Photo-cross-linked poly(D,L-lactide)-based networks. Structural characterization by HR-MAS NMR spectroscopy and hydrolytic degradation behavior

To date, biodegradable networks and particularly their kinetic chain lengths have been characterized by analysis of their degradation products in solution. We characterize the network itself by NMR analysis in the solvent-swollen state under magic angle spinning conditions. The networks were prepared by photoinitiated cross-linking of poly(dl-lactide)−dimethacrylate macromers (5 kg/mol) in the presence of an unreactive diluent. Using diffusion filtering and 2D correlation spectroscopy techniques, all network components are identified. By quantification of network-bound photoinitiator fragments, an average kinetic chain length of 9 ± 2 methacrylate units is determined. The PDLLA macromer solution was also used with a dye to prepare computer-designed structures by stereolithography. For these networks structures, the average kinetic chain length is 24 ± 4 methacrylate units. In all cases the calculated molecular weights of the polymethacrylate chains after degradation are maximally 8.8 kg/mol, which is far below the threshold for renal clearance. Upon incubation in phosphate buffered saline at 37 °C, the networks show a similar mass loss profile in time as linear high-molecular-weight PDLLA (HMW PDLLA). The mechanical properties are preserved longer for the PDLLA networks than for HMW PDLLA. The initial tensile strength of 47 ± 2 MPa does not decrease significantly for the first 15 weeks, while HMW PDLLA lost 85 ± 5% of its strength within 5 weeks. The physical properties, kinetic chain length, and degradation profile of these photo-cross-linked PDLLA networks make them most suited materials for orthopedic applications and use in (bone) tissue engineering.

Planning for sustainable urban futures : an ecological approach to sustainable urban development

In recent years, cities have shown increasing signs of environmental problems due to the negative impacts of urban activities. The degradation and depletion of natural resources, climate change, and development pressure on green areas have become major concerns for cities. In response to these problems, urban planning policies have shifted to a sustainable focus and authorities have begun to develop new strategies for improving the quality of urban ecosystems. An extremely important function of an urban ecosystem is to provide healthy and sustainable environments for both natural systems and communities. Therefore, ecological planning is a functional requirement in the establishment of sustainable built environment. With ecological planning, human needs are supplied while natural resources are used in the most effective and sustainable manner and ecological balance is sustained. Protecting human and environmental health, having healthy ecosystems, reducing environmental pollution and providing green spaces are just a few of the many benefits of ecological planning. In this context, this chapter briefly presents a short overview of the importance of the implementation of ecological planning into sustainable urban development. Furthermore, it presents a conceptual framework for a new methodology for developing sustainable urban ecosystems through ecological planning approach.

Engineering an Ecosystem : Taking Cues from Nature’s Paradigm to Build Tissue in the Lab and the Body

This manuscript took a 'top down' approach to understanding survival of inhabitant cells in the ecosystem bone, working from higher to lower length and time scales through the hierarchical ecosystem of bone. Our working hypothesis is that nature “engineered” the skeleton using a 'bottom up' approach,where mechanical properties of cells emerge from their adaptation to their local me-chanical milieu. Cell aggregation and formation of higher order anisotropic struc- ture results in emergent architectures through cell differentiation and extracellular matrix secretion. These emergent properties, including mechanical properties and architecture, result in mechanical adaptation at length scales and longer time scales which are most relevant for the survival of the vertebrate organism [Knothe Tate and von Recum 2009]. We are currently using insights from this approach to har-ness nature’s regeneration potential and to engineer novel mechanoactive materials [Knothe Tate et al. 2007, Knothe Tate et al. 2009]. In addition to potential applications of these exciting insights, these studies may provide important clues to evolution and development of vertebrate animals. For instance, one might ask why mesenchymal stem cells condense at all? There is a putative advantage to self-assembly and cooperation, but this advantage is somewhat outweighed by the need for infrastructural complexity (e.g., circulatory systems comprised of specific differentiated cell types which in turn form conduits and pumps to overcome limitations of mass transport via diffusion, for example; dif-fusion is untenable for multicellular organisms larger than 250 microns in diameter. A better question might be: Why do cells build skeletal tissue? Once cooperatingcells in tissues begin to deplete local sources of food in their aquatic environment, those that have evolved a means to locomote likely have an evolutionary advantage. Once the environment becomes less aquarian and more terrestrial, self-assembled organisms with the ability to move on land might have conferred evolutionary ad-vantages as well. So did the cytoskeleton evolve several length scales, enabling the emergence of skeletal architecture for vertebrate animals? Did the evolutionary advantage of motility over noncompliant terrestrial substrates (walking on land) favor adaptations including emergence of intracellular architecture (changes in the cytoskeleton and upregulation of structural protein manufacture), inter-cellular con- densation, mineralization of tissues, and emergence of higher order architectures?How far does evolutionary Darwinism extend and how can we exploit this knowl- edge to engineer smart materials and architectures on Earth and new, exploratory environments?[Knothe Tate et al. 2008]. We are limited only by our ability to imagine. Ultimately, we aim to understand nature, mimic nature, guide nature and/or exploit nature’s engineering paradigms without engineer-ing ourselves out of existence.

