Solutions of Inequality Constrained Spline Optimization Problems with the Active Set Method

We solve the problem of finding a near-interpolant curve, subject to constraints, which minimizes the bending energy of the curve. Using B-splines as our tools, we give a brief overview of spline properties and develop several different cases of inequality constrained optimization problems of this type. In particular, we develop the active set method and use it to solve these problems, emphasizing the fact that this algorithm will converge to a solution in finite iterations. Our solution will solve an open problem regarding near-interpolant spline curves. Furthermore, we supplement this with an iterative technique for better choosing data sites so as to further minimize the bending energy of the spline curve, offering an easy solution to the problem of free data sites

From sequence-defined macromolecules to macromolecular pin codes

Dynamic sequence-defined oligomers carrying a chemically written pin code are obtained through a strategy combining multicomponent reactions with the thermoreversible addition of 1,2,4-triazoline-3,5-diones (TADs) to indole substrates. The precision oligomers are specifically designed to be encrypted upon heating as a result of the random reshuffling of the TAD-indole covalent bonds within the backbone, thereby resulting in the scrambling of the encoded information. The encrypted pin code can eventually be decrypted following a second heating step that enables the macromolecular pin code to be deciphered using 1D electrospray ionization-mass spectrometry (ESI-MS). The herein introduced concept of encryption/decryption represents a key advancement compared with current strategies that typically use uncontrolled degradation to erase and tandem mass spectrometry (MS/MS) to analyze, decipher, and read-out chemically encrypted information. Additionally, the synthesized macromolecules are coated onto a high-value polymer material, which demonstrates their potential application as coded product tags for anti-counterfeiting purposes

Microvesicles as biomarkers in diabetes, obesity and non-alcoholic fatty liver disease: current knowledge and future directions

NAFLD is the most common chronic liver disease, frequently associated with diabetes. Both of these insulin resistant states have increased cardiovascular risk factors associated, and a prevalent cause of mortality in these diseases. Microvesicles are heterogonously sized, phospholipid rich spheres released by cells upon activation and apoptosis. Evidence is continuing to accumulate of microvesicles being not only markers of disease severity but as also having a functional role in the pathophysiology of disease progression.<br/

Fluorescence turn-on by photoligation – bright opportunities for soft matter materials

Photochemical ligation has become an indispensable tool for applications that require spatially addressable functionalisation, both in biology and materials science. Interestingly, a number of photochemical ligations result in fluorescent products, enabling a self-reporting function that provides almost instantaneous visual feedback of the reaction\u27s progress and efficiency. Perhaps no other chemical reaction system allows control in space and time to the same extent, while concomitantly providing inherent feedback with regard to reaction success and location. While photoactivable fluorescent properties have been widely used in biology for imaging purposes, the expansion of the array of photochemical reactions has further enabled its utility in soft matter materials. Herein, we concisely summarise the key developments of fluorogenic-forming photoligation systems and their emerging applications in both biology and materials science. We further summarise the current challenges and future opportunities of exploiting fluorescent self-reporting reactions in a wide array of chemical disciplines

The role of the cloud radiative effect in the sensitivity of the Intertropical Convergence Zone to convective mixing

Studies have shown that the location and structure of the simulated Intertropical Convergence Zone (ITCZ) is sensitive to the treatment of sub-gridscale convection and cloud-radiation interactions. This sensitivity remains in idealised aquaplanet experiments with fixed surface temperatures. However, studies have not considered the role of cloud-radiative effects (CRE, atmospheric heating due to cloud-radiation interactions) in the sensitivity of the ITCZ to the treatment of convection. We use an atmospheric energy input (AEI) framework to explore how the CRE modulates the sensitivity of the ITCZ to convective mixing in aquaplanet simulations. Simulations show a sensitivity of the ITCZ to convective mixing, with stronger convective mixing favoring a single ITCZ. For simulations with a single ITCZ, the CRE maintains the positive, equatorial AEI. To explore the role of the CRE further, we prescribe the CRE as either zero or a meridionally and diurnally varying climatology. Removing the CRE is associated with a reduced equatorial AEI and an increase in the range of convective mixing rates that produce a double ITCZ. Prescribing the CRE reduces the sensitivity of the ITCZ to convective mixing by 50%. In prescribed CRE simulations, other AEIcomponents, in particular the surface latent heat flux, modulate the sensitivity of the AEI to convective mixing. Analysis of the meridional moist static energy transport shows that a shallower Hadley circulation can produce an equatorward energy transport at low latitudes even with equatorial ascent