Thermodynamic Study of N-Methylformamide and N,N-Dimethyl-Formamide.

An extensive thermodynamic study of N-methylformamide (CAS RN: 123-39-7) and N,N-dimethylformamide (CAS RN: 68-12-2), is presented in this work. The liquid heat capacities of N-methylformamide were measured by Tian-Calvet calorimetry in the temperature interval (250-300) K. The vapor pressures for N-methylformamide and N,N-dimethylformamide were measured using static method in the temperature range 238 K to 308 K. The ideal-gas thermodynamic properties were calculated using a combination of the density functional theory (DFT) and statistical thermodynamics. A consistent thermodynamic description was developed using the method of simultaneous correlation, where the experimental and selected literature data for vapor pressures, vaporization enthalpies, and liquid phase heat capacities and the calculated ideal-gas heat capacities were treated together to ensure overall thermodynamic consistency of the results. The resulting vapor pressure equation is valid from the triple point to the normal boiling point temperature.

Highly Chemoselective Catalytic Photooxidations by Using Solvent as a Sacrificial Electron Acceptor.

Catalyst recovery is an integral part of photoredox catalysis. It is often solved by adding another component-a sacrificial agent-whose role is to convert the catalyst back into its original oxidation state. However, an additive may cause a side reaction thus decreasing the selectivity and overall efficiency. Herein, we present a novel approach towards chemoselective photooxidation reactions based on suitable solvent-acetonitrile acting simultaneously as an electron acceptor for catalyst recovery, and on anaerobic conditions. This is allowed by the unique properties of the catalyst, 7,8-dimethoxy-3-methyl-5-phenyl-5-deazaflavinium chloride existing in both strongly oxidizing and reducing forms, whose strength is increased by excitation with visible light. Usefulness of this system is demonstrated in chemoselective dehydrogenations of 4-methoxy- and 4-chlorobenzyl alcohols to aldehydes without over-oxidation to benzoic acids achieving yields up to 70 %. 4-Substituted 1-phenylethanols were oxidized to ketones with yields 80-100 % and, moreover, with yields 31-98 % in the presence of benzylic methyl group, diphenylmethane or thioanisole which are readily oxidized in the presence of oxygen but these were untouched with our system. Mechanistic studies based on UV-Vis spectro-electrochemistry, EPR and time-resolved spectroscopy measurements showed that the process involving an electron release from an excited deazaflavin radical to acetonitrile under formation of solvated electron is crucial for the catalyst recovery.

A Decade of Germananes: Four Approaches to Their Functionalization.

Since the first synthesis of germanane (GeH) reported in 2013, two-dimensional germanium-based materials have been intensively studied. Over the past decade, several methodologies for the functionalization of germanane have been introduced. The first approach utilized exfoliation of Zintl phase CaGe2 with alkyl halides. Liu's solvothermal method was used for the synthesis of methyl germanane. Another methodology utilized Ge-H activation with sodium naphthalenide and its subsequent alkylation. All of these methods provide functionalized germananes; thus, a comparison of these methods is needed. In this paper, such a comparison of current synthetic approaches towards alkyl germananes is reported, and additionally, a new method for Ge-H activation utilizing a NaK equimolar alloy is presented as a fourth approach. For this purpose, eight alkyl reagents were chosen representing reactive benzyl bromides as well as linear esters and nitriles because they contain easily trackable functional groups. The materials were characterized using Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis, and the data were compared. The comparison of all methods revealed not only some drawbacks for each method but also their advantages. The method utilizing sodium naphthalenide provided the lowest degree of surface coverage, whereas the solvothermal method seemed to provide materials with the highest degree of functionalization; unfortunately, the functionalization was also accompanied by a high degree of surface oxidation, i.e., (Ge-OH/Ge═O) formation. The highest degree of surface coverage accompanied by the lowest degree of surface oxidation was achieved employing Goldberger's phase transfer direct exfoliation of CaGe2 as well as Ge-H activation using the NaK alloy with subsequent alkylation.

Functional 2D Germanene Fluorescent Coating of Microrobots for Micromachines Multiplexing.

