Two-Step Thermal Transformation of Multilayer Graphene Using Polymeric Carbon Source Assisted by Physical Vapor Deposited Copper.

Direct in situ growth of graphene on dielectric substrates is a reliable method for overcoming the challenges of complex physical transfer operations, graphene performance degradation, and compatibility with graphene-based semiconductor devices. A transfer-free graphene synthesis based on a controllable and low-cost polymeric carbon source is a promising approach for achieving this process. In this paper, we report a two-step thermal transformation method for the copper-assisted synthesis of transfer-free multilayer graphene. Firstly, we obtained high-quality polymethyl methacrylate (PMMA) film on a 300 nm SiO2/Si substrate using a well-established spin-coating process. The complete thermal decomposition loss of PMMA film was effectively avoided by introducing a copper clad layer. After the first thermal transformation process, flat, clean, and high-quality amorphous carbon films were obtained. Next, the in situ obtained amorphous carbon layer underwent a second copper sputtering and thermal transformation process, which resulted in the formation of a final, large-sized, and highly uniform transfer-free multilayer graphene film on the surface of the dielectric substrate. Multi-scale characterization results show that the specimens underwent different microstructural evolution processes based on different mechanisms during the two thermal transformations. The two-step thermal transformation method is compatible with the current semiconductor process and introduces a low-cost and structurally controllable polymeric carbon source into the production of transfer-free graphene. The catalytic protection of the copper layer provides a new direction for accelerating the application of graphene in the field of direct integration of semiconductor devices.

Mechanistic Investigations of Thermal Decomposition of Perfluoroalkyl Ether Carboxylic Acids and Short-Chain Perfluoroalkyl Carboxylic Acids.

In this study, we investigated the thermal decomposition mechanisms of perfluoroalkyl ether carboxylic acids (PFECAs) and short-chain perfluoroalkyl carboxylic acids (PFCAs) that have been manufactured as replacements for phased-out per- and polyfluoroalkyl substances (PFAS). C-C, C-F, C-O, O-H, and C═C bond dissociation energies were calculated at the M06-2X/Def2-TZVP level of theory. The α-C and carboxyl-C bond dissociation energy of PFECAs declines with increasing chain length and the attachment of an electron-withdrawing trifluoromethyl (-CF3) group to the α-C. Experimental and computational results show that the thermal transformation of hexafluoropropylene oxide dimer acid to trifluoroacetic acid (TFA) occurs due to the preferential cleavage of the C-O ether bond close to the carboxyl group. This pathway produces precursors of perfluoropropionic acid (PFPeA) and TFA and is supplemented by a minor pathway (CF3CF2CF2OCFCF3COOH → CF3CF2CF2· + ·OCFCF3COOH) through which perfluorobutanoic acid (PFBA) is formed. The weakest C-C bond in PFPeA and PFBA is the one connecting the α-C and the ß-C. The results support (1) the C-C scission in the perfluorinated backbone as an effective PFCA thermal decomposition mechanism and (2) the thermal recombination of radicals through which intermediates are formed. Additionally, we detected a few novel thermal decomposition products of studied PFAS.

Identifying the fate of nitrogenous species during sewage sludge pyrolysis via in-situ tracing of protein-sludge inherent components interactions.

