomposite with hydrophobicity, and adsorption of aromatic compounds in the aqueous phase has been investigated for decades by using montmorillonite, a representative layered clay mineral, as the host material. Usage of the organocation has been believed to be effective due to the π-π interaction with the aromatic adsorbate, the presence of which is not verified spectroscopically in the water-immersed state. Considering that the organocation is generally regarded as a pillar to keep the interlayer space, the interaction between the organocation and adsorbate has not yet been clarified sufficiently. In the present study, we revealed the role of the organocation by the molecular dynamics method, where tetramethylammonium (TMA) and trimethylphenylammonium (TMPA) ions were selected as the representative and simple organocations, and benzene was the adsorbate to exclude the effect of the substitution group. Both H2O and benzene molecules were introduced in the interlayer of TMA- or TMPA-modified montmorillonite to model the water-immersed adsorption structure. It was found that H2O is preferentially distributed on the clay surface, followed by the center of the interlayer when the amount of H2O is large. In the adsorption model, benzene was vertically adsorbed on the clay surface. Radial distribution function analysis revealed that benzene is distributed around both the methyl and the phenyl groups in the TMA and TMPA cations, but the orientation of the phenyl ring is not consistent with that of benzene. Thus, benzene was found not to form the π-π interaction in montmorillonite modified with the TMPA cations in the water-immersed state. Furthermore, the surface was partly covered with the phenyl group in the TMPA cation, decreasing the adsorption area. Therefore, the experimental suggestion that benzene is adsorbed on the clay surface was reproduced by our simulation, and the interaction between the organocation and benzene and surface occupancy should be paid attention to maximize the adsorption property.

NHC-Supported 2-Sila and 2-Germavinylidenes: Synthesis, Dynamics, First Reactivity and Theoretical Studies.

2-tetrelavinylidenes (C=EH2 ; E=Si, Ge) are according to quantum chemical studies the least stable isomers on the [E,C,2H] potential energy hypersurface isomerizing easily via the trans-bent tetrelaacetylenes HE≡CH to the thermodynamically most stable 1-tetrelavinylidenes (E=CH2 ). Consequently, experimental studies on 2-tetrelavinylidenes (C=ER2 ) and their derivatives are lacking. Herein we report experimental and theoretical studies of the first N-heterocyclic carbene (NHC) supported 2-silavinylidene (NHC)C=SiBr(Tbb) (1-Si: NHC=C[N(Dipp)CH]2 , Dipp=2,6-diisopropylphenyl, Tbb=2,6-bis[bis(trimethylsilyl)methyl]-4-tert-butylphenyl) and the isovalent 2-germavinylidenes (NHC)C=GeBr(R) (1-Ge, 1-GeMind: R=Tbb, Mind (1,1,3,3,5,5,7,7-octamethyl-s-hydrindacene-4-yl)). The NHC-supported 2-tetrelavinylidenes were obtained selectively from the 1,2-dibromoditetrelenes (E)-(R)BrE=EBr(R) using the diazoolefin (NHC)CN2 as vinylidene transfer reagent. 1-E (E=Si, Ge) have a planar vinylidene core, a bent-dicoordinated vinylidene carbon atom (CVNL ), a very short E=CVNL bond and an almost orthogonal orientation of the NHC five-membered ring to the vinylidene core. Quantum chemical analysis of the electronic structures of 1-E suggest a significantly bent 1-tetrelaallene and tetrelyne character. NMR studies shed light into the dynamics of 1-E involving NHC-rotation around the CVNL -CNHC bond with a low activation barrier. Furthermore, the synthetic potential of 1-E is demonstrated by the synthesis and full characterization of the unprecedented NHC-supported bromogermynes BrGe=C(EBr2 Tbb)(NHC) (2-SiGe: E=Si; 2-GeGe: E=Ge).

Surface adsorption of L-phenylalanine on silver colloidal nanoparticles investigated by surface-enhanced Raman spectroscopy

L-phenylalanine (L-Phe) is one of three aromatic amino acids frequently used in numerous vibrational applications, including surface-enhanced Raman spectroscopy (SERS). Despite the wide applications, the spectral analyses and vibrational assignments of the Raman spectra of L-Phe based on surface adsorption on metallic nanosurfaces are limited. In this work, we report pH-dependent SERS of L-Phe adsorbed on borohydride-reduced silver colloidal nanoparticles, where the spectral changes upon protonation of amine group are understood as the modification in the surface adsorption via the carboxylate and amino group. In-plane and out-of-plane ring stretching and aromatic ν(CH) modes appear sensitive to the surface orientation of the phenyl ring, and the peripheral vibrational modes, including the stretching and bending of carboxylate and amine groups, are crucial to understanding the detailed surface adsorption mechanisms of L-Phe in anionic and zwitterionic forms depending on the solution pH. The pH-dependent intensity changes of the major ring stretching modes show that the surface pKa of L-Phe decreases to ∼6 from the bulk value of 9.13.