Micromachines are at the forefront of materials research as they are self-propelled, smart autonomous systems capable of acting as an intelligent matter. One of the obstacles the field faces is tracking individual micromachines carrying molecular cargo from the rest of the micromachines. Highly stable fluorescent markers based on chemically modified 2D germanene compounds are developed. Two different 2D germanene derivatives, 4-fluorophenylgermanane (2D-Ph-Ge) and methylgermanane (2D-Me-Ge), exhibit different fluorescence under UV light irradiation (excitation at 365 nm), which allows one particular micromotor to be easily distinguished in a mixture of micromotors. This offers a paradigm shift toward a new approach of multiplex detection of self-propelled micromachines. The utility is demonstrated on a drug delivery system, where micromachines carrying a drug are labeled with 2D-Ph-Ge with blue emission while bare micromachines are labeled by 2D-Me-Ge with red emission. This approach of functional fluorescent labeling will pave the way to multiple simultaneous functionalized micromachines identification in complex environments.

Chemistry of Layered Pnictogens: Phosphorus, Arsenic, Antimony, and Bismuth.

Materials with few layers have been subjected to extensive research for the last few decades owing to their remarkable properties as for example catalysts, optical and electrical devices, or sensors. The properties and electronic structure of these materials can be tailored by the introduction of substituents. In the case of more reactive species, the modification also can improve stability, which is also an important factor with respect to device fabrication. This review focuses on monoelemental layered materials of Group 15 elements (pnictogens) and in particular their modification, leading to better ambient stability and/or different properties by covalent and non-covalent modifications. The future modification and application of pnictogens are outlined.

Alkali Metal Arenides as a Universal Synthetic Tool for Layered 2D Germanene Modification.

The rediscovery of graphene in 2004 has started an enormous chase in the research of 2D materials. A new family of layered 2D materials consisting of the 14th group elements beyond carbon has already been reported. Here, a new methodology in germanene chemistry is presented using germanane (Ge6 H6 ) as a stable and easily accessible starting material for effective synthesis of novel germanene derivatives. The modification procedure utilizing strong bases-alkali metal arenides-for deprotonation of germanane and its subsequent functionalization with p-nitrobenzyl bromide is described. Functionalization of germanene is confirmed by FT-IR, Raman, and XPS spectroscopy as well as by X-ray diffraction analysis.

Chemistry of Graphene Derivatives: Synthesis, Applications, and Perspectives.

The chemistry of graphene and its derivatives is one of the hottest topics of current material science research. The derivatisation of graphene is based on various approaches, and to date functionalization with halogens, hydrogen, various functional groups containing oxygen, sulfur, nitrogen, phosphorus, boron, and several other elements have been reported. Most of these functionalizations are based on sp3 hybridization of carbon atoms in the graphene skeleton, which means the formation of out-of-plane covalent bonds. Several elements were also reported for substitutional modification of graphene, where the carbon atoms are substituted with atoms like nitrogen, boron, and several others. From tens of functional groups, for only two of them were reported full functionalization of graphene skeleton and formation of its stoichiometric counterparts, fluorographene and hydrogenated graphene. The functionalization of graphene is crucial for most of its applications including energy storage and conversion devices, electronic and optic applications, composites, and many others.

Covalent Functionalization of Exfoliated Arsenic with Chlorocarbene.

Few-layer and monolayer arsenic (arsenene) materials have been attracting great attention mainly from a theoretical perspective. Chemical modification of these materials would expand significantly the range of their applications. Here, we describe a chlorocarbene-mediated modification of exfoliated layered arsenic materials. Carbene-based species are highly reactive and offer further possibilities of functionalization. Our approach for modifying the arsenic surface by chlorocarbene generated from organolithium and dichloromethane resulted in a large surface coverage and a highly luminescent functionalized material, opening the door for its application in modern optoelectronic devices.

Excited-State Aromatic Interactions in the Aggregation-Induced Emission of Molecular Rotors.

Small, apolar aromatic groups, such as phenyl rings, are commonly included in the structures of fluorophores to impart hindered intramolecular rotations, leading to desirable solid-state luminescence properties. However, they are not normally considered to take part in through-space interactions that influence the fluorescent output. Here, we report on the photoluminescence properties of a series of phenyl-ring molecular rotors bearing three, five, six, and seven phenyl groups. The fluorescent emissions from two of the rotors are found to originate, not from the localized excited state as one might expect, but from unanticipated through-space aromatic-dimer states. We demonstrate that these relaxed dimer states can form as a result of intra- or intermolecular interactions across a range of environments in solution and solid samples, including conditions that promote aggregation-induced emission. Computational modeling also suggests that the formation of aromatic-dimer excited states may account for the photophysical properties of a previously reported luminogen. These results imply, therefore, that this is a general phenomenon that should be taken into account when designing and interpreting the fluorescent outputs of luminescent probes and optoelectronic devices based on fluorescent molecular rotors.

