Eugene Paulechka

A MoS2-Based Capacitive Displacement Sensor for DNA Sequencing

We propose an aqueous functionalized molybdenum disulfide nanoribbon suspended over a solid electrode as a capacitive displacement sensor aimed at determining the DNA sequence. The detectable sequencing events arise from the combination of Watson-Crick base-pairing, one of natures most basic lock-and-key binding mechanisms, with the ability of appropriately sized atomically thin membranes to flex substantially in response to subnanonewton forces. We employ carefully designed numerical simulations and theoretical estimates to demonstrate excellent (79% to 86%) raw target detection accuracy at ∼70 million bases per second and electrical measurability of the detected events. In addition, we demonstrate reliable detection of repeated DNA motifs. Finally, we argue that the use of a nanoscale opening (nanopore) is not requisite for the operation of the proposed sensor and present a simplified sensor geometry without the nanopore as part of the sensing element. Our results, therefore, potentially suggest a realistic, inherently base-specific, high-throughput electronic DNA sequencing device as a cost-effective de novo alternative to the existing methods.

Efficient DLPNO–CCSD(T)-Based Estimation of Formation Enthalpies for C-, H-, O-, and N-Containing Closed-Shell Compounds Validated Against Critically Evaluated Experimental Data

An accurate and cost-efficient methodology for the estimation of the enthalpies of formation for closed-shell compounds composed of C, H, O, and N atoms is presented and validated against critically evaluated experimental data. The computational efficiency is achieved through the use of the resolution-of-identity (RI) and domain-based local pair-natural orbital coupled cluster (DLPNO-CCSD(T)) approximations, which results in a drastic reduction in both the computational cost and the number of necessary steps for a composite quantum chemical method. The expanded uncertainty for the proposed methodology evaluated using a data set of 45 thoroughly vetted experimental values for molecules containing up to 12 heavy atoms is about 3 kJ·mol-1, competitive with those of typical calorimetric measurements. For the compounds within the stated scope, the methodology is shown to be superior to a representative, more general, and widely used composite quantum chemical method, G4.

Candidates to replace R-12 as a radiator gas in Cherenkov detectors

Dichlorodifluoromethane (R-12) has been widely used as a radiator gas in pressure threshold Cherenkov detectors for high-energy particle physics. However, that compound is becoming unavailable due to the Montreal Protocol. To find a replacement with suitably high refractive index, we use a combination of theory and experiment to examine the polarizability and refractivity of several non-ozone-depleting compounds. Our measurements show that the fourth-generation refrigerants R-1234yf (2,3,3,3-tetrafluoropropene) and R-1234ze(E) (trans-1,3,3,3-tetrafluoropropene) have sufficient refractivity to replace R-12 in this application. If the slight flammability of these compounds is a problem, two nonflammable alternatives are R-218 (octafluoropropane), which has a high Global Warming Potential, and R-13I1 (trifluoroiodomethane), which has low Ozone Depletion Potential and Global Warming Potential but may not be sufficiently inert.

Efficient Estimation of Formation Enthalpies for Closed-Shell Organic Compounds with Local Coupled-Cluster Methods

Efficient estimation of the enthalpies of formation for closed-shell organic compounds via atom-equivalent-type computational schemes and with the use of different local coupled-cluster with single, double, and perturbative triple excitation (CCSD(T)) approximations was investigated. Detailed analysis of established sources of uncertainty, inclusive of contributions beyond frozen-core CCSD(T) and errors due to local CCSD(T) approximations and zero-point energy anharmonicity, suggests the lower limit of about 2 kJ·mol-1 for the expanded uncertainty of the proposed estimation framework. Among the tested computational schemes, the best-performing cases demonstrate expanded uncertainty of about 2.5 kJ·mol-1, based on the analysis against 44 critically evaluated experimental values. Computational efficiency, accuracy commensurable with that of a typical experiment, and absence of the need for auxiliary reactions and additional experimental data offer unprecedented advantages for practical use, such as prompt validation of existing measurements and estimation of missing values, as well as resolution of experimental conflicts. The utility of the proposed methodology was demonstrated using a representative sample of the most recent experimental measurements.

Aqueous Ion Trapping and Transport in Graphene-Embedded 18-Crown-6 Ether Pores

Using extensive room-temperature molecular dynamics simulations, we investigate selective aqueous cation trapping and permeation in graphene-embedded 18-crown-6 ether pores. We show that in the presence of suspended water-immersed crown-porous graphene, K+ ions rapidly organize and trap stably within the pores, in contrast with Na+ ions. As a result, significant qualitative differences in permeation between ionic species arise. The trapped ion occupancy and permeation behaviors are shown to be highly voltage-tunable. Interestingly, we demonstrate the possibility of performing conceptually straightforward ion-based logical operations resulting from controllable membrane charging by the trapped ions. In addition, we show that ionic transistors based on crown-porous graphene are possible, suggesting utility in cascaded ion-based logic circuitry. Our results indicate that in addition to numerous possible applications of graphene-embedded crown ether nanopores, including deionization, ion sensing/sieving, and energy storage, simple ion-based logical elements may prove promising as building blocks for reliable nanofluidic computational devices.

Chapter 5. Calorimetric Determination of Enthalpies of Vaporization

A review of calorimeters and experimental procedures used for the measurement of enthalpies of vaporization for pure liquids is presented. The calorimetric approaches that are illustrated give an insight into direct determination of enthalpies of vaporization starting from the very first steps in the mid-19th century to modern techniques that allow measurements on a few milligrams of material or even less. In the most accurate techniques, home-made instruments or commercial calorimeters, mostly of the Calvet type, are used. The current focus in instrument development involves fast, though less accurate, power-compensation differential scanning calorimeters.