Deciphering the controlling factors for phase transitions in zeolitic imidazolate frameworks.

Zeolitic imidazolate frameworks (ZIFs) feature complex phase transitions, including polymorphism, melting, vitrification, and polyamorphism. Experimentally probing their structural evolution during transitions involving amorphous phases is a significant challenge, especially at the medium-range length scale. To overcome this challenge, here we first train a deep learning-based force field to identify the structural characteristics of both crystalline and non-crystalline ZIF phases. This allows us to reproduce the structural evolution trend during the melting of crystals and formation of ZIF glasses at various length scales with an accuracy comparable to that of ab initio molecular dynamics, yet at a much lower computational cost. Based on this approach, we propose a new structural descriptor, namely, the ring orientation index, to capture the propensity for crystallization of ZIF-4 (Zn(Im)2, Im=C3H3N2-) glasses, as well as for the formation of ZIF-zni (Zn(Im)2) out of the high-density amorphous phase. This crystal formation process is a result of the reorientation of imidazole rings by sacrificing the order of the structure around the zinc-centered tetrahedra. The outcomes of this work are useful for studying phase transitions in other metal-organic frameworks (MOFs) and may thus guide the development of MOF glasses.

Developing A Robot to Improve The Accuracy of Ring Retrieval and Throwing at The ABU Robocon Indonesia Robot Competition

This article outlines the creation and application of a technologically improved robot designed to amplify the precision and effectiveness of ring retrieval and projection tasks in the ABU Robocon Indonesia Robot Challenge. The ABU Robocon competition is an annual event that tasks teams with crafting robots capable of accomplishing specific assignments under a predetermined time limit. The ring retrieval and projection task, historically known for its precision requirements, has proven to be quite demanding. Our strategy entailed the incorporation of cutting-edge technologies into the robot's design, encompassing computer vision and machine learning algorithms, to augment its accuracy and performance. We equipped the robot with cameras and sensors for the detection and analysis of ring positions and orientations. Real-time decisions regarding the optimal approach for retrieving and accurately projecting the rings were made using machine learning models that had undergone training. The outcomes of our experiments reveal a marked enhancement in the robot's performance when compared to conventional methods. The tech-enhanced robot consistently exhibited a heightened success rate when performing ring retrieval and projection tasks. This development not only boosts the competitiveness of our robot in the ABU Robocon competition but also underscores the potential of advanced technologies in enhancing the performance of robotics systems when confronted with intricate tasks.

Palladium(II) and Platinum(II) Bis(Stibinidene) Complexes with Intramolecular Hydrogen-Bond Enforced Geometries.

The coordination capability of two N,C,N pincer coordinated stibinidenes, i.e. bis(imino)- [2,6-(DippN=CH)2C6H3]Sb (1) or imino-amino- [2-(DippN=CH)-6-(DippNHCH2)C6H3]Sb (2) toward palladium(II) and platinum(II) centers was examined. In the course of this study, seven new square-planar bis(stibinidene) complexes were synthesized and characterized by NMR, IR, Raman, UV-vis spectroscopy and single crystal (sc)-X-ray diffraction analysis. In all cases, both stibinidene ligands 1 or 2 adopt trans positions, but differ significantly in the torsion angle describing mutual orientation of aromatic rings of the stibinidenes along the Sb-Pd/Pt-Sb axes. Furthermore, majority of complexes form isomers in solution most probably due to a hindered rotation around Sb-Pd/Pt bonds caused by bulkiness of 1 and 2. This phenomenon also seems to be influenced by the absence/presence of a pendant -CH2NH- group in 1/2 that is able to form intramolecular hydrogen bonds with the adjacent chlorine atom(s) attached to the metal centers. The whole problem was subjected to a theoretical study focusing a role of hydrogen bonds in structure architecture of the complexes. To describe the UV-vis spectra of these highly coloured complexes, TD-DFT calculations were employed. These outline differences between the stibinidene ligands, the transition metals as well as between the charge of the complexes (neutral or anionic).

