Bridging Mode Research Articles

Triperiodic frameworks in the uranyl–2,5-thiophenedicarboxylate system: Effect of unidentate auxiliary ligands

2,5-Thiophenedicarboxylic acid (H2tdc) has been reacted with uranyl nitrate hexahydrate under solvo-hydrothermal conditions with N,N-dimethylacetamide (dma) as an organic cosolvent, giving the complex [UO2(tdc)(dma)] (1), isomorphous to the previously reported [UO2(tdc)(nmp)] (nmp = N-methyl-2-pyrrolidone). With tdc2− adopting the bis(μ2-κ1O:κ1O’)-bridging coordination mode, complex 1 crystallizes as a triperiodic framework with the point symbol {42.84}. With acetonitrile as an organic cosolvent and in the presence of [Ni(PPh3)2Br2], triphenylphosphine oxide is formed in situ and it binds to uranyl to give [UO2(tdc)(OPPh3)] (2). Complex 2 is also a triperiodic framework, with the point symbol {4.102}2{42.104} and the dmd topological type with uranium as 3-coordinated (3-c) nodes and tdc2− as either a 4-c node in its bis(μ2-κ1O:κ1O’)-bridging mode, or a simple edge in the bis(κ2O,O’)-chelating mode. In both 1 and 2, as in the previously described nmp complex, but not in [UO2(tdc)(dmf)] (dmf = N,N-dimethylformamide), coordination of a unidentate ligand disrupts the most common formation of diperiodic networks with tdc2− and tris-chelated uranyl, and promotes formation of frameworks in which channels accommodate the pendant, unidentate ligands. Complex 2 has a photoluminescence quantum yield of 3 % in the solid state, and its emission spectrum displays the typical vibronic progression with peak positions in the range usual for complexes with an O5 equatorial uranyl environment; the “hot band” observed at room temperature disappears at 77 K.

Homogeneous catalytic oxidation of thymol with dinuclear Cu(II)-2-phenyl propionate-bipyridine complex

A carboxylate-bridged dinuclear copper(II) complex, [Cu2(μ2-η2:η1(ppa)2(μ2-η1:η1 (ppa)bpy)2]·ClO4·H2O (ppa (C9H9OO) = 2-phenyl propionate, bpy = 2,2′-bipyridine), was prepared and its structure was determined by X-ray diffraction analysis. The octacoordinated Cu(II) dimer complex exhibits an asymmetric conformation, with the metal centers linked by two distinct modes of the carboxylate group. These include an asymmetric chelating bridging bidentate involving two ppa ligands and a syn-syn bidentate bridging mode involving one ppa ligand. The complex was employed as a catalyst for the oxidation of thymol, demonstrating a high degree of quantitative conversion and selectivity with TBHP across a range of solvents at moderate temperatures. The homogeneous catalytic system, comprising Cu(II)-2-phenyl propionate-bipyridine, tert-butylhydroperoxide (TBHP) as oxidant, and a polar aprotic solvent (acetonitrile or acetone), demonstrated high turnover numbers (TOF) in the absence of any additives. The impact of temperature, solvent, the ratio of thymol to TBHP, different oxidants and the quantity of catalyst on the catalytic activity and product selectivity was examined. Under optimized conditions, the maximum conversion of thymol (100 %) was obtained with 100 % selectivity to thymoquinone with TBHP after 35 min at the thymol to catalyst mole ratio of 267 (TOF = 449 h−1) in acetonitrile (MeCN) at 55 °C. Based on the available evidence, this activity and selectivity to thymoquinone represent the highest reported level of performance achieved by a homogeneously copper-catalysed process.