Fluorographene Modified by Grignard Reagents: A Broad Range of Functional Nanomaterials.

Fluorographene is the youngest stoichiometric derivative of graphene; hence, its reactivity is only poorly explored. Compared to graphene, the significantly higher reactivity of C-F bonds makes this material a suitable platform for a large number of chemical modifications. Fluorographene is also the only member of the halographene family that can be prepared in the stoichiometric composition (C1 F1 ). Herein, the chemical modification of fluorographene with Grignard reagents, which are well known in organic synthesis for the formation of new C-C bonds, is presented. The reaction with alkyl magnesium bromides led to successful modification of fluorographene with ethyl, vinyl, ethynyl and propargyl groups. Chemical characterisation showed the presence of covalently bonded functional groups in a high concentration exceeding one functional group per C6 motif. The reactivity of Grignard reagents with fluorographene decreased from ethyl to ethynyl. The terminal carbon-carbon triple bonds were used for click reactions with organic azides leading to the formation of triazole rings. These findings open up a broad spectrum of opportunities for simple and robust modification of graphene by chemical reactions proceeding at room temperature under mild conditions. These results have major application potential in sensing, biomedical and energy-related applications.

Mesomeric Effects of Graphene Modified with Diazonium Salts: Substituent Type and Position Influence its Properties.

In the last decade, graphene and graphene derivatives have become some of the most intensively studied materials. Tuning of the electronic and electrochemical properties of graphene is of paramount importance. In this study, six diazonium-modified graphenes containing different functional groups according to the diazonium salt precursor were investigated. These diazonium moieties have a strong mesomeric (resonance) effect and act as either electron-donating or -withdrawing species. Different graphene precursors, such as thermally and chemically reduced graphenes were studied. All the products were characterized in detail by elemental combustion analysis, FTIR spectroscopy, Raman spectroscopy, high-resolution X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry. Resistivity and zeta potential measurements were consistent with theoretical (DFT) calculations. The results show that chemical modification of graphene by diazotation strongly influences its properties, creating a huge application potential in microelectronics, energy storage and conversion devices, and electrocatalysis.

Electron-deficient heteroarenium salts: an organocatalytic tool for activation of hydrogen peroxide in oxidations.

A series of monosubstituted pyrimidinium and pyrazinium triflates and 3,5-disubstituted pyridinium triflates were prepared and tested as simple catalysts of oxidations with hydrogen peroxide, using sulfoxidation as a model reaction. Their catalytic efficiency strongly depends on the type of substituent and is remarkable for derivatives with an electron-withdrawing group, showing reactivity comparable to that of flavinium salts which are the prominent organocatalysts for oxygenations. Because of their high stability and good accessibility, 4-(trifluoromethyl)pyrimidinium and 3,5-dinitropyridinium triflates are the catalysts of choice and were shown to catalyze oxidation of aliphatic and aromatic sulfides to sulfoxides, giving quantitative conversions, high preparative yields and excellent chemoselectivity. The high efficiency of electron-poor heteroarenium salts is rationalized by their ability to readily form adducts with nucleophiles, as documented by low pKR+ values (pKR+ < 5) and less negative reduction potentials (Ered > -0.5 V). Hydrogen peroxide adducts formed in situ during catalytic oxidation act as substrate oxidizing agents. The Gibbs free energies of oxygen transfer from these heterocyclic hydroperoxides to thioanisole, obtained by calculations at the B3LYP/6-311++g(d,p) level, showed that they are much stronger oxidizing agents than alkyl hydroperoxides and in some cases are almost comparable to derivatives of flavin hydroperoxide acting as oxidizing agents in monooxygenases.

A Click Chemistry Approach towards Flavin-Cyclodextrin Conjugates-Bioinspired Sulfoxidation Catalysts.

A click chemistry approach based on the reaction between alkynylflavins and mono(6-azido-6-deoxy)-ß-cyclodextrin has proven to be a useful tool for the synthesis of flavin-cyclodextrin conjugates studied as monooxygenase mimics in enantioselective sulfoxidations.

