Effects of the architecture of tissue engineering scaffolds on cell seeding and culturing

The advance of rapid prototyping techniques has significantly improved control over the pore network architecture of tissue engineering scaffolds. In this work we assessed the influence of scaffold pore architecture on cell seeding and static culturing, by comparing a computer‐designed gyroid architecture fabricated by stereolithography to a random‐pore architecture resulting from salt���leaching. The scaffold types showed comparable porosity and pore size values, but the gyroid type showed a more than tenfold higher permeability due to the absence of size‐limiting pore interconnections. The higher permeability significantly improved the wetting properties of the hydrophobic scaffolds, and increased the settling speed of cells upon static seeding of immortalised mesenchymal stem cells. After dynamic seeding followed by 5 days of static culture, gyroid scaffolds showed large cell populations in the centre of the scaffold, while salt���leached scaffolds were covered with a cell‐sheet on the outside and no cells were found in the scaffold centre. It was shown that interconnectivity of the pores and permeability of the scaffold prolongs the time of static culture before overgrowth of cells at the scaffold periphery occurs. Furthermore, novel scaffold designs are proposed to further improve the transport of oxygen and nutrients throughout the scaffolds, and to create tissue engineering grafts with designed, pre‐fabricated vasculature.

Three-dimensional hydrogen-bonded structures in the guanidinium salts of the monocyclic dicarboxylic acids rac-trans-cyclohexane-1,2-dicarboxylic acid (2:1, anhydrous), isophthalic acid (1:1, monohydrate) and terephthalic acid (2:1, trihydrate).

The structures of bis(guanidinium)rac-trans-cyclohexane-1,2-dicarboxylate, 2(CH6N3+) C8H10O4- (I), guanidinium 3-carboxybenzoate monohydrate CH6N3+ C8H5O4- . H2O (II) and bis(guanidinium) benzene-1,4-dicarboxylate trihydrate, 2(CH6N3+) C8H4O4^2- . 3H2O (III) have been determined and the hydrogen bonding in each examined. All three compounds form three-dimensional hydrogen-bonded framework structures. In anhydrous (I), both guanidinium cations give classic cyclic R2/2(8) N--H...O,O'(carboxyl) and asymmetric cyclic R1/2(6) hydrogen-bonding interactions while one cation gives an unusual enlarged cyclic interaction with O acceptors of separate ortho-related carboxyl groups [graph set R2/2(11)]. Cations and anions also associate across inversion centres giving cyclic R2/4(8) motifs. In the 1:1 guanidinium salt (II), the cation gives two separate cyclic R1/2(6) interactions, one with a carboxyl O-acceptor, the other with the water molecule of solvation. The structure is unusual in that both carboxyl groups give short inter-anion O...H...O contacts, one across a crystallographic inversion centre [2.483(2)\%A], the other about a two-fold axis of rotation [2.462(2)\%A] with a half-occupancy hydrogen delocalized on the symmetry element in each. The water molecule links the cation--anion ribbon structures into a three-dimensional framework. In (III), the repeating molecular unit comprises a benzene-1,4-dicarboxylate dianion which lies across a crystallographic inversion centre, two guanidinium cations and two water molecules of solvation (each set related by two-fold rotational symmetry), and a single water molecule which lies on a two-fold axis. Each guanidinium cation gives three types of cyclic interactions with the dianions: one R^1^~2~(6), the others R2/3(8) and R3/3(10) (both of these involving the water molecules), giving a three-dimensional structure through bridges down the b cell direction. The water molecule at the general site also forms an unusual cyclic R2/2(4) homodimeric association across an inversion centre [O--H...O, 2.875(2)\%A]. The work described here provides further examples of the common cyclic guanidinium cation...carboxylate anion hydrogen-bonding associations as well as featuring other less common cyclic motifs.

Bis(4-carbamoylpiperidinium)biphenyl-4,4'-disulfonate

In the title isonipecotamide salt 2C6H13N2O+.C12H8O6S22-,the asymmetric unit comprises one biphenyl-4,4'-disulfonate dianion which lies across a crystallographic inversion centre and another in a general position [dihedral angle between the two phenyl rings is 37.1(1)deg], together with three isonipecotamide cations. Two of these cations give a cyclic homomeric amide-amide dimer interaction [graph set R2/2(8)],the other giving a similar dimeric interaction but across an inversion centre, both dimers then forming lateral cyclic R2/4(8) pyrimidinium N-H...O interactions. These units are linked longitudinally to the sulfonate groups of the dianions through piperidinium N-H...O hydrogen bonds, giving a three-dimensional framework structure.