Rare Earth 4‐Hydroxyphenylacetate Complexes: Synthesis, Structural Characterization, and Corrosion Inhibition Properties#

Four different structural types of rare earth aqua 4‐hydroxyphenylacetate complexes {[Ce(L)3(H2O)2]⋅H2O}n (a), {[RE2(L)6(H2O)]⋅4H2O]}n (RE = Nd (b), Gd (c)), {[RE2(L)6(H2O)]⋅3H2O]}n (RE = Dy (d), Y (e)), {[RE2(L)6(H2O)]⋅5H2O]}n (RE = Er (f), Yb (g)), (L = 4‐hydroxyphenylacetate) have been synthesized by the metathesis reactions of corresponding rare earth metals chlorides or nitrates and sodium 4‐hydroxyphenylacetate (NaL). All compounds were obtained as 1‐D polymeric structures, with a common carboxylate coordination mode of chelating bridging. The structure of a differs in being a monometallic repeating unit and having two coordinated waters whilst the others have binuclear repeating units that resulted from the alternating coordination of one water molecule along the chain. Corrosion tests by the weight loss method and potentiodynamic polarisation tests revealed that {[Gd2(L)6(H2O)]⋅4H2O}n has the best corrosion inhibition properties for mild steel in 0.01 M NaCl. Furthermore, all a‐g complexes are more effective corrosion inhibitors than both the aqua and 2,2’‐bipyridine (bpy) complexes of unsubstituted phenylacetate indicating that 4‐OH substitution of phenylacetate enhances anti‐corrosion properties.

Design of dual-defective polymeric carbon nitride with compact interlayer stacking for boosting photocatalytic H2O2 production: Insight of various configurations

Polymeric carbon nitride (PCN) is an environmentally friendly photocatalyst for solar-driven H2O2 production, but the activity of original PCN is still not satisfactory. The main limitation is the sluggish exciton dissociation leading to slow generation and conversion of superoxide radical (•O2−) intermediate. Herein, the PCN with dual defect sites and compact interlayer is rationally designed for H2O2 photosynthesis with an ultrahigh rate of 3930.9 μmol g−1h−1 and rapid •O2− yield rate of 1.92 min−1. The enhanced activity is attributed to effective exciton dissociation during interlayer and intralayer process. Moreover, nitrogen vacancies change the oxygen adsorption configuration (formation of C − O − O − C bridge mode), thus promoting O2 adsorption and activation. A well-matched linear relationship was established between the concentration of nitrogen vacancies and •O2−/H2O2 production. This work not only provides in-depth insights for the photocatalytic H2O2 generation mechanism, but also offers a new paradigm for designing efficient PCN-based photocatalysts for energy conversion.

Unveiling Heterogeneous Catalytic Potential of Distinctly Coordinated Polymers Toward Henry and Morita‐Baylis‐Hillman Reactions

AbstractThree 1D coordination polymers (CPs), {[CuL2(H2O)] ⋅ (H2O)3}n (1) {[CoL2(H2O)2] ⋅ (H2O)}n (2) and {[NiL2(H2O)] ⋅ (H2O)3}n (3), (L1=N‐nicotinoylglycinato) have been synthesized by adopting a solvothermal reaction strategy and characterized through several spectral techniques i. e., elemental analyses, FT‐IR, TGA, EDX, DSC, AAS, and PXRD. X‐ray single crystal analysis revealed the 5‐, 6‐ and 7‐coordinated structures respectively for CPs 1, 2 and 3 wherein, L1 connects the metal ions in a bridging mode. The CPs entail H‐bonding, π–π stacking along with other non‐covalent interactions and expand into 3D supramolecular networks. Further, FESEM and HRTEM provided morphological insight for 1–3 and aid in obtaining interplanar spacings. CPs 1–3 possessing distinct coordination numbers and good thermal stability have been subjected to catalysis after optimization and notably, these serve as efficient, easy to work up, and reusable porous heterogeneous catalysts for Henry and Morita‐Baylis‐Hillman (MBH) reactions with reasonably good yields (97–93 %). Remarkably, catalyzed by 1–3 can be reused at least seven times for the Henry reaction and six times for the MBH reaction, retaining their catalytic efficiency. Relative catalytic efficacy toward the Henry and MBH reactions follows the order 1>2>3. Present findings are based on a rational approach of varying coordination number (5, 6 and 7) and metal ions [Cu(II), Co(II) and Ni(II)] respectively in 1–3 having structural evidence and examine their catalytic performances for typical Henry and MBH reactions.