Decoding Niobium Carbide MXene Dual-Functional Photoactive Cathode in Photoenhanced Hybrid Zinc-Ion Capacitor.

The coupling of energy harvesting and energy storage discrete modules in a single architecture as a "two-in-one" concept is significant in off-grid energy storage devices. This approach can decrease the device size and the loss of energy transmission in common integrated energy harvesting and storage systems. This work systematically investigates the photoactive characteristics of niobium carbide MXene, Nb2CTx, in a photoenhanced hybrid zinc-ion capacitor (P-ZIC). The unique configuration of the Nb2CTx photoactive cathode absorbs light to charge the capacitor and enables it to operate continuously in the light-powered mode. The Nb2CTx-based P-ZIC shows a photodriven capacitance enhancement of over 60% at the scan rate of 10 mV s-1 under 50 mW cm-2 illumination with 435 nm wavelength. Furthermore, a photoenhanced specific capacitance of ∼27 F g-1, an impressive photocharging voltage response of 1.0 V, and capacitance retention of ∼85% (over 3000 cycles) are obtained.

Impedimetric detection of gut-derived metabolites using 2D Germanene-based materials.

Apart from the extensively researched graphene under the Group 14 2D materials, monolayered germanene and its derivatives have been gaining interest lately as alternative class of 2D materials owing to their facile synthesis, and attractive electronic and optical properties. Herein, three different functionalized germanene-based nanomaterials, namely Ge-H, Ge-CH3 and Ge-C3-CN were investigated on their novel incorporation in impedimetric immunosensors for the detection of gut-derived metabolites associated with neurological diseases, such as kynurenic acid (KA) and quinolinic acid (QA). The designed germanene-based immunosensor relies on an indirect competitive mechanism using disposable electrode printed chips. The competition for a fixed binding site of a primary antibody occurs between the bovine serum albumin-conjugated antigens on the electrode surface and the free antigens in the solution. Among the three materials, Ge-H displayed superior bioanalytical performance in KA and QA detection. Lower limits of detection of 5.07-11.38 ng/mL (26.79-68.11 nM) were attained for KA and QA with a faster reaction time than previously reported methods. Also, minimal cross-reactivity with interfering compounds, good reproducibility in impedimetric responses (RSD = 2.43-7.51 %) and long-term stability up to a month at 4 °C were the other attributes that the proposed Ge-H competitive impedimetric immunosensor has accomplished. The application of the developed Ge-H immunosensor to serum samples allowed an accurate KA and QA quantification at physiologically relevant levels. This work serves as a stepping-stone in the development of germanene-based nanomaterials for their implementation into cost-effective, miniaturized, portable and rapid impedimetric immunosensors, which are highly desirable for point-of-care testing in clinical settings.

Tuning Germanane Band Gaps via Cyanoethyl Functionalization for Cutting-Edge Photoactive Cathodes: Photoenhanced Hybrid Zinc-Ion Capacitor Evaluation.

Energy harvesting and storing by dual-functional photoenhanced (photo-E) energy storage devices are being developed to battle the current energy hassles. In this research work, our investigations on the photoinduced efficiency of germanane (Ge-H) and its functionalized analogue cyanoethyl (Ge-C2-CN) are assessed as photocathodes in photo-E hybrid zinc-ion capacitors (ZICs). The evaluated self-powered photodetector devices made by these germanene-based samples revealed effective performances in photogenerated electrons and holes. The photo-E ZICs findings provided a photoinduced capacitance enhancement of ∼52% (for Ge-H) and ∼26% (for Ge-C2-CN) at a scan rate of 10 mV s-1 under 100 mW cm-2 illumination with 435 nm wavelength. Further characterizations demonstrated that the photo-E ZIC with Ge-C2-CN supply higher specific capacitance (∼6000 mF g-1), energy density (∼550 mWh kg-1), and power density (∼31,000 mW kg-1), compared to the Ge-H. In addition, capacitance retention of photo-E ZIC with Ge-C2-CN is ∼91% after 3000 cycles which is almost 6% greater than Ge-H. Interestingly, the photocharging voltage response in photo-E ZIC made by Ge-C2-CN is 1000 mV, while the photocharging voltage response with Ge-H is approximately 970 mV. The observed performances in Ge-H-based photoactive cathodes highlight the pivotal role of such two-dimensional materials to be applied as single architecture in new unconventional energy storage systems. They are particularly noteworthy when compared to the other advanced photo-E supercapacitors and could even be enhanced greatly with other suitable inorganic and organic functional precursors.

