Experimental and theoretical insights for designing Zn2+ complexes to trigger chemo-selective hetero-coupling of alcohols.

Designing well-defined Zn-complexes for sustainable dehydrogenative catalysis overcoming the difficulties associated with activating Zn2+(d10)-metal species is considered paramount goal in catalysis. Herein, we explore the plausibility of ß-alkylation of secondary alcohols with primary alcohols by well-defined 3d10 Zn-complexes. Detailed organometallic and catalytic investigations, in conjunction with computational analyses, were conducted to ascertain the potential involvement of the catalyst at various stages of the catalytic process.

Understanding the basis of thermostability for enzyme "Nanoluc" towards designing industry-competent engineered variants.

As a leading contender in the study of luminescence, nanoluciferase has recently attracted attention and proven effective in a wide variety of research areas. Although numerous attempts have been made to improve activity, there has yet to be a thorough exploration of further possibilities to improve thermostability. In this study, protein engineering in tandem with molecular dynamics simulation at various temperatures (300 K, 400 K, 450 K and 500 K) was used to improve our understanding of nanoluciferase dynamics and identification of factors that could significantly enhance the thermostability. Based on these, three novel mutations have been narrowed down, which were hypothesised to improve thermostability. Root mean square deviation and root mean square fluctuation studies confirmed higher stability of mutant at high temperature. Solvent-accessible surface area and protein unfolding studies revealed a decreased tendency of mutant to unfold at higher temperatures. Further free energy landscape and principal component analysis was adapted to get deeper insights into the thermodynamic and structural behavior of these proteins at elevated temperature. Thus, this study provides a deeper insight into the dynamic factors for thermostability and introduces a novel, enhanced nanoluciferase candidate with potential use in industry.Communicated by Ramaswamy H. Sarma.

First-principles study of room-temperature ferromagnetism in transition-metal doped H-SiNWs.

Hydrogen-saturated silicon nanowires (H-SiNWs) are the most attractive materials for nanoelectronics due to their special tunable electronic properties. The incorporation of magnetism in H-SiNWs can be extremely beneficial for a wide range of emerging spintronic devices, which can offer a more effective way to control spin. Here, we investigate the energetic stability, electronic properties, and magnetic properties of transition metal (TM), i.e., Fe and Mn doped Hydrogen-saturated silicon nanowires (TM:H-SiNWs) that have a diameter of 1 nm directed in (100), (110), and (111) facets using spin-polarized density functional theory (DFT). The calculations showed that the TM-doped H-SiNWs (TM:H-SiNWs) convince the electronic and magnetic alterations of H-SiNWs semiconductors. It can be ascertained that the total magnetization of the studied configurations is contributed by the hybridization between a localized p orbital of Si and a d orbital of the TM atoms. In addition, we report the Curie temperature of the TM:H-SiNWs using a mean-field approximation and a Monte Carlo simulation based on the Ising model. We obtain the above room temperature ferromagnetism in the (100) and (111) direction-oriented Mn:H-SiNWs. This study provides an in-depth knowledge of the properties of TM-doped H-SiNWs and can be used as a reference in silicon-based spintronic devices.

Variable-Barrier Quantum Coulomb Blockade Effect in Nanoscale Transistors.

Current-voltage characteristics of a quantum dot in double-barrier configuration, as formed in the nanoscale channel of silicon transistors, were analyzed both experimentally and theoretically. Single electron transistors (SET) made in a SOI-FET configuration using silicon quantum dot as well as phosphorus donor quantum dots were experimentally investigated. These devices exhibited a quantum Coulomb blockade phenomenon along with a detectable effect of variable tunnel barriers. To replicate the experimental results, we developed a generalized formalism for the tunnel-barrier dependent quantum Coulomb blockade by modifying the rate-equation approach. We qualitatively replicate the experimental results with numerical calculation using this formalism for two and three energy levels participated in the tunneling transport. The new formalism supports the features of most of the small-scaled SET devices.

Progressive study on ruthenium catalysis for de(hydrogenative) alkylation and alkenylation using alcohols as a sustainable source.

At present, alcohols are considered sustainable starting materials that can be used in organic synthesis for various organic transformations and the preparation of commodity chemicals. Acceptorless dehydrogenation (AD) and borrowing hydrogen (BH) are two important methods for activating alcohols for alkenylation and alkylation. These approaches are sustainable because their process liberates water and in some cases (i.e., AD) molecular hydrogen as clean byproducts. Moreover, this area of research has attracted significant attention in the catalysis community, and various transition metals have been used to explore the same. Herein, in this review, we focus on the development of Ru-based catalyst systems for C-alkylation/alkenylation reactions via the AD or BH approach. This review also features a comparative study of the various Ru-catalysts used to optimize the reaction conditions. Furthermore, we extensively cover the outcomes of the mechanistic studies to describe the reaction pathways.

