Cross-polarization Magic Angle Spinning Research Articles

Pd8(PDip)6: Cubic, Unsaturated, Zerovalent.

Atomically precise nanoclusters hold promise for supramolecular assembly and (opto)electronic- as well as magnetic materials. Herein, this work reports that treating palladium(0) precursors with a triphosphirane affords strongly colored Pd8(PDip)6 that is fully characterized by mass spectrometry, heteronuclear and Cross-Polarization Magic-Angle Spinning (CP-MAS) NMR-, infrared (IR), UV-vis, and X-ray photoelectron (XP) spectroscopies, single-crystal X-Ray diffraction (sc-XRD), mass spectrometry, and cyclovoltammetry (CV). This coordinatively unsaturated 104-electron Pd(0) cluster features a cubic Pd8-core, µ4-capping phosphinidene ligands, and is air-stable. Quantum chemical calculations provide insight to the cluster's electronic structure and suggest 5s/4d orbital mixing as well as minor Pd─P covalency. Trapping experiments reveal that cluster growth proceeds via insertion of Pd(0) into the triphosphirane. The unsaturated cluster senses ethylene and binds isocyanides, which triggers the rearrangement to a tetrahedral structure with a reduced frontier orbital energy gap. These experiments demonstrate facile cluster manipulation and highlight non-destructive cluster rearrangement as is required for supramolecular assembly.

Noncontact In Situ Multidiagnostic NMR/Dielectric Spectroscopy.

Introduction of a dielectric material in a nuclear magnetic resonance (NMR) probe head modifies the frequency response of the probe circuit, a phenomenon revealed by detuning of the probe. For NMR spectroscopy, this detuning is corrected for by tuning and matching the probe head prior to the NMR measurement. The magnitude of the probe detuning, "the dielectric shift", provides direct access to the dielectric properties of the sample, enabling NMR spectrometers to simultaneously perform both dielectric and NMR spectroscopy. By measuring sample dielectric permittivity as a function of frequency, dielectric permittivity spectroscopy can be performed using the new methodology. As a proof of concept, this was evaluated on methanol, ethanol, 1-propanol, 1-pentanol, and 1-octanol using a commercial cross-polarization magic angle spinning (CPMAS) NMR probe head. The results accurately match the literature data collected by standard dielectric spectroscopy techniques. Subsequently, the method was also applied to investigate the solvent-surface interactions of water confined in the micropores of an MFI-type, hydrophilic zeolite with a Si/Al ratio of 11.5. In the micropores, water adsorbs to Bro̷nsted acid sites and defect sites, resulting in a drastically decreased dielectric permittivity of the nanoconfined water. Theoretical background for the new methodology is provided using an effective electric circuit model of a CPMAS probe head with a solenoid coil, describing the detuning resulting from the insertion of dielectric samples in the probe head.

Multi-components reactions on construction carboxylic-rich conjugated polymeric crown ethers as sustainable materials for CO2-fixation and iodine vapor adsorption: Experimental and kinetics

Carbon dioxide, as an industrial waste gas, has a severe impact on the climate. Thus, efficient catalytic conversion of CO2 has attracted considerable attention worldwide. In this study, a series of crown ether-conjugated microporous polymer materials containing carboxylic groups (CCMPs) were synthesized through multi-components reactions in one pot. This synthesis involved the reaction of dialdehydebenzo-18-crown-6 with different monomers of amino and pyruvate in the presence of DDQ. Fourier transform infrared spectroscopy, carbon-13 cross-polarization magic angle spinning nuclear magnetic resonance, scanning electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy were used to characterize the CCMPs. Then, CCMPs were used in CO2 fixation and iodine vapor adsorption. The co-catalyst KI and CCMP-4 exhibited excellent activity in mild conditions, resulting in a 94% yield. The catalytic activity of the CCMP-4 was maintained after the five cycles. The kinetics of CCMP-4 was studied, and a potential reaction mechanism was proposed. The iodine adsorption experiments were conducted on CCMPs. The results showed that CCMPs exhibited excellent adsorption effects at 75 °C. The adsorption capacities of CCMP-1, CCMP-2, CCMP-3 and CCMP-4 were 3.02, 2.68, 2.72 and 3.21 g·g−1, respectively. The experimental results showed that CCMPs effectively absorbed iodine vapor and exhibited an excellent catalytic effect on CO2 cycloaddition under mild conditions, which is proved by density functional theory calculations further.