Single and mixed dithiocarbamato metal(III) complexes (Co, Rh, and Ir): Crystal and molecular structure description and interplay

This review focuses on the crystal and molecular structures of single and mixed dithiocarbamate ligands of cobalt, rhodium, and iridium in the +3 oxidation state. The complexities of their chelating and bridging modes come into play through modification of the substituents on the carbamate nitrogen atoms of the ligands and additional coordination of secondary phosphino-containing ligands, culminating in various applications such as biological, analytical, medicine, and catalysis. Other considerations include the geometrical coordination environments around the metal centres and their comparison with isostructural congeners. The distortions around the metal centres and their subsequent effects on the symmetries of bonds in the primary and secondary coordination spheres are discussed. The trans-effects of secondary P-ligands and their effects on geometrical alignment and structural stability have become valuable yardsticks in analyzing structural modifications and stabilities.

[Cu(en)2]2+ - [W(CN)6(bpy)]2- interactions in cyanido bridged and not linked complexes – structural study

Five heterobimetallic Cu(II)-W(IV) complexes with the general formulas [Cu(en)2][W(CN)6(bpy)], {[Cu(en)2][W(CN)6(bpy)]}2∙[Cu(en)2(H2O)2]X2 (where X = Cl or Br), Na4K2[Cu(en)2][W(CN)6(bpy)]4, Li2[Cu(en)2(H2O)2][W(CN)6(bpy)]2 were synthesized and described by elemental analyses, magnetic measurements, IR and UV–Vis spectra, as well as the single crystal X-ray structure measurements. In structures, the copper atoms adopt the geometry of a slightly distorted octahedron. The effect of the addition of a halogen or alkali metal on the different modes of cyanide bridging in all structures was discussed. These results provide an important contribution to the knowledge on the controllable synthesis of coordination networks based on cyanide bridges.

Structural Diversity and Dimensionality of Three Cu(II)-dpds-C5O5 2- Coordination Polymers Controlled by the Coordination Sphere of Cu(II) Centers and the Coordination Modes of C5O5 2- (dpds = 4,4'-Dipyridyldisulfide).

Three supramolecular architectures, [Cu2(dpds)2(C5O5)2(H2O)4]·3H2O (1), [Cu(dpds)(C5O5)]·3H2O (2), and [Cu2(dpds)2(C5O5)2]·9H2O·C2H5OH (3) (dpds = 4,4'-dipyridyldisulfide and C5O5 2- (croconate) = dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione), have been synthesized and structurally characterized. Compound 1 contains two crystallographically independent Cu(II) ions, which are both distorted octahedral geometry with elongation along the croconate- and H2O-bound axial positions and bonded with two N atoms of two dpds, two O atoms of one C5O5 2-, and two H2O molecules. Two crystallographically independent dpds ligands, both adopting the bis-monodentate bridging mode, connect two Cu(II) ions to form a one-dimensional zigzag chain-like coordination polymer. In 2 and 3, there are two and three crystallographically independent Cu(II) ions, respectively, which are all distorted octahedral geometries with elongation along the croconate-bound axial positions six-coordinated and bonded with two N atoms of two dpds ligands in cis- or/and trans-forms and four O atoms of two C5O5 2- ligands. The dpds ligands in 2 and 3 all adopt the bis-monodentate bridging mode, and the C5O5 2- ligands act as bridging ligands with bridging bis-bidentate through three C5O5 2- oxygen atoms in 2 and bridging bis-bidentate through four adjacent C5O5 2- oxygen atoms in 3, respectively, linking the Cu(II) ions to generate a two-dimensional layered and a three-dimensional metal-organic framework, respectively. The structural diversity and dimensionality observed in 1-3 may be attributed to the cis- or/and trans-coordination sphere of Cu(II) centers with two dpds ligands and the coordination modes of croconate ligands. Thermal stability and in situ temperature-dependent structural variations of 1-3 have been verified by thermogravimetric analysis and powder X-ray diffraction measurements. Compounds 1 and 3 both exhibit water vapor capture behaviors with hysteresis isotherms.

Effect of Damping on the Identification of Bridge Properties Using Vehicle Scanning Methods.

