Self-Assembly Propensity Dictates Lifetimes in Transient Naphthalimide–Dipeptide Nanofibers

Transient self-assembly of dipeptide nanofibers with lifetimes that are predictably variable through dipeptide sequence design are presented. This was achieved using 1,8-naphthalimide ( NI ) amino acid methyl-esters (Phe, Tyr, Leu) that are biocatalytically coupled to amino acid-amides (Phe, Tyr, Leu, Val, Ala, Ser) to form self-assembling NI -dipeptides. However, competing hydrolysis of the dipeptides results in disassembly. It was demonstrated that the kinetic parameters like lifetimes of these nanofibers can be predictably regulated by the thermodynamic parameter, namely the self-assembly propensity of the constituent dipeptide sequence. These lifetimes could vary from minutes, to hours, to permanent gels that do not degrade. Moreover, the in-built NI fluorophore was utilized to image the transient nanostructures in solution with stimulated emission depletion (STED) based super-resolution fluorescence microscopy.     

Progress and Perspectives on Covalent-Organic Frameworks (COFs) and Composites for Various Energy Applications

Covalent-organic frameworks (COFs), being a new member of the crystalline porous materials family, have emerged as important materials for energy storage/conversion/generation devices. They possess high surface areas, ordered micro/mesopores, designable structures and an ability to precisely control electro-active groups in their pores, which broaden their application window. Thanks to their low weight density, long range crystallinity, reticular nature and tunable synthesis approach towards two and three dimensional (2D and 3D) networks, they have been found suitable for a range of challenging electrochemical applications. Our review focuses on the progress made on the design, synthesis and structure of COFs and their composites for various energy applications, such as metal-ion batteries, supercapacitors, water-splitting and solar cells. Additionally, attempts have been made to correlate the structural and mechanistic characteristics of COFs with their applications.     

Cytotoxic evaluation of semisynthetic ester and amide derivatives of oleanolic acid

Although a number of chemicals have been isolated from Lantana camara, only a few have been evaluated for their biological significance. As part of our drug discovery program for cytotoxic agents from Indian medicinal plants, roots of L. camara L. were chemically investigated, which resulted in the isolation and identification of a cytotoxic agent, oleanolic acid (1b) as a major constituent. Oleanolic acid was converted into six semi-synthetic ester (2-7) and seven amide (8-14) derivatives. The ester derivatives (2-7) showed 3-6 times more selective activity than 1b against the human ovarian cancer cell line (IGR-OV-1), while amide derivatives 8-14 showed 16-53 times more selective activity against the human lung cancer cell line (HOP-62). Structure activity relationship within the ester (2-7) and amide (8-14) derivatives are discussed.     

Ab initio calculations of the reaction mechanisms for metal-nitride deposition from organo-metallic precursors onto functionalized self-assembled monolayers

An atomistic mechanism has been derived for the initial stages of the adsorption reaction for metal-nitride atomic layer deposition (ALD) from alkylamido organometallic precursors of Ti and Zr on alkyltrichorosilane-based self-assembled monolayers (SAMs). The effect of altering the terminal functional group on the SAM (including -OH, -NH2, -SH, and -NH(CH3)) has been investigated using the density functional theory and the MP2 perturbation theory. Reactions on amine-terminated SAMs proceed through the formation of a dative-bond complex with an activation barrier of 16-20 kcal/mol. In contrast, thiol-terminated SAMs form weak hydrogen-bonded intermediates with activation barriers between 7 and 10 kcal/mol. The deposition of Ti organometallic precursors on hydroxyl-terminated SAMs proceeds through the formation of stronger hydrogen-bonded complexes with barriers of 7 kcal/mol. Zr-based precursors form dative-bonded adducts with near barrierless transitions. This variety allows us to select a kinetically favorable substrate for a chosen precursor. The predicted order of reactivity of differently terminated SAMs and the temperature dependence of the initial reaction probability have been confirmed for Ti-based precursors by recent experimental results. We predict that the replacement of methyl groups by trifluoromethyl groups on the SAM backbone decreases the activation barrier for amine-terminated SAMs by 5 kcal/mol. This opens a route to alter the native reactivities of a given SAM termination, in this case making amine termination energetically viable. The surface distribution of SAM molecules has a strong effect on the adsorption kinetics of Ti-based precursors. Unimolecular side decomposition reactions were found to be kinetically competitive with adsorption at 400 K.     