Designed tissue engineering scaffolds prepared by stereolithography

For the fabrication of tissue engineering scaffolds, the intended tissue formation process imposes requirements on the architecture. The chosen porosity often is a tradeoff between volume and surface area accessible to cells, and mechanical properties of the construct. Interconnectivity of the pores is essential for cell migration through the scaffold and for mass transport. Conventional techniques such as salt leaching often result in heterogeneous structures and do not allow for a precise control of the architecture. Stereolithography is a rapid prototyping method that can be utilised to make 3D constructs with high spatial control by radical photopolymerisation. In this study, a regular structure based on cyclic repetition of cell units were designed through CAD modelling.. One of these structures was built on a stereolithography apparatus (SLA). Furthermore, a polylactide-based resin was developed that can be applied in stereolithography. Polylactide has proven before to be a well-performing polymer in bone tissue engineering. The final objective in this study is to build newly designed PDLLA scaffolds with a precise SLA fabrication technique to study the effect of scaffold architecture on mechanical and biological properties.

Micro-CT analysis of tissue engineering scaffold architectures

A novel method was developed for a quantitative assessment of pore interconnectivity using micro-CT data. This method makes use of simulated spherical particles, percolating through the interconnected pore network. For each sphere diameter, the accessible pore volume is calculated. This algorithm was applied to compare pore interconnectivity of two different scaffold architectures; one created by salt-leaching and the other by stereolithography. The algorithm revealed a much higher pore interconnectivity for the latter one.

Organometallic macrocyclic chemistry. 8.(1) : an unusual metallacycle derived from phosphine−alkynyl thioether coupling

The α,ω-diyne 4,7,10-trithiatrideca-2,11-diyne reacts with [RuCl2(PPh3)3] and KPF6 to form the phosphonio-substituted metallatricyclic salt [RuCl(PPh3){κ4C,S,S′,S′′-S(C≡CMe)C2H4SC2H4SC(PPh3)CMe}]PF6 arising from the activation of one alkynyl group toward nucleophilic attack by extraneous phosphine.

The formation of, and change in, the psychological contracts of graduates entering the Queensland public sector

The workplace is evolving and the predicted impact of demographic changes (Salt, 2009; Taylor, 2005) has seen organisations focus on strategic workforce planning. As part of this, many organisations have established or expanded formalised graduate programs to attract graduates and transition them effectively into organisations (McDermott, Mangan, & O'Connor, 2005; Terjesen, Freeman, & Vinnicombe, 2007). The workplace context is also argued to be changing because of the divergence in preferences and priorities across the different generations in the workplace - a topic which is prolific in the popular culture media but is yet to be fully developed in the academic literature (Jorgenson, 2003). The public sector recruits large numbers of graduates and maintains well established graduate programs. Like the workplace context, the public sector is seen to be undergoing a transition to more closely align its practices and processes with that of the private sector (Haynes & Melville Jones, 1999; N. Preston, 1995). Consequently, questions have been raised as to how new workforce entrants see the public sector and its associated attractiveness as an employment option. This research draws together these issues and reviews the formation of, and change in, the psychological contracts of graduates across ten Queensland public sector graduate programs. To understand the employment relationship, the theories of psychological contract and public service motivation are utilised. Specifically, this research focuses on graduates' and managers' expectations over time, the organisational perspective of the employment relationship and how ideology influences graduates' psychological contract. A longitudinal mixed method design, involving individual interviews and surveys, is employed along with significant researcher-practitioner collaboration throughout the research process. A number of important qualitative and quantitative findings arose from this study and there was strong triangulation between results from the two methods. Prior to starting with the organisation, graduates found it difficult to articulate their expectations; however, organisational experience rapidly brought these to the fore. Of the expectations that became salient, most centred on their relationship with their supervisor. Without experience and quality information on which to base their expectations, graduates tended to over-rely on sectoral stereotypes which negatively impacted their psychological contracts. Socialisation only limited affected graduates' psychological contracts and public service motivation. The graduate survey, measured thrice throughout the first 12 months of the graduate program, revealed that the psychological contract and public service motivation results followed a similar trajectory of beginning at mediocre levels, declining between times one and two and increasing between times two and three (although this is not back to original levels). Graduates attributed these to a number of sectoral, organisational, team, supervisory and individual factors. On a theoretical level, this research provides support for the notion of ideology within the psychological contract although it raises some important questions about how it is conceptualised. Additionally, support is given for the manager to be seen as the primary organisational counterpart to the employee in future theoretical and practical work. The research also argues to extend current notions of time within the psychological contract as this seems to be the most divergent and combustible issue across the generations in terms of how the workplace is perceived. A number of practical implications also transpire from the study and the collaborative foundation was highly successful. It is anticipated that this research will make a meaningful contribution to both the theory and practice of the employment relationship with particular regard to graduates entering the public sector.