Vehicle scanning methods are gaining popularity because of their ability to identify modal properties of several bridges with only one instrumentation setup, and several methods have been proposed in the last decade. In the numerical models used to develop and validate such methods, bridge damping is often overlooked, and its impact on the efficacy of vehicle scanning methods remains unknown. The present article addresses this knowledge gap by systematically investigating the effects of bridge damping on the efficacy of vehicle scanning methods in identifying the modal properties of bridges. For this, acceleration responses obtained from a numerical model of a bridge and vehicle are used. Four different scenarios are considered where vehicle damping, presence of road roughness, and traffic on the bridge are varied. Bridge damping is modeled using mass-proportional, stiffness-proportional, and Rayleigh damping models. The impacts of ignoring bridge damping or considering one of these damping models on the modal frequencies and mode shapes identified using the vehicle response are investigated by comparing the results. The outcomes of the numerical analysis show that ignoring bridge damping in vehicle scanning applications can significantly increase the efficacy of these methods. They also show that the identifiability of the bridge frequencies and bridge mode shapes from the vehicle response decreases significantly when bridge damping is considered. Further, the damping model used impacts which bridge modes can be identified because different damping models provide different modal damping ratios for each mode. The results highlight the importance of correctly simulating damping behavior of bridges, which is often ignored, to be able to correctly evaluate the efficacy of vehicle scanning methods, and they provide an important stepping stone for future studies in this field.

Failure analysis and structural resilience of a masonry arch Bridge subjected to blast loads: The Case study, Halilviran Bridge

This study investigates the dynamic response of masonry bridges under blast-induced shock waves, focusing on the structural integrity and safety of these critical infrastructure components under extreme conditions. The research employs theoretical approaches to analyze the effects of blast-induced shock waves on masonry bridge structures. A comprehensive numerical simulation framework is developed using finite element analysis (FEA) to model the dynamic interactions between blast waves and the masonry materials. Key parameters, including the blast load intensity, duration, and distance from the blast source, are varied to assess their impact on bridge performance. The results reveal significant insights into the deformation patterns, stress distribution, and potential failure modes of masonry bridges under blast loading scenarios. The findings underscore the importance of incorporating blast resistance measures in the design and retrofitting of masonry bridges to enhance their resilience against explosive events. This study contributes to the advancement of safety standards and design guidelines for masonry bridge structures in the context of blast loading, providing valuable information for engineers, policymakers, and infrastructure managers.

Discrete Element Study on Mechanical Properties of MICP-Treated Sand under Triaxial Compression

Microbial-induced calcium carbonate precipitation (MICP) has attracted much attention as a promising technology for soil improvement in the infrastructures of marine engineering. This paper introduces a novel numerical sample preparation technique for MICP-treated sand, with particular attention paid to the distribution patterns of calcium carbonate, including contact cementing, bridging, and grain coating. The effect of calcium carbonate content (CCC) on the deformation and failure mechanism is studied at macroscopic and granular scales. The findings show that a small amount of calcium carbonate can quickly increase the strength of sand. The strength improvement and deformation control of MICP technology are better than those of traditional compaction treatment. As the calcium carbonate content increases, the mechanical coordination number of the sand also increases, indicating a more stable microstructure of the sand phase. In the contact bonding mode, initial failure occurs as shear failure between sand and calcium carbonate. In the bridge mode, initial failure manifests as shear failure between calcium carbonate particles. In the coating mode, initial failure occurs as tensile failure between sand and calcium carbonate. Calcium carbonate contributes to a reduction in both sliding and rolling movements among sand particles.

Bridge vs Terminal Cyano-coordination in Binuclear Cobalt Porphyrin Dimers: Interplay of Electrons between Metal and Ligand and Spin-Coupling via Bridge.