The effect of interactions between different components in sewage sludge on the thermochemical transformation of nitrogenous species is usually neglected, which is important to explain the generation mechanism of some key nitrogenous by-products. Here, we investigated the distribution, form, and chemical properties of the products from sludge-extracted protein (PR) under different pyrolysis scenarios using several in-situ probe techniques, to elucidate the critical role of typical sludge organics/inorganics on the evolution of nitrogenous intermediates and by-products. The results suggested that Ca/Fe/Si/Al-containing inorganics significantly affected the pyrolytic behavior of PR and the thermal transformation of nitrogenous species, while sludge organics, including humic acids and polysaccharides, had limited effects on the temperature-dependent evolution of nitrogenous species in PR. Among them, calcium oxide catalyzed the ring-opening reaction of heterocyclic-N with aromatic-like structures, resulting in a 21.1 %-68.8 % reduction in nitrogen fixation efficiency in the char. At lower temperatures (350-450 °C), calcium oxide caused more nitrogen to be transferred to the gas/tar phases in the form of NH3 and heterocyclic-N, and it also enhanced the conversion of nitrile-N → HCN → NO at temperatures above 450 °C. In contrast, polyferric salts inhibited the devolatilization of mono-heterocyclic-N and enhanced the thermal stability of poly-heterocyclic-N, resulting in a maximum increase of 18.5 mg·g-1 of nitrogen content in the char, while reducing the release of NH3 and HCN by 71.1 % and 32.0 %. This work elucidated the interaction between PR and inherent components in sludge, providing key information for the control of nitrogenous volatiles and NOx.

Structural and antimicrobial property changes of veterinary antibiotics in thermal treatment.

Agricultural application contributes major consumption of antibiotics worldwide. As veterinary antibiotics are poorly metabolized by animals, most of them end up in agricultural waste, which is increasingly subject to thermal treatment, such as torrefaction, pyrolysis, etc. However, there is a lack of research on their thermal decomposition mechanisms and products elucidation. Therefore, this study investigated the thermal decomposition of four major veterinary antibiotics groups (ß-lactams, tetracyclines, fluoroquinolones, sulfonamides) with emphasis on their thermal stability, structural transformation and antibacterial activity. Results show that thermal treatment can remove the parent antibiotics with their antibacterial activity except for gatifloxacin (GAT). Although the parent form of GAT was fully removed at 200 °C, its products showed significant antibacterial activity against E. coli. We present novel evidence that the PhO-CH3 chemical bond on GAT preferentially brake to generate methyl radical, which underwent a substitution reaction at the para position of phenol. This reaction also occurred during the thermal decomposition of antibiotic analogues, balofloxacin and moxifloxacin, whose thermolysis products also showed significant antibacterial activity. Furthermore, these thermolysis products may present potentially cardiotoxic and pose higher risks to human health than their parent forms, based on the comparison with a group of drugs withdrawn from the market.

Transformations and antioxidative activities of lignans and stilbenes at high temperatures.

Thermal transformations of polyphenols from the lignan and stilbene families were investigated at temperatures ranging from 200 °C to 250 °C, in polyethylene glycol (PEG-400), dimethylformamide (DMF) and in sunflower oil (SO). The polyphenols showed varying degrees of thermal stabilities and in some cases intramolecular transformations were observed. The formed products were isolated and characterized. Oligomerization of the polyphenols at thermo-oxidative conditions was also investigated. Finally, the antioxidative activity of the polyphenols against thermo-oxidative degradation α-linoleic acid was investigated at 200 °C. The results suggested that the studied substrates retained their antioxidative properties at elevated temperatures, with stilbenes showing most efficient protection against thermo-oxidative degradation of polyunsaturated fatty acids.

Thermally-induced color transformation of hematite: insight into the prehistoric natural pigment preparation.

Since the prehistoric era, hematite has been known as a reddish color pigment on rock art, body paint, and decorating substances for objects discovered almost worldwide. Recently, studies about purple hematite used in prehistoric pigment have been done vigorously to investigate the origin of the purple pigment itself. These previous studies indicate that the differentiation of crystallinity, crystal size, morphology, and electronic structure can cause the color shift, resulting in purple hematite. In this study, we conducted a detailed study of the sintering temperature effects on the formation of hematite minerals. This study aims to reveal the structural, crystallography, and electronic transformation in hematite due to heating treatment at various temperatures. The hematite was synthesized using precipitation to imitate the primary method of hematite formation in nature. The sintering process was carried out with temperature variations from 600 °C to 1100 °C and then characterized by crystallographic and structural properties (XRD, Raman Spectroscopy, FTIR), particle size (TEM), as well as electronic properties (DRS, XANES). The crystallinity and particle size of hematite tend to increase along with higher sintering temperatures. Moreover, we noted that the octahedral distortion underwent an intensification with the increase in sintering temperature, which affected the electronic structure of hematite. Specifically, the 1s → 3d transition exhibited lower energy for hematite produced at a higher temperature. This induced a shift in the absorbed energy of the polychromatic light that led to a color shift within hematite, from red to purple. Our finding emphasizes the importance of electronic structure in explaining hematite pigment's color change rather than relying on simple reasons, such as particle size and crystallinity. In addition, this might strengthen the hypothesis that the prehistoric human created a purple hematite pigment through heating.

