Post-assembly modification of kinetically metastable Fe(II)2L3 triple helicates.

We report the covalent post-assembly modification of kinetically metastable amine-bearing Fe(II)2L3 triple helicates via acylation and azidation. Covalent modification of the metastable helicates prevented their reorganization to the thermodynamically favored Fe(II)4L4 tetrahedral cages, thus trapping the system at the non-equilibrium helicate structure. This functionalization strategy also conveniently provides access to a higher-order tris(porphyrinatoruthenium)-helicate complex that would be difficult to prepare by de novo ligand synthesis.This work was supported by the UK Engineering and Physical Sciences Research Council (EPSRC). D.A.R. acknowledges the Gates Cambridge Trust for Ph.D. (Gates Cambridge Scholarship) and conference funding.This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/ja5042397

Higher Education Funding Issues: U.S. / UK Comparison

The paper compares and contrasts higher education funding sources and systems in the U.S. and the UK. The issues raised in the paper pertain to the major challenge of academia: finding financial support in times of limited resources and enhanced competition. The issues discussed throughout the paper are: funding and quality assessment of universities; funding and equity of access to post-secondary education; marketization and privatization of universities; funding, autonomy and accountability of higher education institutions

Optimization of Enzymatic Biochemical Logic for Noise Reduction and Scalability: How Many Biocomputing Gates Can Be Interconnected in a Circuit?

We report an experimental evaluation of the "input-output surface" for a biochemical AND gate. The obtained data are modeled within the rate-equation approach, with the aim to map out the gate function and cast it in the language of logic variables appropriate for analysis of Boolean logic for scalability. In order to minimize "analog" noise, we consider a theoretical approach for determining an optimal set for the process parameters to minimize "analog" noise amplification for gate concatenation. We establish that under optimized conditions, presently studied biochemical gates can be concatenated for up to order 10 processing steps. Beyond that, new paradigms for avoiding noise build-up will have to be developed. We offer a general discussion of the ideas and possible future challenges for both experimental and theoretical research for advancing scalable biochemical computing

Multi‐Scale Responses of Liquid Crystals Triggered by Interfacial Assemblies of Cleavable Homopolymers

Liquid crystals (LCs) offer the basis of stimuli-responsive materials that can amplify targeted molecular events into macroscopic outputs. However, general and versatile design principles are needed to realize the full potential of these materials. To this end, we report the synthesis of two homopolymers with mesogenic side chains that can be cleaved upon exposure to either H2O2 (polymer P1) or UV light (polymer P2). Optical measurements reveal that the polymers dissolve in bulk LC and spontaneously assemble at nematic LC-aqueous interfaces to impose a perpendicular orientation on the LCs. Subsequent addition of H2O2 to the aqueous phase or exposure of the LC to UV was shown to trigger a surface-driven ordering transition to a planar orientation and an accompanying macroscopic optical output. Differences in the dynamics of the response to each stimulus are consistent with sequential processing of P1 at the LC-aqueous interface (H2O2) and simultaneous transformation of P2 within the LC (UV). The versatility of the approach is demonstrated by creating stimuli-responsive LCs as films or microdroplets, and by dissolving mixtures of P1 and P2 into LCs to create LC materials that respond to two stimuli. Overall, our results validate a simple and generalizable approach to the rational design of polymers that can be used to program stimuli-responsiveness into LC materials.11Nsciescopu