Azo-linked corner porphyrin systems: synthesis, crystal structures and spectroscopic investigation

1,2-Bis[10,15-di(3,5-di-tert-butyl)phenylporphyrinatonickel(II)-5-yl]diazene was synthesised via copper catalysed coupling of aminated nickel(II) 5,10-diarylporphyrin (“corner porphyrin”) and its X-ray crystal structure was determined. Two different crystals yielded different structures, one with the free meso positions in a trans-like orientation, and the other with a cis-like disposition. The free meso positions of the obtained dimer have been further functionalised while the synthesis of a zinc analogue has so far been unsuccessful. The X-ray crystal structure of the dinitro derivative of the dinickel(II) azoporphyrin was determined, and the structure showed a cis-like disposition of the nitro groups.

One-dimensional hydrogen-bonded structures in the 1:1 proton-transfer salts of 4,5-dichlorophthalic acid with the aliphatic Lewis bases diisopropylamine and hexamethylenetetramine

The crystal structures of the 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with the aliphatic Lewis bases diisopropylamine and hexamethylenetetramine, viz. diisopropylaminium 2-carboxy-4,5-dichlorobenzoate (1) and hexamethylenetetraminium 2-carboxy-4,5-dichlorobenzoate hemihydrate (2), have been determined. Crystals of both 1 and 2 are triclinic, space group P-1, with Z = 2 in cells with a = 7.0299(5), b = 9.4712(7), c = 12.790(1)Å, α = 99.476(6), β = 100.843(6), γ = 97.578(6)o (1) and a = 7.5624(8), b = 9.8918(8), c = 11.5881(16)Å, α = 65.660(6), β = 86.583(4), γ = 86.987(8)o (2). In each, one-dimensional hydrogen-bonded chain structures are found: in 1 formed through aminium N+-H...Ocarboxyl cation-anion interactions. In 2, the chains are formed through anion carboxyl O...H-Obridging water interactions with the cations peripherally bound. In both structures, the hydrogen phthalate anions are essentially planar with short intra-species carboxylic acid O-H...Ocarboxyl hydrogen bonds [O…O, 2.381(3) Å (1) and 2.381(8) Å (2)].

Performance of reinforced concrete columns under the vehicular impacts

Frontal columns in buildings and columns in car parks are vulnerable to vehicular impacts. This paper treats the impact response of such concrete columns under vehicular loads and the use of polymer wrap to enhance their impact capacity. Comprehensive dynamic computer simulation techniques are used along with strain rate effects and hour glass control to evaluate the impact response. Results indicate the effectiveness of wraps in enhancing the impact capacity of these columns.

Low-dimensional hydrogen-bonded structures in the 1:1 and 1:2 proton-transfer compounds of 4,5-dichlorophthalic acid with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine

The structures of proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine, namely triethylaminium 2-carboxy-4,5-dichlorobenzoate C~6~H~16~N^+^ C~8~H~3~Cl~2~O~4~^-^ (I), diethylaminium 2-carboxy-4,5-dichlorobenzoate C~4~H~12~N^+^ C~8~H~3~Cl~2~O~4~^-^ (II), bis(n-butylaminium) 4,5-dichlorophthalate monohydrate 2(C~4~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (III) and bis(piperidinium) 4,5-dichlorophthalate monohydrate 2(C~5~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (IV)have been determined at 200 K. All compounds have hydrogen-bonding associations giving in (I) discrete cation-anion units, linear chains in (II) while (III) and (IV) both have two-dimensional structures. In (I) a discrete cation-anion unit is formed through an asymmetric R2/1(4) N+-H...O,O' hydrogen-bonding association whereas in (II), one-dimensional chains are formed through linear N-H...O associations by both aminium H donors. In compounds (III) and (IV) the primary N-H...O linked cation-anion units are extended into a two-dimensional sheet structure via amide N-H...O(carboxyl) and ...O(carbonyl) interactions. In the 1:1 salts [(I) and (II)], the hydrogen 4,5-dichlorophthalate anions are essentially planar with short intramolecular carboxylic acid O-H...O(carboxyl) hydrogen bonds [O...O, 2.4223(14) and 2.388(2)A respectively]. This work provides a further example of the uncommon zero-dimensional hydrogen-bonded DCPA-Lewis base salt and the one-dimensional chain structure type, while even with the hydrate structures of the 1:2 salts with the primary and secondary amines, the low dimensionality generally associated with 1:1 DCPA salts is also found.

Axial shortening in reinforced concrete members using vibration characteristics - Part 1 - Theory

Differential axial shortening in vertical members of reinforced concrete high-rise buildings occurs due to shrinkage, creep and elastic shortening, which are time dependent effects of concrete. This has to be quantified in order to make adequate provisions and mitigate its adverse effects. This paper presents a novel procedure for quantifying the axial shortening of vertical members using the variations in vibration characteristics of the structure, in lieu of using gauges which can pose problems in use during and after the construction. This procedure is based on the changes in the modal flexiblity matrix which is expressed as a function of the mode shapes and the reciprocal of the natural frequencies. This paper will present the development of this novel procedure.

Axial shortening in reinforced concrete members using vibration characteristics - part 2 - Application

Controlling differential axial shortening in vertical load bearing concrete elements is a major concern for new generation tall buildings with complex geometries and mechanisms. Quantification of axial shortening using gauges to verify the pre-estimated numerical values used at the design stage is a well established method. This method makes adequate provision to mitigate the adverse effects during the construction. However, this method is becoming increasingly unusable due to its drawbacks. This highlights the need a novel method to quantify the axial shortening using ambient measurements. This paper will first brief introduce the method and then illustrate its application to a high-rise building with two outrigger and belt systems. Moreover, this procedure can be used as a health or performance monitoring tool of the building structure, both during and after construction.