Change in the Product Selectivity in the Visible Light-Induced Selenium Radical-Mediated 1,4-Aryl Migration Process.

Herein, we demonstrate a visible light-induced selenium radical-mediated domino reaction of aryl alkynoates, for the synthesis of 1,1-diselenide alkene derivatives and selenium-containing α,ß-unsaturated carboxylic acid. The process is mild, metal free, easy to handle, and scalable. The decarboxylation step can be controlled by applying a catalytic amount of Eosin Y dye and cesium carbonate as a base. The methodology shows good functional group tolerance and provides decent yields of the products. In addition, the synthetic utility of this protocol was expanded further by preparing the allylic alcohol, α,ß-unsaturated ester, and vinylic halides.

Ru Doped Hydrotalcite Catalyzed Borrowing Hydrogen-Mediated N-Alkylation of Benzamides, Sulfonamides, and Dehydrogenative Synthesis of Quinazolinones.

An efficient Ru doped hydrotalcite catalyzed N-alkylation of benzamides and sulfonamides with alcohols via borrowing hydrogen catalysis is illustrated. Various primary alcohols, including benzyl, heteroaryl, and aliphatic alcohols, were alkylated in good to excellent yields. To shed light on the mechanistic details, several control studies and deuterium labeling experiments were performed. Mechanistic studies underpin that the reaction is going via a borrowing hydrogen pathway rather than an SN1 type mechanism. The reaction can be easily scaled up without any detrimental effect on the yield. The catalyst is also capable of synthesizing quinazolinone directly from 2-aminobenzamide and alcohols. Successful recyclability and high reactivity highlight the practical applicability of the catalyst.

Effect of dietary phytobiotic mixture on growth performance, nutrient utilization, and immunity in weaned piglets.

This study investigated the effects of dietary phytobiotic mixture on growth performance, blood profiles, immune response, and fecal microorganisms in weaned piglets. Twenty four weaned crossbred piglets were equally divided into four groups in a completely randomized design. The animals in 4 groups were fed a basal diet added with (1) no antibiotics and phytobiotics (CON), (2) bacitracin (0.5 g/kg; AB), (3) a blend of Cinnamomum zeylanicum and Trachyspermum copticum essential oils (0.3 g/kg and 0.4 g/kg, respectively; EO), and (4) plant extracts (PEO) of Mikania micrantha and Garcinia lanceifolia (2.8 g/kg and 1.4 g/kg, respectively) and C. zeylanicum and T. copticum essential oils (0.3 g/kg and 0.4 g/kg, respectively). Inclusion of AB, EO, and PEO did not affect final body weight, average daily gain, feed intake, feed efficiency, and nutrient digestibility. Compared with the CON, serum protein profiles were not affected, but a few lipid profiles were improved, particularly cholesterol, low-density lipoprotein, and high-density lipoprotein in the EO and PEO groups. Lymphocyte proliferation index and concentrations of IgG and IgA and TNF-α were not affected by any treatments. The concentrations of IgM increased (P = 0.04) at 28 days and tended to increase (P = 0.10) at 56 days in the EO group. Serum IL-1ß levels decreased on days 28 and 56 in the EO and PEO groups. Fecal Lactobacilli population generally increased (P < 0.01) in the AB, EO, and PEO groups compared with the CON. Fecal enterobacterial numbers were always greater for AB than for CON, EO, or PEO, but enterobacterial populations were sometimes lower in the EO group than the CON group. In conclusion, dietary EO or PEO has no effect on the growth performance, but it may improve a few lipid profiles, immune responses, and fecal microbial populations in piglets.

Electric-field-assisted formation of an interfacial double-donor molecule in silicon nano-transistors.

Control of coupling of dopant atoms in silicon nanostructures is a fundamental challenge for dopant-based applications. However, it is difficult to find systems of only a few dopants that can be directly addressed and, therefore, experimental demonstration has not yet been obtained. In this work, we identify pairs of donor atoms in the nano-channel of a silicon field-effect transistor and demonstrate merging of the donor-induced potential wells at the interface by applying vertical electric field. This system can be described as an interfacial double-donor molecule. Single-electron tunneling current is used to probe the modification of the potential well. When merging occurs at the interface, the gate capacitance of the potential well suddenly increases, leading to an abrupt shift of the tunneling current peak to lower gate voltages. This is due to the decrease of the system's charging energy, as confirmed by Coulomb blockade simulations. These results represent the first experimental observation of electric-field-assisted formation of an interfacial double-donor molecule, opening a pathway for designing functional devices using multiple coupled dopant atoms.