Hydrogen bonding in proton-transfer compounds of 5-sulfosalicylic acid with a series of aliphatic nitrogen Lewis bases

The crystal structures of the proton-transfer compounds of 5-sulfosalicylic acid (3-carboxy-4-hydroxybenzenesulfonic acid) with the aliphatic nitrogen Lewis bases, hydroxylamine, triethylamine, pyrrolidine, morpholine, N-methylmorpholine and piperazine, viz. hydroxyammonium 3-carboxy-4-hydroxybenzenesulfonate (1), triethylaminium 3-carboxy-4-hydroxybenzenesulfonate (2), pyrrolidinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate (3), morpholinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate (4), N-methylmorpholinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate (5) and piperazine-1,4-diium bis(3-carboxy-4-hydroxybenzenesulfonate) hexahydrate (6) have been determined and their comparative structural features and hydrogen-bonding patterns described. Crystals of 4 are triclinic, space group P-1 while the remainder are monoclinic with space group either P21/c (1 - 3) or P21/n (5, 6). Unit cell dimensions and contents are: for 1, a = 5.0156(3), b = 10.5738(6), c = 18.4785(9) Å, β = 96.412(5)o, Z = 4; for 2, a = 8.4998(4), b = 12.3832(6), c = 15.4875(9) Å, β = 102.411(5)o, Z = 4; for 3, a = 6.8755(2), b = 15.5217(4), c = 12.8335(3) Å, β = 92.074(2)o, Z = 4; for 4, a = 6.8397(2), b = 12.9756(5), c = 15.8216(6) Å, α = 90.833(3), β = 95.949(3), γ = 92.505(3)o, Z = 4; for 5, a = 7.0529(3), b = 13.8487(7), c = 15.6448(6) Å, β = 90.190(6)o, Z = 4; for 6, a = 7.0561(2), b = 15.9311(4), c = 12.2102(3) Å, β = 100.858(3)o, Z = 2. The hydrogen bonding generates structures which are either two-dimensional (2 and 5) or three-dimensional (1, 3, 4 and 6). Compound 6 represents the third reported structure of a salt of 5-sulfosalicylic acid having a dicationic piperazine species.

Source apportionment of fine particles at a suburban site in Queensland, Australia

Airborne fine particles were collected at a suburban site in Queensland, Australia between 1995 and 2003. The samples were analysed for 21 elements, and Positive Matrix Factorisation (PMF), Preference Ranking Organisation METHods for Enrichment Evaluation (PROMETHEE) and Graphical Analysis for Interactive Assistance (GAIA) were applied to the data. PROMETHEE provided information on the ranking of pollutant levels from the sampling years while PMF provided insights into the sources of the pollutants, their chemical composition, most likely locations and relative contribution to the levels of particulate pollution at the site. PROMETHEE and GAIA found that the removal of lead from fuel in the area had a significant impact on the pollution patterns while PMF identified 6 pollution sources including: Railways (5.5%), Biomass Burning (43.3%), Soil (9.2%), Sea Salt (15.6%), Aged Sea Salt (24.4%) and Motor Vehicles (2.0%). Thus the results gave information that can assist in the formulation of mitigation measures for air pollution.