Unveiling the structural organisation of carvacrol through X-ray scattering and molecular Dynamics: A comparative study with liquid thymol

An integrated approach involving Small and Wide Angle X-ray scattering and computational tools, Molecular Dynamics (MD) and Density Functional Theory (DFT) calculations, was employed to describe the microscopic structural arrangement in carvacrol (2-methyl-5-(1-methylethyl)phenol) at 300 K and 353 K. Carvacrol is a phenol derivative, with an aromatic nature and amphiphilic features and is liquid at room temperature. Its structural organization in the liquid state was compared with the one found for its structural isomer, thymol (5-methyl-2-(1-methylethyl)phenol), at 353 K (in its liquid state), through MD simulations: significant differences between the two compounds have emerged. For carvacrol, at both 300 K and 353 K, there is an inclination for the aromatic rings to orient perpendicularly, maintaining a first neighbour separation of around 6 Å. Conversely, liquid thymol at 353 K exhibits a more heterogeneous structural organisation and is characterised by both parallel and antiparallel orientations of neighbour rings already at shorter distances of approximately 4.5 Å. On a local scale, liquid thymol tends to establish hydrogen bonds (HBs) between its hydroxyl groups, reminiscent of its solid crystalline form. Conversely, carvacrol exhibits a stronger inclination towards O-H···π hydrogen bonding interactions. On a mesoscopic scale, both carvacrol and thymol are characterised by an X-ray scattering low Q peak, which fingerprints the existence of nm-scale structural heterogeneities due to the segregation of HB-interacting polar moieties, embedded within the apolar matrix. Notably, the low Q peak is more pronounced in liquid thymol where the preferential HBs between hydroxyl groups have been observed. Overall, the different structural arrangements of liquid carvacrol and thymol have the potential to influence various bulk and macroscopic properties, including melting points and solvation capabilities. Given these differences, one might envisage the use of carvacrol as a replacement to thymol, in order to fine-tune specific chemical physical properties of applicative interest, including deep eutectic solvents formulation.

Metal-organic frameworks for efficient mephedrone detoxification or supervised withdrawal – synthesis, characterisation, and in vivo studies

In this study, we describe the innovative use of metal–organic frameworks (MOFs) as propranolol (PRO) carriers for mephedrone (4-MMC) overdose treatment or supervised withdrawal. The group of model Zr-based MOFs including UiO-66, UiO-67, MOF-808, and NU-1000, and PRO@MOF composites were synthesised and characterised. The PRO release was tested in water and simulated body fluid (SBF) environments. The prepared PRO@MOF differed in the amount and pore sizes, as well as in the surface properties, which affected the kinetics of PRO release. The inhibitory effect of SBF resulted in a more gradual, and controlled PRO release from PRO@MOF composites, further confirming the feasibility of this type of solution in real applications. The sorption mechanism in prepared PRO@MOF composites was studied by molecular dynamics (MD) and density functional theory (DFT) calculations. The molecular calculations (ring orientation, partial charges and bond orders) confirmed π–π stacking as the main contribution to the interaction between the electronic structures of PRO molecule and MOFs linker. The in vivo studies demonstrated the lack of cytotoxicity of MOFs and composites, and pre-evidence confirmed the effectiveness of using PRO-loaded MOFs as drug carriers in a 4-MMC overdose. The study provides a new potential detoxification system for addicts.

Probing Substituent Effect on Nickel-Sulfur Bond Covalency in Ni(II)-Dithiophosphinate Complexes by Sulfur K-Edge XAS and DFT Calculations.

Complexes of Ni(II) with a series of aryl or alkyl substituent dithiophosphinic acids were characterized by crystallographic structure, sulfur K-edge X-ray absorption spectroscopy (XAS), and density functional theory (DFT). In these complexes, Ni(II) coordinates with four sulfur atoms from two dithiophosphinate anions form a well-defined square-planar structure. Despite the minor differences in the geometry parameters among the complexes, the electronic structure is affected significantly by the substituent group attached to dithiophosphinic acid. In particular, the addition of ortho-CF3 group to the aryl ring constrains the orientation of the aryl ring and enhances the conjugation between the aryl ring and the coordinating core. Sulfur K-edge XAS spectra help further reveal the electronic structure of the complexes. Both the pre-edge feature and rising-edge feature provide abundant information on the molecular orbitals and show a distinctive effect of the substituent groups on the electronic structure of the complexes, which is supposedly relevant to the ligand's performance in Ln(III)/An(III) separation.

