Discrete thermodynamics of chemical equilibria and classical limit in thermodynamic simulation

This article sets forth comprehensive basic concepts of the discrete thermodynamics of chemical equilibrium as balance between internal and external thermodynamic forces. Conditions of chemical equilibrium in the open chemical system are obtained in the form of a logistic map, containing only one new parameter that defines the chemical system's resistance to external impact and its deviation from thermodynamic equilibrium. Solutions to the basic map are bifurcation diagrams that have quite traditional shape but the diagram areas feature specific meanings for chemical systems and constitute the system's domain of states. The article is focused on two such areas: the area of “true” thermodynamic equilibrium and the area of open chemical equilibrium. The border between them represents the classical limit, a transition point between the classical and newly formulated equilibrium conditions. This limit also separates regions of the system ideality, typical for isolated classical systems, and non-ideality due to the limitations imposed on the open system from outside. Numerical examples illustrating the difference between results of classical and discrete thermodynamic simulation methods are presented. The article offers an analytical formula to find the classical limit, compares analytical results with these obtained by simulation, and shows the classical limit dependence upon the chemical reaction stoichiometry and robustness.     

Graphene Microbolometers with Superconducting Contacts for Terahertz Photon Detection

We report on noise and thermal conductance measurements taken in order to determine an upper bound on the performance of graphene as a terahertz photon detector. The main mechanism for sensitive terahertz detection in graphene is bolometric heating of the electron system. To study the properties of a device using this mechanism to detect terahertz photons, we perform Johnson noise thermometry measurements on graphene samples. These measurements probe the electron–phonon behavior of graphene on silicon dioxide at low temperatures. Because the electron–phonon coupling is weak in graphene, superconducting contacts with large gap are used to confine the hot electrons and prevent their out-diffusion. We use niobium nitride leads with a \(T_\mathrm {c}\approx 10\)  K to contact the graphene. We find these leads make good ohmic contact with very low contact resistance. Our measurements find an electron–phonon thermal conductance that depends quadratically on temperature above 4 K and is compatible with single terahertz photon detection.     

Gold nanorods with a hematoporphyrin-loaded silica shell for dual-modality photodynamic and photothermal treatment of tumors in vivo

Nanocomposites （NCs） consisting of a gold nanorod core and a mesoporous silica shell doped with hematoporphyrin （HP） have been fabricated in order to improve the efficiency of cancer treatment by combining photothermal and photodynamic therapies （PDT ＋ PTT） in vivo. In addition to the long-wavelength plasmon resonance near 810-830 nm, the fabricated NCs exhibited a 400-nm absorbance peak corresponding to bound HP, generated singlet oxygen under 633-nm excitation near the 632.5-nm Q-band, and produced heat under a 808-nm near-infrared （NIR） laser irradiation. These modalities were used for a combined PDT ＋ PTT treatment of large （about 3 cm3） solid tumors in vivo with a xenorafted tumor rat model. NCs were directly injected into tumors and irradiated simultaneously with 633-nm and 808-nm lasers to stimulate the combined photodynamic and photothermal activities of NCs. The efficiency of the combined therapy was evaluated by optical coherence tomography, histological analysis, and by measurements of the tumor volume growth during a 21-day period. The NC-mediated PDT led to weak changes in tissue histology and to a moderate 20% decrease in the tumor volume. In contrast, the combined PDT ＋ PTT treatment resulted in the large-area tumor necrosis and led to dramatic decrease in the tumor volume.     

An Atomistic Tomographic Study of Oxygen and Hydrogen Atoms and their Molecules in CVD Grown Graphene

The properties and growth processes of graphene are greatly influenced by the elemental distributions of impurity atoms and their functional groups within or on the hexagonal carbon lattice. Oxygen and hydrogen atoms and their functional molecules (OH, CO, and CO₂) positions' and chemical identities are tomographically mapped in three dimensions in a graphene monolayer film grown on a copper substrate, at the atomic part‐per‐million (atomic ppm) detection level, employing laser assisted atom‐probe tomography. The atomistic plan and cross‐sectional views of graphene indicate that oxygen, hydrogen, and their co‐functionalities, OH, CO, and CO₂, which are locally clustered under or within the graphene lattice. The experimental 3D atomistic portrait of the chemistry is combined with computational density‐functional theory (DFT) calculations to enhance the understanding of the surface state of graphene, the positions of the chemical functional groups, their interactions with the underlying Cu substrate, and their influences on the growth of graphene.     