The first quantitative investigation of compounds generated from PFAS, PFAS-containing aqueous film-forming foams and commercial fluorosurfactants in pyrolytic processes.

Pyrolysis as a thermochemical technology is commonly used in waste management and remediation of organic-contaminated soil. This study, for the first time, investigated fluorinated and non-fluorinated compounds emitted from per- and polyfluoroalkyl substances (PFAS) and relevant products upon pyrolysis (200-890 °C) and their formation mechanisms. Approximately 30 non-fluorinated compounds were detected from PFAS-containing aqueous film-forming foams (AFFFs) and commercial surfactant concentrates (SCs) after heating, including glycols and glycol ethers that were predominant at 200 °C. Oxygen (e.g., 1,4-dioxane) and nitrogen heterocycles and benzene were unexpectedly observed at higher temperatures (300-890 °C), which were likely formed as a consequence of the thermal dehydration, dehydrogenation, and intermolecular cyclization of glycols and glycol ethers. Fluorinated volatiles in six major classes were detected at low and moderate temperatures (200-500 °C), including perfluoroalkenes, perfluoroalkyl aldehydes, fluorotelomer alcohols, and polyfluorinated alkanes/alkenes. Several features of the pyrolyses of PFAS suggest that the underlying decomposition mechanism is radical-mediated. Perfluoroheptene thermally decomposed at 200 °C to shorter-chain homologues following a radical chain-scission mechanism. Most of these volatiles observed at low/moderate temperatures were not detected at 890 °C. Ultra-short-chain fluorinated greenhouse gases (e.g., perfluoromethane) were not found.

Application of Nontarget Analysis and High-Resolution Mass Spectrometry for the Identification of Thermal Transformation Products of Oxytetracycline in Pacific White Shrimp.

ABSTRACT: Oxytetracycline (OTC) is an antibiotic authorized for use in aquaculture; it is often detected in seafood products, especially shrimp. Previous studies investigating the fate of OTC in shrimp tissues after cooking were limited to quantification of parent compound residues and did not describe any potential transformation products formed. Hence, the main objective of this study was to apply a nontarget analysis workflow to study the fate of OTC in shrimp muscle. Furthermore, "water" and "spiked" models were evaluated for their suitability to track the transformation of OTC in incurred muscle and to determine whether the matrix plays a role in the transformation pathway. First, four different extraction methods were compared for the determination of OTC in muscle. Second, raw and cooked samples were then extracted using a suitable method (acidified water-methanol-acetonitrile, with cleanup of samples achieved using freezing) and were analyzed by high-performance liquid chromatography quadrupole time-of-flight mass spectrometry. OTC levels were reduced by 75 and 87% in muscle and water, respectively. Identification of thermal transformation products was limited to formula generation, but results showed that different compounds were identified in spiked and incurred muscle.

Physico-Chemical Characteristics of Spodumene Concentrate and Its Thermal Transformations.