The hidden depths of forest soil organic carbon chemistry in a pumice soil

Forest ecosystems can store massive amounts of organic carbon (OC) deep in their soils. Soil OC (SOC) is composed of several complex organic compounds of which groupings of these organic compounds can provide an insight into evaluating the formation and fate of SOC. However, there is little information available regarding the chemical composition of deep forest SOC and how they compare to upper soil depths. The objective of this study was to explore the SOC chemistry changes with increasing soil depth on a fine spatial scale in a planted forest soil derived from young volcanic erupted airfall deposits. Soil core samples to 1 m depth were collected from Puruki Experimental Forest (New Zealand) and examined for incremental depth changes in SOC functional groups, or chemical shift regions, using solid-state 13C cross polarisation magic angle spinning nuclear magnetic resonance (13C CPMAS-NMR) spectroscopy. The results showed that soil depth was a driver of change in soil chemical shift regions. The presence of a coarse-textured soil horizon, lapilli layer, at depth was a driver of significant (p < 0.05) differences between SOC functional groups. In the upper soil profile (0–10 cm), the chemical shift distribution was dominated by O-alkyl C (39%) followed by alkyl C (32%), aromatic C (23%), and carboxyl C (6%). In the deep soil layers, we found alkyl C increased below the lapilli layer (varying depth > 50 cm) compared to above the lapilli layer. In the deep soil layers the alkyl C was the dominant functional group (55%), followed by O-alkyl C (28%). Furthermore, there was a decrease at depth in aromatic (12%) and carboxyl C (5%). The A/O-A ratio increased with depth from soil above the lapilli layer compared to soils below the lapilli layer indicating a greater degree of organic matter decomposition and a corresponding decrease in the labile OC fractions. Within the lapilli layer the SOC functional groups and A/O-A ratio were highly variable. These results highlight that changes in SOC chemical composition occur with increasing soil depth, a property of deep soil that is frequently understudied, and are highly influenced by the multi layered nature of soil derived from volcanic airfall deposits.

Carbon-13 chemical shift tensor measurements for nitrogen-dense compounds.

This paper reports the principal values of the 13 C chemical shift tensors for five nitrogen-dense compounds (i.e., cytosine, uracil, imidazole, guanidine hydrochloride, and aminoguanidine hydrochloride). Although these are all fundamentally important compounds, the majority do not have 13 C chemical shift tensors reported in the literature. The chemical shift tensors are obtained from 1 H→13 C cross-polarization magic-angle spinning (CP/MAS) experiments that were conducted at a high field of 18.8T to suppress the effects of 14 N-13 C residual dipolar coupling. Quantum chemical calculations using density functional theory are used to obtain the 13 C magnetic shielding tensors for these compounds. The best agreement with experiment arises from calculations using the hybrid functional PBE0 or the double-hybrid functional PBE0-DH, along with the triple-zeta basis sets TZ2P or pc-3, respectively, and intermolecular effects modeled using large clusters of molecules with electrostatic embedding through the COSMO approach. These measurements are part of an ongoing effort to expand the catalog of accurate 13 C chemical shift tensor measurements, with the aim of creating a database that may be useful for benchmarking the accuracy of quantum chemical calculations, developing nuclear magnetic resonance (NMR) crystallography protocols, or aiding in applications involving machine learning or data mining. This work was conducted at the National High Magnetic Field Laboratory as part of a 2-week school for introducing undergraduate students to practical laboratory experience that will prepare them for scientific careers or postgraduate studies.

BF3‐induced reversible covalent organic framework radicals

AbstractThe integration of radials into covalent organic frameworks (COFs) would have a profound effect on their applications in spin devices since such radical arrays can offer scientists an additional dimension to manipulate electron spins and maximize the function of organic optoelectrical devices. However, such realization (especially reversible radicals) is very challenging. In this article, using a fluorene‐based benzoquinone‐derived monomer (M) as the building unit, we successfully synthesized a boroxine‐linked COF (named CityU‐3), whose crystallinity and chemical composition were confirmed by powder X‐ray diffraction (PXRD), Fourier‐transform infrared (FT‐IR) spectroscopy, solid‐state 13C cross‐polarization magic‐angle‐spinning (CP/MAS) NMR, and X‐ray photoelectron spectroscopy (XPS). Interestingly, CityU‐3 can be converted into its radical form by treating with BF3·Et2O, which is associated with a color change from red to black, and vice versa upon heating. The as‐formed radicals have been confirmed by electron paramagnetic resonance (EPR) spectroscopy. It is worth pointing out that the cycles between radical formation and disappearance would not affect its crystallinity and structure. The reversible COF radicals would have great applications in organic spin devices.