4-Carbamoylpiperidinium 2-carboxybenzoate-benzene-1,2-dicarboxylic acid (1/1)

In the structure of the title salt adduct, C6H13N2O+ C8H5O4- . C8H6O4, the asymmetric unit comprises one isonipecotamide cation, a hydrogen phthalate anion and a phthalic acid adduct molecule and form a two-dimensional hydrogen-bonded network through head-to-tail cation-anion-adduct molecule interactions which include a cyclic heteromolecular amide--carboxylate motif [graph set R2/2(8)], conjoint cyclic R2/2(6) and R3/3(10) piperidinium N-H...O(carboxyl) associations, as well as strong carboxylic acid O-H...O(carboxyl) hydrogen bonds.

2-(4-Aminophenyl)-1-phenyldiazenium 2,4,6-trinitrophenolate

In the structure of the title salt, C12H12N3+ C6H2N3O7-, the diazenyl group of the 4-(phenyldiazenyl)aniline molecule is protonated and forms a hydrogen bond with the phenolate O acceptor of the picrate anion. Structure extension occurs through two symmetrical inter-ion three-centre amine N---H...O,O'(nitro) hydrogen-bonding associations [graph set R2/1(4)] giving a convoluted two-dimensional network structure.

Improved salinity management for the Nebine / Mungallala / Wallam catchment

The low stream salinity naturally in the Nebine-Mungallala Catchment, extent of vegetation retention, relatively low rainfall and high evaporation indicates that there is a relatively low risk of rising shallow groundwater tables in the catchment. Scalding caused by wind and water erosion exposing highly saline sub-soils is a more important regional issue, such as in the Homeboin area. Local salinisation associated with evaporation of bore water from free flowing bore drains and bores is also an important land degradation issue particularly in the lower Nebine, Wallam and Mungallala Creeks. The replacement of free flowing artesian bores and bore drains with capped bores and piped water systems under the Great Artesian Basin bore rehabilitation program is addressing local salinisation and scalding in the vicinity of bore drains and preventing the discharge of saline bore water to streams. Three principles for the prevention and control of salinity in the Nebine Mungallala catchment have been identified in this review: • Avoid salinity through avoiding scalds – i.e. not exposing the near-surface salt in landscape through land degradation; • Riparian zone management: Scalding often occurs within 200m or so of watering lines. Natural drainage lines are most likely to be overstocked, and thus have potential for scalding. Scalding begins when vegetation is removed, and without that binding cover, wind and water erosion exposes the subsoil; and • Monitoring of exposed or grazed soil areas. Based on the findings of the study, we make the following recommendations: 1. Undertake a geotechnical study of existing maps and other data to help identify and target areas most at risk of rising water tables causing salinity. Selected monitoring should then be established using piezometers as an early warning system. 2. SW NRM should financially support scald reclamation activity through its various funding programs. However, for this to have any validity in the overall management of salinity risk, it is critical that such funding require the landholder to undertake a salinity hazard/risk assessment of his/her holding. 3. A staged approach to funding may be appropriate. In the first instance, it would be reasonable to commence funding some pilot scald reclamation work with a view to further developing and piloting the farm hazard/risk assessment tools, and exploring how subsequent grazing management strategies could be incorporated within other extension and management activities. Once the details of the necessary farm level activities have been more clearly defined, and following the outcomes of the geotechnical review recommended above, a more comprehensive funding package could be rolled out to priority areas. 4. We recommend that best-practice grazing management training currently on offer should be enhanced with information about salinity risk in scald-prone areas, and ways of minimising the likelihood of scald formation. 5. We recommend that course material be developed for local students in Years 6 and 7, and that arrangements be made with local schools to present this information. Given the constraints of existing syllabi, we envisage that negotiations may have to be undertaken with the Department of Education in order for this material to be permitted to be used. We have contact with key people who could help in this if required. 6. We recommend that SW NRM continue to support existing extension activities such as Grazing Land Management and the Monitoring Made Easy tools. These aids should be able to be easily expanding to incorporate techniques for monitoring, addressing and preventing salinity and scalding. At the time of writing staff of SW NRM were actively involved in this process. It is important that these activities are adequately resourced to facilitate the uptake by landholders of the perception that salinity is an issue that needs to be addressed as part of everyday management. 7. We recommend that SW NRM consider investing in the development and deployment of a scenario-modelling learning support tool as part of the awareness raising and education activities. Secondary salinity is a dynamic process that results from ongoing human activity which mobilises and/or exposes salt occurring naturally in the landscape. Time scales can be short to very long, and the benefits of management actions can similarly have immediate or very long time frames. One way to help explain the dynamics of these processes is through scenario modelling.