Tunneling in Systems of Coupled Dopant-Atoms in Silicon Nano-devices.

Following the rapid development of the electronics industry and technology, it is expected that future electronic devices will operate based on functional units at the level of electrically active molecules or even atoms. One pathway to observe and characterize such fundamental operation is to focus on identifying isolated or coupled dopants in nanoscale silicon transistors, the building blocks of present electronics. Here, we review some of the recent progress in the research along this direction, with a focus on devices fabricated with simple and CMOS-compatible-processing technology. We present results from a scanning probe method (Kelvin probe force microscopy) which show direct observation of dopant-induced potential modulations. We also discuss tunneling transport behavior based on the analysis of low-temperature I-V characteristics for devices representative for different regimes of doping concentration, i.e., different inter-dopant coupling strengths. This overview outlines the present status of the field, opening also directions toward practical implementation of dopant-atom devices.

Quantum size effects on the optical properties of nc-Si QDs embedded in an a-SiOx matrix synthesized by spontaneous plasma processing.

Quantum confinement effects on optical transitions in ensembles of nc-Si QDs in an a-SiOx matrix has become evident by simultaneously considering the dielectric function dispersions obtained by optical modeling with spectroscopic ellipsometry, the absorption edge, and the photoluminescence peak. Diminution of the peak amplitude in the ε2-spectra for reducing the diameter of nc-Si QDs could arise due to the disappearance of excitonic effects in the E1 transition, while the peak broadening indicates an amplification of disorder in Si QDs. An energy blue shift happens to take place in an analogous fashion for all the characteristic parameters, upon decreasing the size of the nc-Si QDs for diameters in the range 6.5 < d < 2.0 nm. The band gap widening with the reduction of QD size is well supported by the first-principles calculations based on quantum confinement, while studies on the Stokes shift in the optical gap from the PL data could provide an understanding of the imperfect passivation of the surface defects on tiny nc-Si QDs. Low dimensional nc-Si QDs (∼2 nm in diameter) assembled in a large density (∼2.3 × 10(12) cm(-2)) embedded in an a-SiOx matrix synthesized by spontaneous and low-temperature (300 °C) RF plasma processing, compatible to CMOS technology, are highly conducive for device applications. Systematic changes in composition and characteristics, including the thickness, of the individual sub-layers of the nc-Si QD thin films can be comprehensively pursued through a nondestructive process by ellipsometric simulation which could, thereby, enormously contribute to the precise optimization of the deposition parameters suitable for specific device fabrication e.g., all-silicon tandem solar cells and light emitting diodes, using silicon nanotechnology.

Transport spectroscopy of coupled donors in silicon nano-transistors.

The impact of dopant atoms in transistor functionality has significantly changed over the past few decades. In downscaled transistors, discrete dopants with uncontrolled positions and number induce fluctuations in device operation. On the other hand, by gaining access to tunneling through individual dopants, a new type of devices is developed: dopant-atom-based transistors. So far, most studies report transport through dopants randomly located in the channel. However, for practical applications, it is critical to control the location of the donors with simple techniques. Here, we fabricate silicon transistors with selectively nanoscale-doped channels using nano-lithography and thermal-diffusion doping processes. Coupled phosphorus donors form a quantum dot with the ground state split into a number of levels practically equal to the number of coupled donors, when the number of donors is small. Tunneling-transport spectroscopy reveals fine features which can be correlated with the different numbers of donors inside the quantum dot, as also suggested by first-principles simulation results.

Photoluminescent silicon quantum dots in core/shell configuration: synthesis by low temperature and spontaneous plasma processing.

Quantum confinement in zero-dimensional silicon nanocrystals (nC) in the quantum dot (QD) configuration has triggered a tremendous interest in nanostructured device technology. However, the formation of Si-QDs eventually proceeds through multi-step routes and involves high temperature processing that impedes preferred device configuration. The present work demonstrates the formation of nC-Si QDs of controlled size, density and distribution through one-step and spontaneous plasma processing, at a low substrate temperature (300 °C) compatible for device fabrication. Direct growth of nC-Si/SiO(x) core/shell quantum dots embedded in the a-Si matrix, 6.4-3.7 nm in diameter and with number density in the range ∼ 6 × 10(9)-1 × 10(11) cm(-2) has been accomplished, following a novel route where He dilution to SiH(4) in RF plasma CVD has been found instrumental. On gradual reduction in the size of QDs, splitting of the energy bands widens the optical band gap and induces visible photoluminescence that appears controllable by tuning the size and density of the dots. This low temperature and spontaneous plasma processing of nC-Si/SiO(x) core/shell QDs that exhibit the quantum size effect in photoluminescence is being reported for the first time.