Biocatalytic Synthesis of Polymers of Precisely Defined Structures

The fabrication of functional nanoscale devices requires the construction of complex architectures at length scales characteristic of atoms and molecules. Currently microlithography and micro-machining of macroscopic objects are the preferred methods for construction of small devices, but these methods are limited to the micron scale. An intriguing approach to nanoscale fabrication involves the association of individual molecular components into the desired architectures by supramolecular assembly. This process requires the precise specification of intermolecular interactions, which in turn requires precise control of molecular structure

Exponential Barycenters of the Canonical Cartan Connection and Invariant Means on Lie Groups

International audienceWhen performing statistics on elements of sets that possess a particular geometric structure, it is desirable to respect this structure. For instance in a Lie group, it would be judicious to have a notion of a mean which is stable by the group operations (composition and inversion). Such a property is ensured for Riemannian center of mass in Lie groups endowed with a bi-invariant Riemannian metric, like compact Lie groups (e.g. rotations). However, bi-invariant Riemannian metrics do not exist for most non compact and non-commutative Lie groups. This is the case in particular for rigid-body transformations in any dimension greater than one, which form the most simple Lie group involved in biomedical image registration. In this paper, we propose to replace the Riemannian metric by an affine connection structure on the group. We show that the canonical Cartan connections of a connected Lie group provides group geodesics which are completely consistent with the composition and inversion. With such a non-metric structure, the mean cannot be defined by minimizing the variance as in Riemannian Manifolds. However, the characterization of the mean as an exponential barycenter gives us an implicit definition of the mean using a general barycentric equation. Thanks to the properties of the canonical Cartan connection, this mean is naturally bi-invariant. We show the local existence and uniqueness of the invariant mean when the dispersion of the data is small enough. We also propose an iterative fixed point algorithm and demonstrate that the convergence to the invariant mean is at least linear. In the case of rigid-body transformations, we give a simple criterion for the global existence and uniqueness of the bi-invariant mean, which happens to be the same as for rotations. We also give closed forms for the bi-invariant mean in a number of simple but instructive cases, including 2D rigid transformations. For general linear transformations, we show that the bi-invariant mean is a generalization of the (scalar) geometric mean, since the determinant of the bi-invariant mean is the geometric mean of the determinants of the data. Finally, we extend the theory to higher order moments, in particular with the covariance which can be used to define a local bi-invariant Mahalanobis distance

In quest of a systematic framework for unifying and defining nanoscience

This article proposes a systematic framework for unifying and defining nanoscience based on historic first principles and step logic that led to a “central paradigm” (i.e., unifying framework) for traditional elemental/small-molecule chemistry. As such, a Nanomaterials classification roadmap is proposed, which divides all nanomatter into Category I: discrete, well-defined and Category II: statistical, undefined nanoparticles. We consider only Category I, well-defined nanoparticles which are >90% monodisperse as a function of Critical Nanoscale Design Parameters (CNDPs) defined according to: (a) size, (b) shape, (c) surface chemistry, (d) flexibility, and (e) elemental composition. Classified as either hard (H) (i.e., inorganic-based) or soft (S) (i.e., organic-based) categories, these nanoparticles were found to manifest pervasive atom mimicry features that included: (1) a dominance of zero-dimensional (0D) core–shell nanoarchitectures, (2) the ability to self-assemble or chemically bond as discrete, quantized nanounits, and (3) exhibited well-defined nanoscale valencies and stoichiometries reminiscent of atom-based elements. These discrete nanoparticle categories are referred to as hard or soft particle nanoelements. Many examples describing chemical bonding/assembly of these nanoelements have been reported in the literature. We refer to these hard:hard (H-n:H-n), soft:soft (S-n:S-n), or hard:soft (H-n:S-n) nanoelement combinations as nanocompounds. Due to their quantized features, many nanoelement and nanocompound categories are reported to exhibit well-defined nanoperiodic property patterns. These periodic property patterns are dependent on their quantized nanofeatures (CNDPs) and dramatically influence intrinsic physicochemical properties (i.e., melting points, reactivity/self-assembly, sterics, and nanoencapsulation), as well as important functional/performance properties (i.e., magnetic, photonic, electronic, and toxicologic properties). We propose this perspective as a modest first step toward more clearly defining synthetic nanochemistry as well as providing a systematic framework for unifying nanoscience. With further progress, one should anticipate the evolution of future nanoperiodic table(s) suitable for predicting important risk/benefit boundaries in the field of nanoscience