High-κ Wide-Gap Layered Dielectric for Two-Dimensional van der Waals Heterostructures.

van der Waals heterostructures of two-dimensional materials have unveiled frontiers in condensed matter physics, unlocking unexplored possibilities in electronic and photonic device applications. However, the investigation of wide-gap, high-κ layered dielectrics for devices based on van der Waals structures has been relatively limited. In this work, we demonstrate an easily reproducible synthesis method for the rare-earth oxyhalide LaOBr, and we exfoliate it as a 2D layered material with a measured static dielectric constant of 9 and a wide bandgap of 5.3 eV. Furthermore, our research demonstrates that LaOBr can be used as a high-κ dielectric in van der Waals field-effect transistors with high performance and low interface defect concentrations. Additionally, it proves to be an attractive choice for electrical gating in excitonic devices based on 2D materials. Our work demonstrates the versatile realization and functionality of 2D systems with wide-gap and high-κ van der Waals dielectric environments.

Hydrogen-Terminated Two-Dimensional Germanane/Silicane Alloys as Self-Powered Photodetectors and Sensors.

2D monoelemental materials, particularly germanene and silicene (the single layer of germanium and silicon), which are the base materials for modern electronic devices demonstrated tremendous attraction for their 2D layer structure along with the tuneable electronics and optical band gap. The major shortcoming of synthesized thermodynamically very unstable layered germanene and silicene with their inclination toward oxidation was overcome by topochemical deintercalation of a Zintl phase (CaGe2, CaGe1.5Si0.5, and CaGeSi) in a protic environment. The exfoliated Ge-H, Ge0.75Si0.25H, and Ge0.5Si0.5H were successfully synthesized and employed as the active layer for photoelectrochemical photodetectors, which showed broad response (420-940 nm), unprecedented responsivity, and detectivity on the order of 168 µA W-1 and 3.45 × 108 cm Hz1/2 W-1, respectively. The sensing capability of exfoliated germanane and silicane composites was explored using electrochemical impedance spectroscopy with ultrafast response and recovery time of less than 1 s. These positive findings serve as the application of exfoliated germanene and silicene composites and can pave a new path to practical applications in efficient future devices.

Universal Capacitance Boost-Smart Surface Nanoengineering by Zwitterionic Molecules for 2D MXene Supercapacitor.

Two-dimensional nanomaterials, as one of the most widely used substrates for energy storage devices, have achieved great success in terms of the overall capacity. Despite the extensive research effort dedicated to this field, there are still major challenges concerning capacitance modulation and stability of the 2D materials that need to be overcome. Doping of the crystal structures, pillaring methods and 3D structuring of electrodes have been proposed to improve the material properties. However, these strategies are usually accompanied by a significant increase in the cost of the entire material preparation process and also a lack of the versatility for modification of the various types of the chemical structures. Hence in this work, versatile, cheap, and environmentally friendly method for the enhancement of the electrochemical parameter of various MXene-based supercapacitors (Ti3 C2 , Nb2 C, and V2 C), coated with functional and charged organic molecules (zwitterions-ZW) is introduced. The MXene-organic hybrid strategy significantly increases the ionic absorption (capacitance boost) and also forms a passivation layer on the oxidation-prone surface of the MXene through the covalent bonds. Therefore, this work demonstrates a new, cost-effective, and versatile approach (MXene-organic hybrid strategy) for the design and fabrication of hybrid MXene-base electrode materials for energy storage/conversion systems.

Black Phosphorus: Fundamental Properties and Influence of Impurities Induced by Its Synthesis.

Black phosphorus (BP) has been among the most widely explored materials in recent years because of its exceptional properties. A vapor transport method using tin and iodide as mineralizers was used to synthesize large crystals which can be used for fundamental physical characterization including electrical and heat transport and heat capacity. This method is compared to other reported procedures (high-pressure crystal growth and mercury catalysis) which are broadly used and the most dominant procedures for the obtainment of bulk layered BP. In addition, we have investigated any possible impurities which could have been introduced by synthesis and their possible incorporation into BP and their influence on the physical properties of BP.