Three cyano-coordinated cobalt porphyrin dimers were synthesized and thoroughly characterized. The X-ray structure of the complexes reveals that cyanide binds in a terminal fashion in both the anti and trans isomers of ethane- and ethylene-bridged cobalt porphyrin dimers, while in the cis ethylene-bridged dimer, cyanides bind in both terminal and bridging modes. The nonconjugated ethane-bridged complex stabilizes exclusively a diamagnetic metal-centered oxidation of type CoIII(por)(CN)2 both in the solid and in solution. In contrast, the complexes with the conjugated ethylene-bridge contain signatures of both paramagnetic ligand-centered oxidation of the type CoII(por•+)(CN)2 and diamagnetic metal-centered oxidation of type CoIII(por)(CN)2 with the metal-centered oxidized species being the major component in the solid state as observed in XPS, while the ligand-centered oxidized species are present in a significant amount in solution. 1H NMR spectrum in solution displays two set of signals corresponding to the simultaneous presence of both the diamagnetic and paramagnetic species. EPR and magnetic investigation reveal that there is a moderate ferromagnetic coupling between the unpaired electrons of the low-spin CoII center and the porphyrin π-cation radical in CoII(por•+)(CN)2 species as well as an antiferromagnetic coupling between the two CoII(por•+) units through the ethylene and CN bridges.

Review of Vehicle Scanning Method for Bridges from 2004 to 2024

The vehicle scanning method (VSM), originally known as the indirect method, is an efficient method for bridge health monitoring that utilizes mainly the responses collected by the moving test vehicles. This method offers the advantage of mobility, efficiency, and cost-effectiveness as it requires only one or a few vibration sensors mounted on the test vehicle, eliminating the need for deployment of numerous sensors on the bridge. Since its initial proposal by Yang and co-workers in 2004, the VSM has gained intensive attention from researchers worldwide. Over the past two decades, significant progress has been made in various aspects of the VSM, including the identification of bridge frequencies, mode shapes, damping ratios, damages, and surface roughness, as well as its application to railways. Previously, some review papers and the book Vehicle Scanning Method for Bridges were published on the subject. However, research on the subject continues to boom at a speed that cannot be adequately by existing review papers or book, as judged by the fast-increasing number of relevant publications. In order to provide researchers with an overall understanding of the up-to-date researches on the VSM, a state-of-the-art review of the related research conducted worldwide is compiled in this paper. Comments and recommendations will be provided at appropriate points, and concluding remarks, including future research directions, will be presented at the end of the paper.

Impact of Mo+2 addition and thermal annealing on the surface morphology, electrical transport properties and Mott's parameters of WO3 films for potential photonic devices

This work investigates the compositional dependence and thermal annealing of the morphological properties, electrical conductivity mechanisms and Mott's parameters of sprayed MoxW1-xO3 (x = 0, 0.05, 0.10 and 0,20) thin films. The prepared thin films were examined using field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDX) and Fourier transform infrared spectroscopy (FTIR) techniques. In addition, the two-point probe method was used to calculate the electrical properties of MoxW1-xO3 thin films. The FTIR results revealed that; the tungsten hydroxyl bond (W-OH) and the surface hydroxyl group vibrated within the ranges of 1558.62–1645.56 cm−1 and, 3296.76 and 3424.34 cm−1, respectively. Furthermore, a prominent band in the spectrum spanning from 850 to 650 cm−1 represents the W-O-W bridge mode. The FE-SEM investigations found that the molybdenum (Mo) dopant caused significant changes in the surface morphology of the films. The EDX results showed that the percentages of the isotropic elements MoxW1-xO3 agreed well with those obtained by atomic weight. Studies of the conduction mechanism indicate that the transition temperature was approximately 393K. Corresponding to Mott's model, the conduction mechanism below this temperature was across the variable hopping conduction band near the Fermi level. The mechanism exhibited a cycle of localised states through activated thermionic emission above 393K. Mott parameters were also estimated in addition to barrier potential energies, trapping state energies, local state densities, and other variables. The results revealed that both temperature areas had a rise in ρo and ρ1 values during and after annealing. The ΔEo and ΔE1 values in each temperature area decreased as the Mo-ion concentration increased. Furthermore, the conversion temperature gradually reduced as Mo was added. Based on these properties, the study's overall findings indicate that MoxW1-xO3 is suitable for future photonic devices and optoelectronic applications.