Does sea-level rise have an impact on saltwater intrusion?

Climate change effects are expected to substantially raise the average sea level. It is widely assumed that this raise will have a severe adverse impact on saltwater intrusion processes in coastal aquifers. In this study we hypothesize that a natural mechanism, identified as the “lifting process” has the potential to mitigate or in some cases completely reverse the adverse intrusion effects induced by sea-level rise. A detailed numerical study using the MODFLOW-family computer code SEAWAT, was completed to test this hypothesis and to understand the effects of this lifting process in both confined and unconfined systems. Our conceptual simulation results show that if the ambient recharge remains constant, the sea-level rise will have no long-term impact (i.e., it will not affect the steady-state salt wedge) on confined aquifers. Our transient confined flow simulations show a self-reversal mechanism where the wedge which will initially intrude into the formation due to the sea-level rise would be naturally driven back to the original position. In unconfined systems, the lifting process would have a lesser influence due to changes in the value of effective transmissivity. A detailed sensitivity analysis was also completed to understand the sensitivity of this self-reversal effect to various aquifer parameters.

Bis(guanidinium) 4,5-dichlorophthalate monohydrate

In the structure of the title hydrate salt 2(CH6N3)+ C8H2Cl2O42- . H2O, the planes of the carboxylate groups of the dianion are rotated out of the plane of the benzene ring [dihedral angles 48.42(10) and 55.64(9)deg.]. A duplex-sheet structure is formed through guanidinium-carboxylate N-H...O, guanidinium-water N-H...O, and water-carboxylate O-H..O hydrogen-bonding associations.

Proton-transfer compounds of isnipecotamide with the aromatic dicarboxylic acids 4-nitrophthalic, 4,5-dichlorophthalic, 5-nitroisophthalic and terephthalic acid

The structures of the 1:1 proton-transfer compounds of isonipecotamide (4-piperidinecarboxamide) with 4-nitrophthalic acid, 4-carbamoylpiperidinium 2-carboxy-4-nitrobenzoate, C6H13N2O8+ C8H4O6- (I), 4,5-dichlorophthalic acid, 4-carbamoylpiperidinium 2-carboxy-4,5-dichlorobenzoate, C6H13N2O8+ C8H3Cl2O4- (II) and 5-nitroisophthalic acid, 4-carbamoylpiperidinium 3-carboxy-5-nitrobenzoate, C6H13N2O8+ C8H4O6- (III) as well as the 2:1 compound with terephthalic acid, bis(4-carbamoylpiperidinium)benzene-1,2-dicarboxylate dihydrate, 2(C6H13N2O8+) C8H4O42- . 2H2O (IV)have been determined at 200 K. All salts form hydrogen-bonded structures, one-dimensional in (II) and three-dimensional in (I), (III) and (IV). In (I) and (III) the centrosymmetric R2/2(8) cyclic amide-amide association is found while in (IV) several different types of water-bridged cyclic associations are present [graph sets R2/4(8), R3/4(10), R4/4(12), R3/3(18) and R4/6(22)]. The one-dimensional structure of (I), features the common 'planar' hydrogen 4,5-dichlorophthalate anion together with enlarged cyclic R3/3(13) and R3/4(17) associations. With the structures of (I) and (III) the presence of head-to-tail hydrogen phthalate chain substructures is found. In (IV) head-to-tail primary cation-anion associations are extended longitudinally into chains through the water-bridged cation associations and laterally by piperidinium N-H...O(carboxyl) and water O-H...O(carboxyl) hydrogen bonds. The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. An additional example of cation--anion association with this cation is also shown in the asymmetric three-centre piperidinium N-H...O,O'(carboxyl) interaction in the first-reported structure of a 2:1 isonipecotamide-carboxylate salt.