A correlation model to compute the incidence angle modifier and to estimate its effect on collectible solar radiation

Radiation transmittance and absorptance of materials vary according to the angle of incidence of the incoming solar radiation. Therefore, the efficiency of most solar converters (thermal or photovoltaic) at a given radiation amount is a function of the sun's position through the angle of incidence. This problem is accounted for by the Incidence Angle Modifier, which is considered in this paper. An analytic expression for the incidence angle modifier, based on meteorological data or on geographic and geometric parameters, has been developed; this expression includes the effect of beam and diffuse radiation as well as the global influence. A comparison between measured data and computed from our model has given a very good correlation, the results being within a ±3% of difference for horizontal and tilted planes, and within ±17% for vertical surfaces, on average. The method also computes the collectible solar energy within a 5% error for thresholds up to 300 W m⁻². The method has been validated for more than 30 locations of south and west Europe.     

Mass-sensitive detection of gas-phase volatile organics using disk microresonators

The detection of volatile organic compounds (VOCs) in the gas phase by mass-sensitive disk microresonators is reported. The disk resonators were fabricated using a CMOS-compatible silicon micromachining process and subsequently placed in an amplifying feedback loop to sustain oscillation. Sensing of benzene, toluene, and xylene was conducted after applying controlled coatings of an analyte-absorbing polymer. An analytical model of the resonator's chemical sensing performance was developed and verified by the experimental data. Limits of detection for the analytes tested were obtained, modeled, and compared to values obtained from other mass-sensitive resonant gas sensors.     

Infrared hollow waveguide sensors for simultaneous gas phase detection of benzene, toluene, and xylenes in field environments

Simultaneous and molecularly selective parts-per-billion detection of benzene, toluene, and xylenes (BTX) using a thermal desorption (TD)-FTIR hollow waveguide (HWG) trace gas sensor is demonstrated here for the first time combining laboratory calibration with real-world sample analysis in field. A calibration range of 100-1000 ppb analyte/N(2) was developed and applied for predicting the concentration of blinded environmental air samples within the same concentration range, and demonstrate close agreement with the validation method used here, GC-FID. The analyte concentration prediction capability of the TD-FTIR-HWG trace gas sensor also compares well with the industrial standard and other experimental techniques including GC-PID, ultrafast GC-FID, and GC-DMS, which were simultaneously operated in the field. With the advent of a quantum cascade laser with emission frequencies specifically tailored to efficiently overlap benzene absorption as the most relevant analyte, the overall sensor footprint could be considerably reduced to ultimately yield hand-held trace gas sensors facilitating direct and real-time detection of BTX in air down to low ppb levels.     

High-throughput, accurate mass metabolome profiling of cellular extracts by flow injection-time-of-flight mass spectrometry

Direct injection of samples on high-resolving mass spectrometers is an effective way to maximize analytical throughput and yet allow analyte discrimination in complex samples by mass-to-charge ratio. We present a platform of flow injection electrospray-time-of-flight mass spectrometry to profile small molecules in >1400 biological extracts per day at native mass resolution. We comprehensively benchmark the performance with more than 5000 injections of chemically defined standards and Escherichia coli cellular extracts obtained from miniscale cultivations. For at least 90% of tested compounds, we attain a linear response over 3 decades of concentration, interday coefficient of variation of <20%, and a mass accuracy of <0.001 amu. In polar Escherichia coli fractions, we reproducibly detected >1500 distinct ions in each mode. The accurate mass and correlation analysis enabled one to assign with good confidence 400-800 ions to electrospray derivatives of metabolites listed in the genome-wide reconstruction of Escherichia coli metabolism. Hence, we attain a coverage of about one-quarter of the total number of compounds listed in the reconstruction. Finally, we present an exemplary screen with Escherichia coli deletion mutants to show the exquisite capacity of the platform to identify lesions in primary metabolism at high throughputs.