Choosability with union separation

List coloring generalizes graph coloring by requiring the color of a vertex to be selected from a list of colors specific to that vertex. One refinement of list coloring, called choosability with separation, requires that the intersection of adjacent lists is sufficiently small. We introduce a new refinement, called choosability with union separation, where we require that the union of adjacent lists is sufficiently large. For $t\ge k$, a $(k,t)$-list assignment is a list assignment $L$ where $\left|L\left(v\right)\right|\ge k$ for all vertices $v$ and $|L\left(u\right)\cup L\left(v\right)|\ge t$ for all edges $uv$. A graph is $(k,t)$-choosable if there is a proper coloring for every $(k,t)$-list assignment. We explore this concept through examples of graphs that are not $(k,t)$-choosable, demonstrating sparsity conditions that imply a graph is $(k,t)$-choosable, and proving that all planar graphs are $(3,11)$-choosable and $(4,9)$-choosable.     

Can correlations drive a band insulator metallic?

We analyze the effects of the on-site Coulomb repulsion U on a band insulator using dynamical mean field theory (DMFT). We find the surprising result that the gap is suppressed to zero at a critical Uc1 and remains zero within a metallic phase. At a larger Uc2 there is a second transition from the metal to a Mott insulator, in which the gap increases with increasing U. These results are qualitatively different from Hartree-Fock theory which gives a monotonically decreasing but nonzero insulating gap for all finite U.     

Strong valid inequalities for orthogonal disjunctions and bilinear covering sets

In this paper, we derive a closed-form characterization of the convex hull of a generic nonlinear set, when this convex hull is completely determined by orthogonal restrictions of the original set. Although the tools used in this construction include disjunctive programming and convex extensions, our characterization does not introduce additional variables. We develop and apply a toolbox of results to check the technical assumptions under which this convexification tool can be employed. We demonstrate its applicability in integer programming by providing an alternate derivation of the split cut for mixed-integer polyhedral sets and finding the convex hull of certain mixed/pure-integer bilinear sets. We then extend the utility of the convexification tool to relaxing nonconvex inequalities, which are not naturally disjunctive, by providing sufficient conditions for establishing the convex extension property over the non-negative orthant. We illustrate the utility of this result by deriving the convex hull of a continuous bilinear covering set over the non-negative orthant. Although we illustrate our results primarily on bilinear covering sets, they also apply to more general polynomial covering sets for which they yield new tight relaxations.     

Sensitivity Analysis of Contact Type Vibration Measuring Sensors

With the Internet of Things (IoT) era dawning in, we are surrounded by a plethora of sensors. The present paper focuses on MEMS-based vibration measuring accelerometers, which are ubiquitously present in smartphones, tablets, smartwatches/bands, etc. These contact type vibration sensors have the unique advantage of being very small, low cost, low power, less weighing, and easily accommodatable in electronics. However, the accuracy of these sensors needs to be quantified with respect to more accurate sensors. With this objective, the paper presents a comparison of the relative sensitivity of a MEMS-based accelerometer (MPU 6050), a Geophone, and a sensor from Xiaomi Y2 smartphone with respect to a more standard Piezoelectric ICP based accelerometer, when all sensors are tested on a shaker table. Data are measured with harmonic excitation over a frequency range of 2–184 Hz. The relative sensitivity of MPU 6050 was 90% accurate in the frequency range 18–116 Hz for RMS measurements. Other sensors such as the one used in the Xiaomi Y2 smartphone and the Geophone were less accurate. The relative sensitivity measured in this work can be used to obtain sensitivity and hence more accurate data from these low-cost accelerometers.