The design, synthesis, and inhibition of Clostridioides difficile spore germination by acyclic and bicyclic tertiary amide analogs of cholate

Clostridioides difficile infection (CDI) is a major identifiable cause of antibiotic-associated diarrhea. In our previous study (J. Med. Chem., 2018, 61, 6759–6778), we have identified N-phenyl-cholan-24-amide as a potent inhibitor of spore germination. The most potent compounds in our previous work are N-arylamides. We were interested in the role that the conformation of the amide plays in activity. Previous research has shown that secondary N-arylamides exist exclusively in the coplanar trans conformation while tertiary N-methyl-N-arylamides exist in a non-planar, cis conformation. The N-methyl-N-phenyl-cholan-24-amide was 17-fold less active compared to the parent compounds suggesting the importance of the orientation of the phenyl ring. To lock the phenyl ring into a trans conformation, cyclic tertiary amides were prepared. Indoline and quinoline cholan-24-amides were both inhibitors of spore germination; however, the indoline analogs were most potent. Isoindoline and isoquinoline amides were inactive. We found that the simple indoline derivative gave an IC50 value of 1 μM, while the 5′-fluoro-substituted compound (5d) possessed an IC50 of 400 nM. To our knowledge, 5d is the most potent known spore germination inhibitor described to date. Taken together, our results indicate that the trans, coplanar conformation of the phenyl ring is required for potent inhibition.

WALLABY pilot survey: the potential polar ring galaxies NGC 4632 and NGC 6156

ABSTRACT We report on the discovery of two potential polar ring galaxies (PRGs) in the WALLABY Pilot Data Release 1 (PDR1). These untargeted detections, cross-matched to NGC 4632 and NGC 6156, are some of the first galaxies where the H i observations show two distinct components. We used the iDaVIE virtual reality software to separate the anomalous gas from the galactic gas and found that the anomalous gas comprises ∼50 per cent of the total H i content of both systems. We have generated plausible 3D kinematic models for each galaxy, assuming that the rings are circular and inclined at 90° to the galaxy bodies. These models show that the data are consistent with PRGs but do not definitively prove that the galaxies are PRGs. By projecting these models at different combinations of main disc inclinations, ring orientations, and angular resolutions in mock data cubes, we have further investigated the detectability of similar PRGs in WALLABY. Assuming that these galaxies are indeed PRGs, the detectability fraction, combined with the size distribution of WALLABY PDR1 galaxies, implies an incidence rate of ∼1–3 per cent. If this rate holds true, the WALLABY survey will detect hundreds of new polar ring galaxies.

Two-step hot isostatic pressing densification achieved non-porous fully-densified wood with enhanced physical and mechanical properties

A new two-step densification method for wooden materials entitled hot isostatic pressing (HIP) is proposed. This method has the advantage over previous densification methods that can achieved almost the full densification of wood, reaching values up to 1.47 kg/m3, which exceeds any value ever reported for a hardwood species. Furthermore, it can preserve about 35% of the original volume, in comparison to other methods which typically can preserve only 20% of the volume. Although not tested in this investigation, in principle, the HIP method should be capable of densifying any shape of wood including circular and tubular cross sections because the main densification mechanism is based on gas pressure that is equally exerted in the entire surface, rather than localized mechanical compression, which can only be effective with rectangular cross sections. In the first stage of the two-step proposed method, the compressive strength of the anatomical wood structure is reduced by delignification, and, in the second, a full densification is achieved by hot isostatic pressing under argon atmosphere. Three tropical hardwood species with distinct anatomical characteristics and properties were used to test the method. The HIP-densified wood’s microstructural, chemical, physical, and mechanical properties were assessed. Apart from the high densification values and volume preservation, the results indicate that proposed method was effective for all the tested species, showing homogenous density patterns, stable densification without noticeable shape recovery, and enhanced mechanical properties. Future research should test the HIP method in softwoods and consider the ring orientation in order to enhance the control of the densified geometry.