Spodumene concentrate from the Pilbara region in Western Australia was characterized by X-ray diffraction (XRD), Scanning Electron Microscope Energy Dispersive Spectroscopy (SEM-EDS) and Mineral Liberation Analysis (MLA) to identify and quantify major minerals in the concentrate. Particle diameters ranged from 10 to 200 microns and the degree of liberation of major minerals was found to be more than 90%. The thermal behavior of spodumene and the concentration of its polymorphs were studied by heat treatments in the range of 900 to 1050 °C. All three polymorphs of the mineral (α, γ and ß) were identified. Full transformation of the α-phase was achieved at 975 °C and 1000 °C after 240 and 60 min treatments, respectively. SEM images of thermally treated concentrate revealed fracturing of spodumene grains, producing minor cracks initially which became more prominent with increasing temperature. Material disintegration, melting and agglomeration with gangue minerals were also observed at higher temperatures. The metastable γ-phase achieved a peak concentration of 23% after 120 min at 975 °C. We suggest 1050 °C to be the threshold temperature for the process where even a short residence time causes appreciable transformation, however, 1000 °C may be the ideal temperature for processing the concentrate due to the degree of material disintegration and α-phase transformation observed. The application of a first-order kinetic model yields kinetic parameters which fit the experimental data well. The resultant apparent activation energies of 655 and 731 kJ mol-1 obtained for α- and γ-decay, respectively, confirm the strong temperature dependence for the spodumene polymorph transformations.

On-line detection and kinetic study of selenium release during combustion, gasification and pyrolysis of sawdust.

An on-line analysis system was firstly developed to quantitatively measure the temporal concentrations of selenium in the flue gas directly. Then the selenium release during air combustion, CO2/argon gasification, and argon pyrolysis of sawdust was systematically studied using the on-line analysis system, based on the inductively coupled plasma optical emission spectroscopy. The peak of selenium concentration in the flue gas ranges from 0.38 to 1.76 mg∙Nm-3 with change of reaction temperature and atmosphere. The overall activation energy for selenium release is 75.3 kJ∙mol-1 in air combustion, 102.4 kJ∙mol-1 in CO2/argon gasification, and 81.9 kJ∙mol-1 in argon pyrolysis, respectively. The results show that the combustion atmosphere contributes to the selenium release more than that in gasification and pyrolysis. The promotion effect of chlorine on selenium release under combustion environment was one to three times higher than that under gasification and pyrolysis atmosphere. Thermodynamic equilibrium calculation showed that selenium oxides were the main gaseous selenium species in combustion, while the dominant gaseous selenium species were H2Se (g) and Se (g) under gasification/pyrolysis condition. The selenium release was increased with different degrees by additive chlorine species, mainly because of the formation of SeCl2 (g). The role of chlorine in selenium transformation has been provided in the proposed reaction pathways of selenium release, based on the new findings using on-line analysis system. The selenium species retained in sawdust can be transformed into selenium oxide (SeO2, SeO, corresponding to the combustion condition) and selenium hydride (H2Se, corresponding to the gasification/pyrolysis conditions).

Thermal Decomposition of Anionic, Zwitterionic, and Cationic Polyfluoroalkyl Substances in Aqueous Film-Forming Foams.

In this study, we investigated thermal decomposition mechanisms of cationic, zwitterionic, and anionic polyfluoroalkyl substances, including those present in aqueous film-forming foam (AFFF) samples. We present novel evidence that polyfluoroalkyl substances gave quantitative yields of perfluoroalkyl substances of different chain lengths during thermal treatment. The results support a radical-mediated transformation mechanism involving random-chain scission and end-chain scission, leading to the formation of perfluoroalkyl carboxylic acids such as perfluorooctanoic acid (PFOA) from certain polyfluoroalkyl amides and sulfonamides. Our results also support a direct thermal decomposition mechanism (chain stripping) on the nonfluorinated moiety of polyfluoroalkyl sulfonamides, resulting in the formation of perfluorooctanesulfonic acid (PFOS) and other structurally related polyfluoroalkyl compounds. Thermal decomposition of 8:2 fluorotelomer sulfonate occurred through end-chain scission and recombination reactions, successively yielding PFOS. All of the studied polyfluoroalkyl substances began to degrade at 200-300 °C, exhibiting near-complete decomposition at ≥400 °C. Using a high-resolution parent ion search method, we demonstrated for the first time that low-temperature thermal treatments of AFFF samples led to the generation of anionic fluoroalkyl substances, including perfluoroheptanesulfonamide, 8:2 fluorotelomer sulfonic acid, N-methyl perfluorooctane sulfonamide, and a previously unreported compound N-2-propenyl-perfluorohexylsulfonamide. This study provides key insights into the fate of polyfluoroalkyl substances in thermal processes.