Structural Studies of Mexican Husk Tomato (Physalis ixocarpa) Fruit Cutin.

Green tomato (Physalis ixocarpa) is a specie native to Mexico, and it is known as "tomatillo" or "husk tomato". The fruit contains vitamins, minerals, phenolic compounds, and steroidal lactones, presenting antimicrobial activity and antinarcotic effects. Therefore, it is not only used in traditional Mexican cuisine, but also in traditional medicine to relieve some discomforts such as fever, cough, and amygdalitis. However, it is a perishable fruit whose shelf life is very short. As a part of the peel, cuticle, and epicuticular waxes represent the most important part in plant protection, and the specific composition and structural characterization are significant to know how this protective biopolymer keeps quality characteristics in fresh fruits. P. ixocarpa cutin was obtained by enzymatic treatments (cellulase, hemicellulose, and pectinase) and different concentrations of TFA, and studied through Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (CPMAS 13C NMR), Ultra-High Performance Liquid Chromatography coupled to Mass Spectrometry (UHPLC-MS), and was morphologically characterized by Confocal Laser Scanning Microscopy (CLSM) and Scanning Electron Microscopy (SEM). The main constituents identified under the basis of UHPLC-MS analysis were 9,10,18-trihydroxy-octadecanoic acid and 9,10-epoxy-18-hydroxy-octadecanoic acid with 44.7 and 37.5%, respectively. The C16 absence and low occurrence of phenolic compounds, besides the presence of glandular trichomes, which do not allow a continuous layer on the surface of the fruit, could be related to a lower shelf life compared with other common fruits such as tomato (Solanum lycopersicum).

A facile approach for estimating radio-frequency field strength of low-receptivity nuclei

Radio-frequency (RF) field calibration is essential in NMR spectroscopy. A common practice is to collect a nutation curve by varying the pulse length in a direct single-pulse excitation experiment or in a cross-polarization magic-angle spinning with a flip-back pulse experiment. From the null points on this curve, one can calculate the RF field strength. Nevertheless, the practical implementation is not always straightforward or can even be unrealizable, especially for low-receptivity nuclei owing to their associated low sensitivity. Several researchers used an approach that involves utilizing other nuclei with more sensitivity but nearly identical Larmor frequencies to that of the nucleus of interest. However, such an approach has not been a common practice so far. In this work, we have systematically revisited this approach using 3.2 mm rotors on different sets of nuclei covering a Larmor frequency range up to 80 MHz. The effect of solid- and solution-states on RF field strength measurements has been investigated. The detection of each set of nuclei is then carried out with a resonant circuit in the NMR probe consisting of identical coils and capacitors. Our methodology is illustrated by recording 135/137Ba NMR spectra of BaTiO3 without prior 135/137Ba RF field calibration.

Effects of dual modification by cationization and acetylation on the physicochemical and structural characteristics of glutinous rice starch

In this research, the effects of cationization, acetylation and dual modification by cationization and acetylation on the physicochemical and structural characteristics of glutinous rice starches were investigated. The rapid viscosity analyzer revealed a substantial increased paste viscosity post modification. Particularly, for dually modified starch, the peak viscosity increased from 3071.67 to 4082.00 cP. The freeze-thaw stability substantially enhanced, with both single cationic and dually-modified starches standing out by exhibiting no water syneresis even at 21 freeze-thaw cycles, while native starch exhibited higher syneresis, up to 74.55 %. Both single cationization and cationization-acetylation destroyed the starch granules, characterized by the roughness and cracks. But, for single acetylation, there was no notable changes on granules' morphology. Fourier transform infrared spectroscopy exhibited notable shifts after modification, both acetylation and dual modification, resulting in a new peak at 1728 cm−1. 13C cross-polarization magic angle spinning nuclear magnetic resonance spectra displayed new peaks at 52–55 and 19–22 ppm following cationization and acetylation, respectively. These structural alterations indicate the successful incorporation of functional groups during modification. Overall, this study provides valuable insights for the industrial utilization of these three modified glutinous rice starches.