Resilient Transportation Systems: Strategies for Mitigating Climate Change Impacts and Enhancing Infrastructure Stability

The transportation sector plays a crucial role in both contributing to climate change and facing its impacts. As extreme weather events become more frequent and severe, transportation infrastructure is increasingly vulnerable to disruptions, posing significant challenges to mobility, safety, and economic stability. strategies for building resilient transportation systems capable of mitigating climate change impacts and enhancing infrastructure stability. Drawing on interdisciplinary research and real-world case studies, this paper explores a range of resilience-enhancing measures applicable to various modes of transportation, including roads, bridges, railways, ports, and airports. These measures encompass both physical infrastructure improvements and operational strategies aimed at reducing vulnerability, enhancing adaptability, and ensuring continuity of service in the face of climate-related hazards.

Study of the Dynamic Reaction Mechanism of the Cable-Stayed Tube Bridge under Earthquake Action

In order to explore the failure mode of the cable-stayed pipe bridge under earthquake action, taking the structural system of an oil and gas pipeline–cable-stayed pipe bridge as the research object, the full-scale finite element calculation model of the cable-stayed pipe bridge–oil and gas pipeline structural system as well as the finite element calculation model considering the additional mass of the oil and gas medium and the fluid–structure interaction effect were established by using ANSYS Workbench finite element software. The stress and displacement of the cable under the earthquake action were analyzed in the time history, as were the response characteristics of the cable when subjected to both methods. The calculation results show that the overall failure of the pipeline is basically the same under the two methods. Compared with the additional mass method, the solution for the fluid–structure coupling method can be derived through a comprehensive analysis of the flow field and structure, respectively, avoiding the sudden change caused by model simplification or calculation error so that the analysis results can better simulate the actual situation. In summary, the fluid–structure interaction method enables a more precise prediction of the dynamic response of the structure, and the findings of this research can provide a theoretical foundation and technical guidance for optimizing the seismic performance of cable-stayed pipe bridges.

Synthesis, Structures, and Magnetic Investigations of Nickel Phosphates: Ni2(PO4)(OH), Ni7(PO4)3(HPO4)(OH)3, and NaNiPO4 Including Potential Haldane Behavior.

Three novel nickel-phosphate structures are reported, Ni2(PO4)(OH) (I), Ni7(PO4)3(HPO4)(OH)3 (II), and NaNiPO4 (III). Each new system was prepared via a high-temperature hydrothermal synthesis at 600-650 °C. All three compounds are built of quasi-one-dimensional (quasi-1-D) Ni2+ containing chains with varying phosphate bridging modes and were characterized by single crystal X-ray diffraction and magnetic susceptibility. All three compounds display very different magnetic behavior. Anisotropic magnetic data is reported for Ni2(PO4)(OH) (I) exhibiting slow antiferromagnetic ordering in the high-temperature regime with substructures that begin to form below 32 K at different field strengths. These characteristics affirm I as being one of the few Haldane-like material candidates. The Ni7(PO4)3(HPO4)(OH)3 (II) material is a member of the unusual ellenbergerite structural family and displays complex inter- and intrachain magnetic interactions while NaNiPO4 (III) shows antiferromagnetic ordering near 18 K. This magnetic behavior is correlated with their structures.

Diverse Coordination Modes and Bidirectional Noninnocence of Pyridyl-β-diketonate on Ruthenium Platforms as a Function of Coligands.

