Self-assembled hyperbranched polymer - gold nanoparticle hybrids : understanding the effect of polymer coverage on assembly size and SERS performance

In the past few years, remarkable progress has been made in unveiling novel and unique optical properties of strongly coupled plasmonic nanostructures. However, application of such plasmonic nanostructures in biomedicine remains challenging due to the lack of facile and robust assembly methods for producing stable nanostructures. Previous attempts to achieve plasmonic nano-assemblies using molecular ligands were limited due to the lack of flexibility that could be exercised in forming them. Here, we report the utilization of tailor-made hyperbranched polymers (HBP) as linkers to assemble gold nanoparticles (NPs) into nano-assemblies. The ease and flexibility in tuning the particle size and number of branch ends of a HBP makes it an ideal candidate as a linker, as opposed to DNA, small organic molecules and linear or dendrimeric polymers. We report a strong correlation of polymer (HBP) concentration with the size of the hybrid nano-assemblies and “hot-spot” density. We have shown that such solutions of stable HBP-gold nano-assemblies can be barcoded with various Raman tags to provide improved surface-enhanced Raman scattering (SERS) compared with non-aggregated NP systems. These Raman barcoded hybrid nano-assemblies, with further optimization of NP shape, size and “hot-spot” density, may find application as diagnostic tools in nanomedicine.

Collective equipments of power: The road and the city

A year ago, I became aware of the historical existence of the group CERFI— Le centre d’etudes, de recherches, et de formation institutionelles, or The Study Center for Institutional Research and Formation. CERFI emerged in 1967 under the hand of Lacanian psychiatrist and Trotskyite activist Félix Guattari, whose antonymous journal Recherches chronicled the group’s subversive experiences, experiments, and government-sponsored urban projects. It was a singularly bizarre meeting of the French bureaucracy with militant activist groups, the French intelligentsia, and architectural and planning practitioners at the close of the ‘60s. Nevertheless, CERFI’s analysis of the problems of society was undertaken precisely from the perspective of the state, and the Institute acknowledged a “deep complicity between the intellectual and statesman ... because the first critics of the State, are officials themselves!”1 CERFI developed out of FGERI (The Federation of Groups for Institutional Study and Research), started by Guattari two years earlier. While FGERI was created for the analysis of mental institutions stemming from Guattari’s work at La Borde, an experimental psychiatric clinic, CERFI marks the group’s shift toward urbanism—to the interrogation of the city itself. Not only a platform for radical debate on architecture and the city, CERFI was a direct agent in the development of urban planning schemata for new towns in France. 2 CERFI’s founding members were Guattari, the economist and urban theorist François Fourquet, feminist philosopher Liane Mozère, and urban planner and editor of Multitides Anne Querrien—Guattari’s close friend and collaborator. The architects Antoine Grumback, Alain Fabre, Macary, and Janine Joutel were also members, as well as urbanists Bruno Fortier, Rainier Hoddé, and Christian de Portzamparc. 3 CERFI was the quintessential social project of post-‘68 French urbanism. Located on the Far Left and openly opposed to the Communist Party, this Trotskyist cooperative was able to achieve what other institutions, according to Fourquet, with their “customary devices—the politburo, central committee, and the basic cells—had failed to do.”4 The decentralized institute recognized that any formal integration of the group was to “sign its own death warrant; so it embraced a skein of directors, entangled, forming knots, liquidating all at once, and spinning in an unknown direction, stopping short and returning back to another node.” Allergic to the very idea of “party,” CERFI was a creative project of free, hybrid-aesthetic blocs talking and acting together, whose goal was none other than the “transformation of the libidinal economy of the militant revolutionary.” The group believed that by recognizing and affirming a “group unconscious,” as well as their individual unconscious desires, they would be able to avoid the political stalemates and splinter groups of the traditional Left. CERFI thus situated itself “on the side of psychosis”—its confessed goal was to serve rather than repress the utter madness of the urban malaise, because it was only from this mad perspective on the ground that a properly social discourse on the city could be forged.