On the Role of a Conserved Tryptophan in the Chromophore Pocket of Cyanobacteriochrome

The cyanobacteriochrome Slr1393 can be photoconverted between a red (Pr) and green absorbing form (Pg). The recently determined crystal structures of both states suggest a major movement of Trp496 from a stacking interaction with ring D of the phycocyanobilin (PCB) chromophore in Pr to a position outside the chromophore pocket in Pg. Here, we investigated the role of this amino acid during photoconversion in solution using engineered protein variants in which Trp496 was substituted by natural and non-natural amino acids. These variants and the native protein were studied by various spectroscopic techniques (UV–vis absorption, fluorescence, IR, NIR and UV resonance Raman) complemented by theoretical approaches. Trp496 is shown to affect the electronic transition of PCB and to be essential for the thermal equilibrium between Pr and an intermediate state O600. However, Trp496 is not required to stabilize the tilted orientation of ring D in Pr, and does not play a role in the secondary structure changes of Slr1393 during the Pr/Pg transition. The present results confirm the re-orientation of Trp496 upon Pr → Pg conversion, but do not provide evidence of a major change in the microenvironment of this residue. Structural models indicate the penetration of water molecules into the chromophore pocket in both Pr and Pg states and thus water-Trp contacts, which can readily account for the subtle spectral changes between Pr and Pg. Thus, we conclude that reorientation of Trp496 during the Pr-to-Pg photoconversion in solution is not associated with a major change in the dielectric environment in the two states.

Homochiral boron imidazolate frameworks built from mixed Chiral and achiral ligands

Chiral metal-organic frameworks (MOFs) have been studied extensively because of the potential application. Based on the complexity of chiral structure, it is a great challenge to study the formation of novel chiral centers under self-assembly conditions. By mixing chiral and achiral ligands, five unusual homochiral BIFs materials were synthesized by using d-camphoric acid (D-H2cam) and KBH(mim)3 (mim = 2-methylimidazole) under solvothermal condition. The orientations of mim rings had been locked to a specific angle in these structures and freed tridentate BH(mim)3- ligands were separated into two enantiomers, S–BH(mim)3- and R–BH(mim)3-. BIF-123 and BIF-124 exhibited similar (3, 4)-connected pillared-layer chiral structures with a pair of opposite helical substructures. BIF-125, 126 and 127 exhibited a 4-connected chiral diamond structure, which incorporates the homochiral helical substructures containing only S–BH(mim)3- ligand. These homochiral BIFs showed high pore volume in gas adsorption measurements and good stability under different solvent environments. Furthermore, the obvious CD signals of BIF-126 proved the chirality of bulk samples.

Natural selection of carotenoid binding in Gloeobacter rhodopsin

Energy transfer from the 4-ketocarotenoid antenna (salinixanthin) and echinenone to xanthorhodopsin has been confirmed in Salinibacter ruber and Gloeobacter violaceus, respectively. Hundreds of carotenoids and numerous rhodopsin homologs are spreading across the life domain. Here, we found that ketocarotenoid binds to Gloeobacter rhodopsin (GR), suggesting an increased likelihood of the existence of the carotenoid-rhodopsin complex. Additionally, the recruitment of the secondary chromophore antenna is precisely controlled by rhodopsin. Therefore, comparing the binding of multiple carotenoids is of interest to GR. Particular attention was paid to the structural interaction of ligands within the protein binding pocket. While different degrees of carotenoid association are evident in the GR-carotenoid experimental data and molecular docking results, the retinal isomerization dynamics defined the relative orientation of the β-ionone ring, and structural changes in the protein acted as modest barriers for the best carotenoid for GR. Notably, the selection of carotenoid binding can be summarized in three points: (1) structural matching of a ligand molecule with the binding pocket; (2) strong binding affinity and rapid binding kinetics; (3) dynamic flexibility that is versatile to rhodopsin activation. The selected carotenoids showed significant enhancement in light-driven proton pumping as extra light-harvesting antennae and provided intrinsic protection from stress.

Autoregulation and Autoinhibition of the Main NO Synthase Isoforms (Brief Review).

Nitric oxide (II) (NO) is the most important mediator of a wide range of physiological and pathophysiological processes. It is synthesized by NO synthases (NOSs), which have three main isoforms differing from each other in terms of activation and inhibition features, levels of NO production, subcellular localization, etc. At the same time, all isoforms are structurally very similar, and these differences are determined by NOS autoregulatory elements. The article presents an analysis of the autoregulatory and autoinhibitory mechanisms of the NOS reductase domain that determine differences in the productivity of isoforms, as well as their dependence on the concentration of Ca2+ ions. The main regulatory elements in NOS that modulate the electron transfer from flavin to heme include calmodulin (CaM), an autoinhibitory insert (AI), and the C-terminal tail (C-tail). Hydrophobic interactions of CaM with the surface of the NOS oxidase domain are assumed to facilitate electron transfer from flavin mononucleotide (FMN). CaM binding causes a change in the inter-domain distances, a shift of AI and the C-tail, and, as a result, a decrease in their inhibitory effect. CaM also shifts the conformational equilibrium of the reductase domain towards more open conformations, reduces the lifetime of conformations, their stereometric distribution, and accelerates the flow of electrons through the reductase domain. The AI element, apparently, induces a conformational change that hinders electron transfer within the reductase domain, similar to the hinge domain in cytochrome P450. Together with CaM, the C-tail regulates the electron flow between flavins, the distance and relative orientation of isoalloxane rings, and also modulates the electron flow from FMN to the terminal acceptor. Together with the C-tail, AI also predetermines the dependence of neuronal and endothelial forms of NOS on the concentration of Ca2+ ions, and the C-tail length affects differences in the productivity of NO synthesis. The inhibitory effect of the C-tail is likely to be reduced by CaM binding due to the C-tail shift due to the electrostatic repulsive forces of the negatively charged phosphate and aspartate residues. The autoregulatory elements of NOS require further study, since the mechanisms of their interaction are complex and multidirectional, and hence provide a wide range of characteristics of the observed isoforms.