The article demonstrated diverse binding modes of deprotonated 1,3-di(2-pyridinyl)-1,3-propanedione (HL) (κ2-[O,O]-, κ2-[N,O]-, and μ-bis-κ2-[N,O]-) on selective ruthenium platforms: Ru(acac)2 (dimeric [1]ClO4), Ru(bpy)2 (monomeric [2]ClO4), Ru(pap)2 (isomeric monomeric [3]ClO4/[4]ClO4, dimeric [5](ClO4)3), and Ru(PPh3)2(CO) (monomeric 6, isomeric dimeric [7]ClO4/[8]ClO4) (acac = acetylacetonate, bpy = 2,2'-bipyridine, pap = 2-phenylazopyridine). Structural authentication of the complexes revealed (i) diverse binding mode of L- including its unprecedented bridging mode in [8]ClO4, (ii) varying degrees of nonplanarity of L-, and (iii) development of 1D polymeric chains or dimeric/tetrameric forms via intermolecular π-π interactions. The preferential binding feature of L- in the complexes could also be corroborated by their calculated relative energies. The analysis of the multiredox steps of the complexes suggested severe mixing of metal-ligand frontier orbitals, which in effect pinpointed the involvement of L- in both the oxidative and reductive processes along the redox chain, suggesting its bidirectional noninnocence under the present coordination situations. Though α-diketone or β-diketiminate was reported to activate O2 on the selective Ru(acac)2 platform, the inability of analogous β-diketonate-derived [1]ClO4 could be attributed to its calculated greater HOMO-LUMO energy gap, which disfavored electron exchange at the metal(RuIII)-ligand(L-) interface to introduce the required unpaired spin at the ligand backbone toward the 3O2 activation event.

Study of the mechanical properties and propagation mechanisms of non-coplanar and discontinuous joints via numerical simulation experiments

Non-coplanar and discontinuously jointed rock masses are more complex than coplanar and discontinuously jointed rock masses. The mechanical properties and propagation mechanisms of non-coplanar and discontinuous joints were studied via direct shear tests with microscopic numerical simulation experiments. The numerical simulation tests were performed under different normal stresses, joint inclination angles, and shear rates. The numerical experimental results show that the microscale failure of non-coplanar and discontinuously jointed rock masses is mainly caused by tensile cracks. Additionally, when the peak shear stress is reached, the growth rate of cracks increases rapidly, and the number of cracks increases with increasing normal stress. The shear strength of non-coplanar and discontinuously jointed rock masses increases with increasing normal stress. Under the same normal stress, the variation curves of the shear strength of non-coplanar and discontinuously jointed rock masses with respect to the dip angle exhibit an “S”-shaped nonlinear pattern. Rock masses with joint inclination angles of approximately 15° and 65° have minimum and maximum shear strengths, respectively. The joint dip angle has a significant impact on the final failure mode of rock bridges in the rock mass. As the joint dip angle increases, the final failure modes of rock bridges change from “end-to-end” connection to a combination of “head-to-head” and “tail-to-tail” connections. The shear rate has a certain impact on the peak shear stress, but the impact is not significant. The spatial distribution of the tensile force chains changes as shearing progresses, and stress concentration occurs at the tips of the original joints, which is the reason for the development of long tensile cracks in the deeper parts.

Unique Use of Dibromo-L-Tyrosine Ligand in Building of Cu(II) Coordination Polymer-Experimental and Theoretical Investigations.

Although the crystals of coordination polymer {[CuCl(μ-O,O'-L-Br2Tyr)]}n (1) (L-Br2Tyr = 3,5-dibromo-L-tyrosine) were formed under basic conditions, crystallographic studies revealed that the OH group of the ligand remained protonated. Two adjacent [CuCl(L-Br2Tyr)] monomers, bridged by the carboxylate group of the ligand in the syn-anti bidentate bridging mode, are differently oriented to form a polymeric chain; this specific bridging was detected also by FT-IR and EPR spectroscopy. Each Cu(II) ion in polymeric compound 1 is coordinated in the xy plane by the amino nitrogen and carboxyl oxygen of the parent ligand and the oxygen of the carboxyl group from the symmetry related ligand of the adjacent [Cu(L-Br2Tyr)Cl] monomer, as well as an independent chlorine ion. In addition, the Cu(II) ion in the polymer chain participates in long-distance intermolecular contacts with the oxygen and bromine atoms of the ligands located in the adjacent chains; these intramolecular contacts were also supported by NCI and NBO quantum chemical calculations and Hirshfeld surface analysis. The resulting elongated octahedral geometry based on the [CuCl(L-Br2Tyr)] monomer has a lower than axial symmetry, which is also reflected in the symmetry of the calculated molecular EPR g tensor. Consequently, the components of the d-d band obtained by analysis of the NIR-VIS-UV spectrum were assigned to the corresponding electronic transitions.