Shear buckling characteristics of cold-formed steel channel beams

Cold-formed steel members are increasingly used as primary structural elements in the building industries around the world due to the availability of thin and high strength steels and advanced cold-forming technologies. Cold-formed lipped channel beams (LCB) are commonly used as flexural members such as floor joists and bearers. However, their shear capacities are determined based on conservative design rules. For the shear design of LCB web panels, their elastic shear buckling strength must be determined accurately including the potential post-buckling strength. Currently the elastic shear buckling coefficients of LCB web panels are determined by assuming conservatively that the web panels are simply supported at the junction between their flange and web elements. Hence finite element analyses were conducted to investigate the elastic shear buckling behavior of LCBs. An improved equation for the higher elastic shear buckling coefficient of LCBs was proposed based on finite element analysis results and included in the ultimate shear capacity equations of the North American cold-formed steel codes. Finite element analyses show that relatively short span LCBs without flange restraints are subjected to a new combined shear and flange distortion action due to the unbalanced shear flow. They also show that significant post-buckling strength is available for LCBs subjected to shear. New equations were also proposed in which post-buckling strength of LCBs was included.

Circulating tumour cells, their role in metastasis and their clinical utility in lung cancer

Circulating tumour cells (CTCs) have attracted much recent interest in cancer research as a potential biomarker and as a means of studying the process of metastasis. It has long been understood that metastasis is a hallmark of malignancy, and conceptual theories on the basis of metastasis from the nineteenth century foretold the existence of a tumour "seed" which is capable of establishing discrete tumours in the "soil" of distant organs. This prescient "seed and soil" hypothesis accurately predicted the existence of CTCs; microscopic tumour fragments in the blood, at least some of which are capable of forming metastases. However, it is only in recent years that reliable, reproducible methods of CTC detection and analysis have been developed. To date, the majority of studies have employed the CellSearch™ system (Veridex LLC), which is an immunomagnetic purification method. Other promising techniques include microfluidic filters, isolation of tumour cells by size using microporous polycarbonate filters and flow cytometry-based approaches. While many challenges still exist, the detection of CTCs in blood is becoming increasingly feasible, giving rise to some tantalizing questions about the use of CTCs as a potential biomarker. CTC enumeration has been used to guide prognosis in patients with metastatic disease, and to act as a surrogate marker for disease response during therapy. Other possible uses for CTC detection include prognostication in early stage patients, identifying patients requiring adjuvant therapy, or in surveillance, for the detection of relapsing disease. Another exciting possible use for CTC detection assays is the molecular and genetic characterization of CTCs to act as a "liquid biopsy" representative of the primary tumour. Indeed it has already been demonstrated that it is possible to detect HER2, KRAS and EGFR mutation status in breast, colon and lung cancer CTCs respectively. In the course of this review, we shall discuss the biology of CTCs and their role in metastagenesis, the most commonly used techniques for their detection and the evidence to date of their clinical utility, with particular reference to lung cancer.

Suitable stiffening systems for LiteSteel beams with web openings subjected to shear

Abstract: LiteSteel beam (LSB) is a new cold-formed steel hollow flange channel section produced using a simultaneous cold-forming and dual electric resistance welding process. It is commonly used as floor joists and bearers with web openings in residential, industrial and commercial buildings. Their shear strengths are considerably reduced when web openings are included for the purpose of locating building services. A cost effective method of eliminating the detrimental effects of a large web opening is to attach suitable stiffeners around the web openings of LSBs. Experimental and numerical studies were undertaken to investigate the shear behaviour and strength of LSBs with circular web openings reinforced using plate, stud, transverse and sleeve stiffeners with varying sizes and thicknesses. Both welding and varying screw-fastening arrangements were used to attach these stiffeners to the web of LSBs. Finite element models of LSBs with stiffened web openings in shear were developed to simulate their shear behaviour and strength of LSBs. They were then validated by comparing the results with experimental test results and used in a detailed parametric study. These studies have shown that plate stiffeners were the most suitable, however, their use based on the current American standards was found to be inadequate. Suitable screw-fastened plate stiffener arrangements with optimum thicknesses have been proposed for LSBs with web openings to restore their original shear capacity. This paper presents the details of the numerical study and the results.