Reticular Synthesis of Highly Crystalline Three-Dimensional Mesoporous Covalent-Organic Frameworks for Lipase Inclusion.

The synthesis and application of three-dimensional (3D) mesoporous covalent-organic frameworks (COFs) are still to be developed. Herein, two mesoporous 3D COFs with an stp topology were synthesized in a highly crystalline form with aniline as the modulator. The chemical composition of these COFs was confirmed by Fourier transform infrared (FT-IR) and 13C cross-polarization magic angle spinning nuclear magnetic resonance (NMR) spectroscopies. These 3D mesoporous COFs were highly crystalline and exhibited permanent porosity and good chemical stability in both aqueous and organic media. The space group and unit cell parameters of COF HFPTP-TAE were verified by powder X-ray diffraction (PXRD), small-angle X-ray scattering, and three-dimensional electron diffraction (3D ED). The appropriate pore size of the COF HFPTP-TAE facilitated the inclusion of enzyme lipase PS with a loading amount of 0.28 g g-1. The lipase⊂HFPTP-TAE (⊂ refers to "include in") composite exhibited high catalytic activity, good thermal stability, and a wide range of solvent tolerance. Specifically, it could catalyze the alcoholysis of aspirin methyl ester (AME) with high catalytic efficiency. Oriented one-dimensional (1D) channel mesopores in HFPTP-TAE accommodated lipase, meanwhile preventing them from aggregation, while windows on the wall of the 1D channel favored molecular diffusion; thus, this COF-enzyme design outperformed its amorphous isomer, two-dimensional (2D) mesoporous COF, 3D mesoporous COF with limited crystallinity, and mesoporous silica as an enzyme host.

Automation in solid state NMR

Automation in solid state NMR (ssNMR) requires appropriate hardware, from rotor loading mechanisms over highly stable rf-transmitters and probe circuitry to automatic tuning and matching capabilities including automatic magic angle adjustment for ssNMR probes. While these hardware capabilities are highly desirable and are, to various degrees, provided by manufacturers, we focus herein on automating experiment setup using radio frequency (rf) fields, which are key parameters in solid state NMR experiments. Specifically, these include spinlock fields during cross polarization (CP), or rf-fields for homo- or heteronuclear spin recoupling or decoupling. Often, these fields have specific relationships to the magic angle spinning (MAS) frequency. Relying on a well-maintained spectrometer, the experiment setup shifts from traditionally required optimization of rf-power values for each element of an experiment sequence to automatically setting all parameters correctly without any need for optimization. The proposed approach allows executing an experiment by reading its rf-amplitude requirements based on the actual MAS rotation frequency just before starting data acquisition, while all other hardware-related parameters are automatically provided through global tables and scripts. Under modest MAS frequencies, no further rf-power optimization is required while providing optimal sensitivity of better than 90% of the optimal signal to noise. Any optional parameter optimization relates only to adjusting rf-nutation frequencies to the requirements of the sample and the sample rotation frequency rather than the spectrometer hardware. Fast MAS CP experiments with MAS frequencies above 40 kHz require a semi-automated setup by optimizing Hartmann-Hahn (HH) matched rf-fields that are synchronously varied relative to the MAS-frequency. This allows for a significant reduction of setup steps by up to one order of magnitude for such experiments, avoiding the traditional grid search for optimal CPMAS conditions. The approach presented here can also be applied to decoupling or recoupling sequences, requiring rotor synchronized rf-fields, reducing the setup to a few steps addressing the spin system’s properties rather than the spectrometer hardware. Our approach permits automating all basic solid state NMR experiments for high throughput analytical tasks.

A new route of production of the meso-porous chitosan with well-organized honeycomb surface microstructure from shrimp waste without destroying the original structure of native shells: Extraction, modification and characterization study

The highly active bio-polysaccharide based compound namely chitin and chitosan have been extracted from shrimp shell which usually expelled out extensively from food processing industries and considered as waste materials. However, by conducting demineralization, de-proteinization and deacetylation on it which could be a new route of production of valuable meso-porous chitosan that possesses a noteworthy well-organized honeycomb like surface microstructure which undoubtedly capable to form sustainable bio-composites. Whereas the honeycomb like microstructures showed a well-defined pore canals (Pc) and pore canal tubes (Pct) onto their surface. The samples were characterized via ATR-FTIR spectroscopy, High resolution SEM, AFM, EDX, XRD and 13C solid-state Cross-Polarization Magic Angle Spinning (CPMAS) NMR. The molecular weight(M‾v) of isolated chitin and chitosan were determined by viscosity and the values were 1.06 × 106(DPv = 5228), 1.8 × 104(DPv = 116) respectively besides degree of deacetylation (DDA) were measured by ATR-FTIR spectroscopy, CPMAS NMR, pH-metric titration and the values were 24&21 for chitin and 84&82 for chitosan. The results suggest that the shrimp shell waste is an attractive source of well-organized honeycomb like meso-porous chitin and chitosan with regular surface microstructures which might have a significant/potential application into the sustainable bio-composite formulation due to various industrial and biomedical sector indeed.