Inclusion of a Catechol-Derived Hydrazinyl-Thiazole (CHT) in β-Cyclodextrin Nanocavity and Its Effect on Antioxidant Activity: A Calorimetric, Spectroscopic and Molecular Docking Approach.

The aim of the present research was to obtain a supramolecular complex between a strong antioxidant compound previously reported by our group, in order to extend its antioxidant activity. The formation of the inclusion complex of a catechol hydrazinyl-thiazole derivative (CHT) and β-cyclodextrin in aqueous solution has been investigated using isothermal titration calorimetry (ITC), spectroscopic and theoretical methods. The stoichiometry of this inclusion complex was established to be equimolar (1:1) and its equilibrium constant was determined. An estimation of the thermodynamic parameters of the inclusion complex showed that it is an enthalpy and entropy-driven process. Our observations also show that hydrophobic interactions are the key interactions that prevail in the complex. 1H NMR spectroscopic method was employed to study the inclusion process in an aqueous solution. Job plots derived from the 1H NMR spectral data demonstrated 1:1 stoichiometry of the inclusion complex in a liquid state. A 2D NMR spectrum suggests the orientation of the aromatic ring of CHT inside the β-CD cavity. The antiradical activity of the complex was evaluated and compared with free CHT, indicating a delayed activity compared with free CHT. To obtain additional qualitative and visual insight into the particularity of CHT and β-CD interaction, molecular docking calculations have been performed.

FRACTURE TESTING OF EDGE-NOTCHED TIMBER BEAMS WITH DIFFERENT GROWTH RING ORIENTATIONS

The purpose of this research is to test Norway spruce specimens with different growth ring orientations weakened by edge-notch until failure. In the experiments the specimens were subjected to 3-point bending, tension and compression tests. In addition, failure mode during loading is investigated using a high-resolution camera. Based on the measurement results the correlation between latewood ratio, ultimate force, ultimate elongation/deflection, calculated moduli, growth ring orientation and diameter of the growth ring at the edge-notch were obtained. Based on the population data of the three tests conducted, only one parameter pair, namely the ratio of latewood to calculated modulus, influences the measurement results to almost the same extent. The other parameter pairs show different values and correlations.

Construction of Five Tryptophan Isomers and Application of the Isomers to Solid-Phase Total Syntheses of Lysocin E Derivatives.

Tryptophan (Trp) plays a unique role in peptides and proteins as its indole ring possesses an electron-rich character and an N1-H hydrogen-bond donor. Because of its non-rotationally symmetric structure, synthetic alterations of the orientation of the indole ring would modulate the intrinsic structures and functions of peptides and proteins. Here we developed synthetic routes to the five Trp isomers in which the C3-substitution of the indole ring was changed to the C2/4/5/6/7-substitutions, and applied the five monomers to Fmoc-based solid-phase peptide synthesis. Specifically, the five monomers were prepared via Negishi cross-coupling reactions of C2/4/5/6/7-iodoindoles. To demonstrate the applicability of the monomers to the solid-phase synthesis, the five Trp isomers of macrocyclic antibiotic lysocin E were selected as target molecules and synthesized through peptide elongation, on-resin macrocyclization, and global deprotection. The Trp isomers displayed markedly weaker antibacterial activity than the parent natural product, revealing the biological importance of the precise three-dimensional shape of the original Trp residue of lysocin E. The present methods for the preparation and application of these five Trp isomers provide a new strategy for analyzing and modifying the specific functions of numerous Trp-containing peptides and proteins beyond this study.