In Situ Transmission Electron Microscopy Analysis of Thermally Decaying Polycrystalline Platinum Nanowires.

Owing to their large surface area, continuous conduction paths, high activity, and pronounced anisotropy, nanowires are pivotal for a wide range of applications, yet far from thermodynamic equilibrium. Their susceptibility toward degradation necessitates an in-depth understanding of the underlying failure mechanisms to ensure reliable performance under operating conditions. In this study, we present an in-depth analysis of the thermally triggered Plateau-Rayleigh-like morphological instabilities of electrodeposited, polycrystalline, 20-40 nm thin platinum nanowires using in situ transmission electron microscopy in a controlled temperature regime, ranging from 25 to 1100 °C. Nanowire disintegration is heavily governed by defects, while the initially present, frequent but small thickness variations do not play an important role and are overridden later during reshaping. Changes of the exterior wire morphology are preceded by shifts in the internal nanostructure, including grain boundary straightening, grain growth, and the formation of faceted voids. Surprisingly, the nanowires segregate into two domain types, one being single-crystalline and essentially void-free, while the other preserves void-pinned grain boundaries. While the single-crystalline domains exhibit fast Pt transport, the void-containing domains are unexpectedly stable, accumulate platinum by surface diffusion, and act as nuclei for the subsequent nanowire splitting. This study highlights the vital role of defects in Plateau-Rayleigh-like thermal transformations, whose evolution not only accompanies but guides the wire reshaping. Thus, defects represent strong parameters for controlling the nanowire decay and must be considered for devising accurate models and simulations.

Divergent and Multi-Stage Photoisomerization of Four-Coordinated Boron Compounds with a Naphthyl-Pyridyl/Thiazolyl Backbone.

Examination of the photoreactivity of a new class of N,C-chelate organoboron compounds, including a series of unsymmetrically substituted boron molecules, B(naph-pyridyl)(Ar1 )(Ar2 ) and B(naph-thiazolyl)(Ar1 )(Ar2 ), led to the discovery of new and divergent photothermal isomerization phenomena. These include the clean and regioselective photoisomerization by unsymmetrical boron, forming borepin isomers, some of which further isomerize to the corresponding boratanorcaradiene diastereomer pairs as a result of the generation of two chiral centers. Significantly, the boratanorcaradienes involving a 3-thienyl substituent on boron were found to thermally convert to BN-fluoranthene annulated borapentalene via an unprecedented reversible boratacyclopropane-boratacyclopentene rearrangement. Changing the pyridyl donor to a thiazolyl donor on the boron was found to provide the B(naph-thiazolyl)(Mes)2 compounds with a distinct new photoisomerization pathway-instead of borepin, forming new blue fluorescent polycyclic azaborinine species. This work illustrates the richness and complexity of boron photochemistry.

Magnetoresistance and Thermal Transformation Arrest in Pd2Mn1.4Sn0.6 Heusler Alloys.

The magnetization, electric resistivity, and magnetoresistance properties of Pd 2 Mn 1 . 4 Sn 0 . 6 Heusler alloys were investigated. The Curie temperature of the parent phase, martensitic transformation temperatures, and magnetic field dependence of the martensitic transformation temperatures were determined. The magnetoresistance was investigated from 10 to 290 K, revealing both intrinsic and extrinsic magnetoresistance properties for this alloy. A maximum of about - 3 . 5 % of intrinsic magnetoresistance under 90 kOe and of about - 30 % of extrinsic magnetoresistance under 180 kOe were obtained. Moreover, the thermal transformation arrest phenomenon was confirmed in the Pd 2 Mn 1 . 4 Sn 0 . 6 alloy, and an abnormal heating-induced martensitic transformation (HIMT) behavior was observed.