Improved correlation-based modal strain energy method for global damage detection of truss bridge structures

The previous investigations have shown that the modal strain energy correlation method, MSEC, could successfully identify the damage of truss bridge structures. However, it has to incorporate the sensitivity matrix to estimate damage and is not reliable in certain damage detection cases. This paper presents an improved MSEC method where the prediction of modal strain energy change vector is differently obtained by running the eigensolutions on-line in optimisation iterations. The particular trail damage treatment group maximising the fitness function close to unity is identified as the detected damage location. This improvement is then compared with the original MSEC method along with other typical correlation-based methods on the finite element model of a simple truss bridge. The contributions to damage detection accuracy of each considered mode is also weighed and discussed. The iterative searching process is operated by using genetic algorithm. The results demonstrate that the improved MSEC method suffices the demand in detecting the damage of truss bridge structures, even when noised measurement is considered.

Numerical simulation of axially loaded concrete columns under transverse impact and vulnerability assessment

With a view to assessing the vulnerability of columns to low elevation vehicular impacts, a non-linear explicit numerical model has been developed and validated using existing experimental results. The numerical model accounts for the effects of strain rate and confinement of the reinforced concrete, which are fundamental to the successful prediction of the impact response. The sensitivity of the material model parameters used for the validation is also scrutinised and numerical tests are performed to examine their suitability to simulate the shear failure conditions. Conflicting views on the strain gradient effects are discussed and the validation process is extended to investigate the ability of the equations developed under concentric loading conditions to simulate flexural failure events. Experimental data on impact force–time histories, mid span and residual deflections and support reactions have been verified against corresponding numerical results. A universal technique which can be applied to determine the vulnerability of the impacted columns against collisions with new generation vehicles under the most common impact modes is proposed. Additionally, the observed failure characteristics of the impacted columns are explained using extended outcomes. Based on the overall results, an analytical method is suggested to quantify the vulnerability of the columns.

Damage detection for truss bridge structures using correlation-based structural modal strain energy

This paper presents the feasibility of using structural modal strain energy as a parameter employed in correlation- based damage detection method for truss bridge structures. It is an extension of the damage detection method adopting multiple damage location assurance criterion. In this paper, the sensitivity of modal strain energy to damage obtained from the analytical model is incorporated into the correlation objective function. Firstly, the sensitivity matrix of modal strain energy to damage is conducted offline, and for an arbitrary damage case, the correlation coefficient (objective function) is calculated by multiplying the sensitivity matrix and damage vector. Then, a genetic algorithm is used to iteratively search the damage vector maximising the correlation between the corresponding modal strain energy change (hypothesised) and its counterpart in measurement. The proposed method is simulated and compared with the conventional methods, e.g. frequency-error method, coordinate modal assurance criterion and multiple damage location assurance criterion using mode shapes on a numerical truss bridge structure. The result demonstrates the modal strain energy correlation method is able to yield acceptable damage detection outcomes with less computing efforts, even in a noise contaminated condition.

Design methods of rhombic tensegrity structures

As a special type of novel flexible structures, tensegrity holds promise for many potential applications in such fields as materials science, biomechanics, civil and aerospace engineering. Rhombic systems are an important class of tensegrity structures, in which each bar constitutes the longest diagonal of a rhombus of four strings. In this paper, we address the design methods of rhombic structures based on the idea that many tensegrity structures can be constructed by assembling one-bar elementary cells. By analyzing the properties of rhombic cells, we first develop two novel schemes, namely, direct enumeration scheme and cell-substitution scheme. In addition, a facile and efficient method is presented to integrate several rhombic systems into a larger tensegrity structure. To illustrate the applications of these methods, some novel rhombic tensegrity structures are constructed.

Post-tensioning and its effect on multi-level formwork load distribution

Multi-level concrete buildings requrre substantial temporary formwork structures to support the slabs during construction. The primary function of this formwork is to safely disperse the applied loads so that the slab being constructed, or the portion of the permanent structure already constructed, is not overloaded. Multi-level formwork is a procedure in which a limited number of formwork and shoring sets are cycled up the building as construction progresses. In this process, each new slab is supported by a number of lower level slabs. The new slab load is, essentially, distributed to these supporting slabs in direct proportion to their relative stiffness. When a slab is post-tensioned using draped tendons, slab lift occurs as a portion of the slab self-weight is balanced. The formwork and shores supporting that slab are unloaded by an amount equivalent to the load balanced by the post-tensioning. This produces a load distribution inherently different from that of a conventionally reinforced slab. Through , theoretical modelling and extensive on-site shore load measurement, this research examines the effects of post-tensioning on multilevel formwork load distribution. The research demonstrates that the load distribution process for post-tensioned slabs allows for improvements to current construction practice. These enhancements include a shortening of the construction period; an improvement in the safety of multi-level form work operations; and a reduction in the quantity of form work materials required for a project. These enhancements are achieved through the general improvement in safety offered by post-tensioning during the various formwork operations. The research demonstrates that there is generally a significant improvement in the factors of safety over those for conventionally reinforced slabs. This improvement in the factor of safety occurs at all stages of the multi-level formwork operation. The general improvement in the factors of safety with post-tensioned slabs allows for a shortening of the slab construction cycle time. Further, the low level of load redistribution that occurs during the stripping operations makes post-tensioned slabs ideally suited to reshoring procedures. Provided the overall number of interconnected levels remains unaltered, it is possible to increase the number of reshored levels while reducing the number of undisturbed shoring levels without altering the factors of safety, thereby, reducing the overall quantity of formwork and shoring materials.