A Porous Crystalline Nitrone-Linked Covalent Organic Framework.

Herein, we report the synthesis of a nitrone-linked covalent organic framework, COF-115, by combining N, N', N', N'''-(ethene-1, 1, 2, 2-tetrayltetrakis(benzene-4, 1-diyl))tetrakis(hydroxylamine) and terephthaladehyde via a polycondensation reaction. The formation of the nitrone functionality was confirmed by solid-state 13 C multi cross-polarization magic angle spinning NMR spectroscopy of the 13 C-isotope-labeled COF-115 and Fourier-transform infrared spectroscopy. The permanent porosity of COF-115 was evaluated through low-pressure N2 , CO2 , and H2 sorption experiments. Water vapor and carbon dioxide sorption analysis of COF-115 and the isoreticular imine-linked COF indicated a superior potential of N-oxide-based porous materials for atmospheric water harvesting and CO2 capture applications. Density functional theory calculations provided valuable insights into the difference between the adsorption properties of these COFs. Lastly, photoinduced rearrangement of COF-115 to the associated amide-linked material was successfully demonstrated.

NMR spectroscopy-based analysis of gallstones of cancerous and benign gallbladders from different geographical regions of the Indian subcontinent.

Analysis of the chemical composition of gallstones is vital for the etiopathogenesis of gallstone diseases that can ultimately help in the prevention of its formation. In the present study, gallstones from seven different regions of India were analyzed to highlight the major difference in their composition. Also, gallstones of different pathological conditions i.e., benign (chronic cholecystitis, CC) and malignant gallbladder disease (gallbladder cancer GBC) were characterized. The type of polymorphs of cholesterol molecules was also studied to provide insight into the structure of gallstones. 1H solution state NMR spectroscopy 1D experiments were performed on a total of 94 gallstone (GS) samples collected from seven different geographical regions of India. Solid-State NMR spectroscopy 13C cross-polarization magic angle spinning (CPMAS) experiments were done on the 20 CC GS samples and 20 GBC GS samples of two regions. 1H NMR spectra from the solution state NMR of all the stones reveal that cholesterol was a major component of the maximum stones of the north India region while in south Indian regions, GS had very less cholesterol. 13C CPMAS experiments reveal that the quantity of cholesterol was significantly more in the GS of CC in the Lucknow region compared with GBC stones of Lucknow and Chandigarh. Our study also revealed that GS of the Lucknow region of both malignant and benign gallbladder diseases belong to the monohydrate crystalline form of cholesterol while GS of Chandigarh region of both malignant and benign gallbladder diseases exists in both monohydrate crystalline form with the amorphous type and anhydrous form. Gallstones have a complicated and poorly understood etiology. Therefore, it is important to understand the composition of gallstones, which can be found in various forms and clinical conditions. Variations in dietary practices, environmental conditions, and genetic factors may influence and contribute to the formation of GS. Prevention of gallstone formation may help in decreasing the cases of gallbladder cancer.

Molecular composition and possible transformations of labile soil organic matter fractions in Mediterranean arable soils: Relevance and implications