Micro-Blooming: Hierarchically Porous Nitrogen-Doped Carbon Flowers Derived from Metal-Organic Mesocrystals.

Synthesis of 3D flower-like zinc-nitrilotriacetic acid (ZnNTA) mesocrystals and their conformal transformation to hierarchically porous N-doped carbon superstructures is reported. During the solvothermal reaction, 2D nanosheet primary building blocks undergo oriented attachment and mesoscale assembly forming stacked layers. The secondary nucleation and growth preferentially occurs at the edges and defects of the layers, leading to formation of 3D flower-like mesocrystals comprised of interconnected 2D micropetals. By simply varying the pyrolysis temperature (550-1000 °C) and the removal method of in the situ-generated Zn species, nonporous parent mesocrystals are transformed to hierarchically porous carbon flowers with controllable surface area (970-1605 m2 g-1 ), nitrogen content (3.4-14.1 at%), pore volume (0.95-2.19 cm3 g-1 ), as well as pore diameter and structures. The carbon flowers prepared at 550 °C show high CO2 /N2 selectivity due to the high nitrogen content and the large fraction of (ultra)micropores, which can greatly increase the CO2 affinity. The results show that the physicochemical properties of carbons are highly dependent on the thermal transformation and associated pore formation process, rather than directly inherited from parent precursors. The present strategy demonstrates metal-organic mesocrystals as a facile and versatile means toward 3D hierarchical carbon superstructures that are attractive for a number of potential applications.

In-situ solid phase thermal transformation of self-assembled melamine phosphotungstates produce efficient visible light photocatalysts.

Visible-light-driven stacked-layer heterogeneous photocatalyst carbonitride/tungstophosphate (TCN) was constructed via in-situ solid-state thermal transformation using melamine phosphotungstate (MPW). The structural, morphological and optical properties of the samples were investigated. Compared to the MPW hybrids and phosphotungstic acid hydrate, the TCN photocatalysts showed excellent visible light photocatalytic activity. During the thermal transformation, the melamine molecules polymerize to form the defective heptazine structure carbonitride attached to the surface of mixed-valence Keggin units. The interfacial POMs anions-π interactions, ligand-to-metal charge transfer and mix-valence organic-POMs structure makes the electrons fully delocalized over the MPW hybrids, and the TCN photocatalysts obtain the extended light absorption. The Keggin units accept and transfer electrons, so the recombination of photogenerated carriers is suppressed. 13TCN-390 obtains the optimal photocatalytic activity, its photocatalytic degradation efficiency of imidacloprid and rate constant k are 6.38 and 13.50 times than that of CN-390, respectively. The enhanced photocatalytic activity arises from the extended light absorption, suppressed photogenerated carriers' recombination, surface structure defect and suitable band structure. h+ and OH are the main reactive species when the proposed photocatalytic mechanism was done. This study provides a promising construction strategy for polymer/POMs photocatalysts using different organic-POMs hybrids.

Transformation of chlorinated paraffins to olefins during metal work and thermal exposure - Deconvolution of mass spectra and kinetics.

Chlorinated paraffins (CPs) are high production volume chemicals widely used as additives in metal working fluids. Thereby, CPs are exposed to hot metal surfaces which may induce degradation processes. We hypothesized that the elimination of hydrochloric acid would transform CPs into chlorinated olefins (COs). Mass spectrometry is widely used to detect CPs, mostly in the selected ion monitoring mode (SIM) evaluating 2-3 ions at mass resolutions R < 20'000. This approach is not suited to detected COs, because their mass spectra strongly overlap with CPs. We applied a mathematical deconvolution method based on full-scan MS data to separate interfered CP/CO spectra. Metal drilling indeed induced HCl-losses. CO proportions in exposed mixtures of chlorotridecanes increased. Thermal exposure of chlorotridecanes at 160, 180, 200 and 220 °C also induced dehydrohalogenation reactions and CO proportions also increased. Deconvolution of respective mass spectra is needed to study the CP transformation kinetics without bias from CO interferences. Apparent first-order rate constants (kapp) increased up to 0.17, 0.29 and 0.46 h-1 for penta-, hexa- and heptachloro-tridecanes exposed at 220 °C. Respective half-life times (τ1/2) decreased from 4.0 to 2.4 and 1.5 h. Thus, higher chlorinated paraffins degrade faster than lower chlorinated ones. In conclusion, exposure of CPs during metal drilling and thermal treatment induced HCl losses and CO formation. It is expected that CPs and COs are co-released from such processes. Full-scan mass spectra and subsequent deconvolution of interfered signals is a promising approach to tackle the CP/CO problem, in case of insufficient mass resolution.