Selective reductions using visible light photocatalysts of supported gold nanoparticles

Photocatalytic synthesis using visible light is a desirable chemical process because of its potential to utilize sunlight. Supported gold nanoparticles (Au-NPs) were found to be efficient photocatalysts and the effects of the supports were identified including CeO2, TiO2, ZrO2, Al2O3, and zeolite Y. In particular Au/CeO2 exhibited the high catalytic activity to reduce nitroaromatics to azo compounds, hydrogenate azobenzene to hydroazobenzene, reduce ketones to alcohols, and deoxygenate epoxides to alkenes at ambient temperatures, under irradiation of visible light (or simulated sunlight). The reac-tive efficiency depends on two primary factors: one is the light adsorption of catalysts and another is the driving ability of catalysts corresponding to the reactants. The light absorption by Au-NPs is due to surface plasmon resonance effect or inter-band electron transition; this is related to the reduction ability of the photocatalysts. Irradiation with shorter wavelengths can excite the conduction electrons in Au-NPs to higher energy levels and as a result, induce reduction with more negative reduction potentials. It is known when irradiated with light the Au-NPs can abstract hydrogen from isopropanol forming Au-H species on the Au-NP surface. Hence, we proposed that the active Au-H species will react with the N=O, N=N, C=O double bonds or epoxide bonds, which are weakened by the interaction with the excited electrons in the Au-NPs, and yield the final reductive products. The reacting power of the Au-H species depends on the energy of the excited electrons in Au-NPs: the higher the electronic energy, the stronger the reduction ability of the Au-H species. This finding demonstrates that we can tune the reduction ability of the photocatalysts by manipulating the irradiation wavelength.

Benchmarking knowledge-based urban development performance : Results from the international comparison of Helsinki

In the era of a global knowledge economy, urban regions that seek to increase their competitive edge, become destinations for talent and investment and provide prosperity and high quality of life to their inhabitants have little chance of achieving these goals without forming effective knowledge-based urban development strategies. The research reported in this paper aims to address the questions of how a knowledge-based urban development performance measurement can be undertaken and the value contribution of such measurement. The paper focuses on the city of Helsinki. This empirical study analytically investigates Helsinki’s performance from the lens of knowledge-based urban development by comparing this urban region with eight international competitors, Boston, San Francisco, Birmingham, Manchester, Melbourne, Sydney, Toronto, and Vancouver. The results of the study not only reveal a clearer understanding of Helsinki’s benchmarked performance and competitive edge considering the regional policy context along with strategic directions in strengthening its international standing and competitiveness but also provide useful insights for other urban regions that aspire to such development.

Cytokine synthesis by intestinal intraepithelial lymphocytes. Both gamma/delta T cell receptor-positive and alpha/beta T cell receptor-positive T cells in the G1 phase of cell cycle produce IFN-gamma and IL-5

Murine intestinal intraepithelial lymphocytes (IEL) have been shown to contain subsets of alpha/beta TCR+ and gamma/delta TCR+ T cells that spontaneously produce cytokines such as IFN-gamma and IL-5. We have now determined the nature and cell cycle stage of these cytokine-producing T lymphocytes in EIL by using IFN-gamma- and IL-5-specific ELISPOT assay, cytokine-specific mRNA-cDNA dot-blot hybridization and polymerase chain reaction, and flow cytometry (FACS) for DNA analysis. When CD3+ T cells from IEL of normal C3H/HeN mice were separated into low and high density fractions by discontinuous Percoll gradients, IFN-gamma and IL-5 spot-forming cells were only found in the former population. Analysis of mRNA for these cytokines by both IFN-gamma- and IL-5-specific dot-blot hybridization and polymerase chain reaction revealed that higher levels of message for IFN-gamma and IL-5 were also seen in the low density fraction. However, cell cycle analysis of these two fractions by FACS using propidium iodide showed a similar pattern of cell cycle stages in both low and high density populations (G0 + G1 approximately 96 to 98% and S/G2 + M approximately 2 to 4%). Finally, mRNA from gamma/delta TCR+ and alpha/beta TCR+ T cells in both low and high density fractions of IEL were analyzed for IFN-gamma and IL-5 message by polymerase chain reaction. After 35 cycles of amplification, both gamma/delta TCR+ and alpha/beta TCR+ T cells in the low density fraction expressed higher levels of message for these two cytokines when compared with the high density population. These results have now shown that both gamma/delta and alpha/beta TCR+ IEL can be separated into low and high density subsets and both fractions possess a similar stage of cell cycle. However, only the low density cells (in G1 phase) of both gamma/delta and alpha/beta TCR types possess increased cytokine-specific mRNA and produce the cytokines IFN-gamma and IL-5. Our results suggest that alpha/beta TCR+ and gamma/delta TCR+ IEL can produce cytokines without cell proliferation.