Subchondral bone osteoblasts can induce chondrocyte mineralization during osteoarthritis and this process is relevant to cartilage degradation

Pathological mineralization of articular cartilage is a characteristic feature of osteoarthritis (OA); however, the underlying mechanisms, and their relevance to cartilage degeneration, are not clear. The involvement of subchondral bone changes in OA have been reported previously with the characterization of abnormal subchondral bone mineral density (BMD), osteiod volume, altered bone mechanical parameters and an increase in bone turnover markers. A number of osteoarthritic animal models have demonstrated that subchondral bone changes often precede cartilage degeneration. In this study site specific localization of mineralization markers were detected in the OA cartilage. Chondrocytes and osteoblasts derived from OA cartilage and subchondral bone showed a significant increase in the mRNA expressions of mineralization markers. Interestingly, osteoblasts from OA subchondral bone could significantly decrease cartilage matrix expression; whereas, increase mineralization of chondrocytes (Figure 1). Osteogenic factors, such as CBFA1, ALP, and type X collagen (Col-X), were detected in chondrocytes under mineralization conditions (Figure 2). Furthermore, chondrocyte mineralization was followed by increased mRNA and protein levels of MMP-2, MMP-9 and MMP-13, all of which are detrimental to cartilage integrity in vivo. The data reported here suggests that the upregulation of subchondral bone-mineralization, typical of OA progression, causes cartilage mineralization, and that the mineralization of chondrocytes induce increased MMP levels with a subsequent degradation of the articular cartilage.

The international regulation of sustainable forest management : doctrinal concepts, governing institutions and implementation

The overarching objective of the research was to identify the existence and nature of international legal principles governing sustainable forest use and management. This research intended to uncover a set of forest legal considerations that are relevant for consideration across the globe. The purpose behind this, is to create a theoretical base of international forest law literature which be drawn upon to inform future international forestry research. This research will be of relevance to those undertaking examination of a particular forest issue or those focusing on forests in a particular region. The thesis explains the underlying legal issues in forest regulation, the dominant international regulatory approaches and makes suggestions as to how international and national forest policy could be improved.

Advances in heterogeneous photocatalytic degradation of phenols and dyes in wastewater : a review

The heterogeneous photocatalytic water purification process has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible light spectrum. This paper aims to review and summarize the recently published works in the field of photocatalytic oxidation of toxic organic compounds such as phenols and dyes, predominant in waste water effluent. In this review, the effects of various operating parameters on the photocatalytic degradation of phenols and dyes are presented. Recent findings suggested that different parameters, such as type of photocatalyst and composition, light intensity, initial substrate concentration, amount of catalyst, pH of the reaction medium, ionic components in water, solvent types, oxidizing agents/electron acceptors, mode of catalyst application, and calcinations temperature can play an important role on the photocatlytic degradation of organic compounds in water environment. Extensive research has focused on the enhancement of photocatalysis by modification of TiO2 employing metal, non-metal and ion doping. Recent advances in TiO2 photocatalysis for the degradation of various phenols and dyes are also highlighted in this review.

Influence of parameters on the heterogeneous photocatalytic degradation of pesticides and phenolic contaminants in wastewater : a short review

In recent years, the application of heterogeneous photocatalytic water purification process has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible light spectrum. This paper aims to review and summarize the recently published works on the titanium dioxide (TiO2) photocatalytic oxidation of pesticides and phenolic compounds, predominant in storm and waste water effluents. The effect of various operating parameters on the photocatalytic degradation of pesticides and phenols are discussed. Results reported here suggested that the photocatalytic degradation of organic compounds depends on the type of photocatalyst and composition, light intensity, initial substrate concentration, amount of catalyst, pH of the reaction medium, ionic components in water, solvent types, oxidizing agents/electron acceptors, catalyst application mode, and calcinations temperature in water environment. A substantial amount of research has focused on the enhancement of TiO2 photocatalysis by modification with metal, non-metal and ion doping. Recent developments in TiO2 photocatalysis for the degradation of various pesticides and phenols are also highlighted in this review. It is evident from the literature survey that photocatalysis has shown good potential for the removal of various organic pollutants. However, still there is a need to find out the practical utility of this technique on commercial scale.

Heterogeneous photocatalytic degradation of phenols in wastewater : a review on current status and developments

In recent years, there has been an enormous amount of research and development in the area of heterogeneous photocatalytic water purification process due to its effectiveness in degrading and mineralising the recalcitrant organic compounds as well as the possibility of utilising the solar UV and visible spectrum. One hundred and twenty recently published papers are reviewed and summarised here with the focus being on the photocatalytic oxidation of phenols and their derivatives, predominant in waste water effluent. In this review, the effects of various operating parameters on the photocatalytic degradation of phenols and substituted phenols are presented. Recent findings suggested that different parameters, such as type of photocatalyst and composition, light intensity, initial substrate concentration, amount of catalyst, pH of the reaction medium, ionic components in water, solvent types, oxidising agents/electron acceptors, mode of catalyst application, and calcination temperatures can play an important role on the photocatalytic degradation of phenolic compounds in wastewater. Extensive research has focused on the enhancement of photocatalysis by modification of TiO2 employing metal, non-metal and ion doping. Recent developments in TiO2 photocatalysis for the degradation of various phenols and substituted phenols are also reviewed.

Recent developments in photocatalytic degradation of pesticides and phenols in storm and wastewater effluent

The heterogeneous photocatalytic oxidation process offers a versatile promise in the detoxification and disinfection of wastewater containing hazardous organic compounds such as pesticides and phenolic compounds in storm and wastewater effluent. This process has gained wide attention due to its effectiveness in degrading and mineralizing the organic compounds into harmless and often useful components. To develop an efficient photocatalytic process, titanium dioxide has been actively studied in recent years due to its excellent performance as a photocatalyst under UV light irradiation. This paper aims at critically evaluating and highlighting the recent developments of the heterogeneous photocatalytic systems with a special focus on storm and wastewater treatment applications.