Selective thermal transformation of old computer printed circuit boards to Cu-Sn based alloy.

This study investigates, verifies and determines the optimal parameters for the selective thermal transformation of problematic electronic waste (e-waste) to produce value-added copper-tin (Cu-Sn) based alloys; thereby demonstrating a novel new pathway for the cost-effective recovery of resources from one of the world's fastest growing and most challenging waste streams. Using outdated computer printed circuit boards (PCBs), a ubiquitous component of e-waste, we investigated transformations across a range of temperatures and time frames. Results indicate a two-step heat treatment process, using a low temperature step followed by a high temperature step, can be used to produce and separate off, first, a lead (Pb) based alloy and, subsequently, a Cu-Sn based alloy. We also found a single-step heat treatment process at a moderate temperature of 900 °C can be used to directly transform old PCBs to produce a Cu-Sn based alloy, while capturing the Pb and antimony (Sb) as alloying elements to prevent the emission of these low melting point elements. These results demonstrate old computer PCBs, large volumes of which are already within global waste stockpiles, can be considered a potential source of value-added metal alloys, opening up a new opportunity for utilizing e-waste to produce metal alloys in local micro-factories.

Highly Efficient Fumed Silica Nanoparticles for Peptide Bond Formation: Converting Alanine to Alanine Anhydride.

In this work, thermal condensation of alanine adsorbed on fumed silica nanoparticles is investigated using thermal analysis and multiple spectroscopic techniques, including infrared (IR), Raman, and nuclear magnetic resonance (NMR) spectroscopies. Thermal analysis shows that adsorbed alanine can undergo thermal condensation, forming peptide bonds within a short time period and at a lower temperature (∼170 °C) on fumed silica nanoparticle surfaces than that in bulk (∼210 °C). Spectroscopic results further show that alanine is converted to alanine anhydride with a yield of 98.8% during thermal condensation. After comparing peptide formation on solution-derived colloidal silica nanoparticles, it is found that fumed silica nanoparticles show much better efficiency and selectivity than solution-derived colloidal silica nanoparticles for synthesizing alanine anhydride. Furthermore, Raman spectroscopy provides evidence that the high efficiency for fumed silica nanoparticles is likely related to their unique surface features: the intrinsic high population of strained ring structures present at the surface. This work indicates the great potential of fumed silica nanoparticles in synthesizing peptides with high efficiency and selectivity.

Thermal transformation of bioactive caffeic acid on fumed silica seen by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry and quantum chemical methods.

Thermochemical studies of hydroxycinnamic acid derivatives and their surface complexes are important for the pharmaceutical industry, medicine and for the development of technologies of heterogeneous biomass pyrolysis. In this study, structural and thermal transformations of caffeic acid complexes on silica surfaces were studied by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry (TPD MS) and quantum chemical methods. Two types of caffeic acid surface complexes are found to form through phenolic or carboxyl groups. The kinetic parameters of the chemical reactions of caffeic acid on silica surface are calculated. The mechanisms of thermal transformations of the caffeic chemisorbed surface complexes are proposed. Thermal decomposition of caffeic acid complex chemisorbed through grafted ester group proceeds via three parallel reactions, producing ketene, vinyl and acetylene derivatives of 1,2-dihydroxybenzene. Immobilization of phenolic acids on the silica surface improves greatly their thermal stability.