With the increased global interest in sequestering carbon in soil, it is necessary to understand the composition of different pools of soil organic matter (SOM) that cycle over suitably short timeframes. To explore in detail the chemical composition of agroecologically relevant yet distinct fractions of SOM, the light fraction of SOM (LFOM), the 53-μm particulate organic matter (POM), and the mobile humic acid (MHA) fractions were sequentially extracted from agricultural soils and characterized using both 13C cross polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) spectroscopy and also Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The NMR results showed a decrease in the O-alkyl C region assigned to carbohydrates (51–110 ppm) and an increase in the aromatic region (111–161 ppm) proceeding from the LFOM to the POM and then to the MHA fraction. Similarly, based on the thousands of molecular formulae assigned to the peaks detected by FT-ICR-MS, condensed hydrocarbons were dominant only in the MHA, while aliphatic formulae were abundant in the POM and LFOM fractions. The molecular formulae of the LFOM and POM were mainly grouped in the high H/C lipid-like and aliphatic space, whereas a portion of the MHA compounds showed an extremely high (17–33, average of 25) double bond equivalent (DBE) values, corresponding to low H/C values of 0.3–0.6, representative of condensed hydrocarbons. The labile components appeared most pronounced in the POM (93% of formulae have H/C ≥ 1.5) similar to the LFOM (89% of formulae have H/C ≥ 1.5) but in contrast to the MHA (74% of formulae have H/C ≥ 1.5). The presence of both labile and recalcitrant components in the MHA fraction suggests that the stability and persistence of soil organic matter is influenced by a complex interaction of physical, chemical, and biological factors in soil. Understanding the composition and distribution of different SOM fractions can provide valuable insights into the processes that govern carbon cycling in soils, which can help inform strategies for sustainable land management and climate change mitigation.

In Situ Multinuclear Magic-Angle Spinning NMR: Monitoring Crystallization of Molecular Sieve AlPO4-11 in Real Time.

Molecular sieves are crystalline three-dimensional frameworks with well-defined channels and cavities. They have been widely used in industry for many applications such as gas separation/purification, ion exchange, and catalysis. Obviously, understanding the formation mechanisms is fundamentally important. High-resolution solid-state NMR spectroscopy is a powerful method for the study of molecular sieves. However, due to technical challenges, the vast majority of the high-resolution solid-state NMR studies on molecular sieve crystallization are ex situ. In the present work, using a new commercially available NMR rotor that can withhold high pressure and high temperature, we examined the formation of molecular sieve AlPO4-11 under dry gel conversion conditions by in situ multinuclear (1H, 27Al, 31P, and 13C) magic-angle spinning (MAS) solid-state NMR. In situ high-resolution NMR spectra obtained as a function of heating time provide much insights underlying the crystallization mechanism of AlPO4-11. Specifically, in situ 27Al and 31P MAS NMR along with 1H → 31P cross-polarization (CP) MAS NMR were used to monitor the evolution of the local environments of framework Al and P, in situ 1H → 13C CP MAS NMR to follow the behavior of the organic structure directing agent, and in situ 1H MAS NMR to unveil the effect of water content on crystallization kinetics. The in situ MAS NMR results lead to a better understanding of the formation of AlPO4-11.

Design of β-Alanine-Derived Novel C18 Stationary Phase Containing Embedded Urea and Amide Groups for the Separation of Versatile Analytes.

Novel stationary phases have been emerging recently. A β-alanine-derived embedded urea and amide group-containing C18 phase (Sil-Ala-C18) was prepared for the first time. The media were packed into a 150 × 2.1 mm HPLC column, and the newly designed column was evaluated with the Tanaka and Neue test protocols in reversed-phase liquid chromatography (RPLC) separation mode. Moreover, it was characterized by the Tanaka test protocol in hydrophilic interaction chromatography (HILIC) separation mode. The new phase was characterized by elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and solid-state 13C cross-polarization magic angle spinning (CP/MAS) NMR spectroscopy at variable temperatures. The chromatographic evaluation involved very good separation of nonpolar shape-constrained isomers, polar and basic compounds in RPLC, and highly polar compounds in HILIC compared to the commercial reference columns. The Sil-Ala-C18 phase was able to separate the challenging β- and γ-isomers of tocopherol. The phase was also successfully applied for the separation of the isomers of tocopherol (vitamin E) and capsaicinoids from real samples of chili peppers (Capsicum spp.) in RPLC and ascorbic acid (vitamin C) in HILIC.

Tricarbonyl-Pyrazine-Molybdenum(0) Metal-Organic Frameworks for the Storage and Delivery of Biologically Active Carbon Monoxide.

Metal-organic frameworks (MOFs) have high potential as nanoplatforms for the storage and delivery of therapeutic gasotransmitters or gas-releasing molecules. The aim of the present study was to open an investigation into the viability of tricarbonyl-pyrazine-molybdenum(0) MOFs as carbon monoxide-releasing materials (CORMAs). A previous investigation found that the reaction of Mo(CO)6 with excess pyrazine (pyz) in a sealed ampoule gave a mixture comprising a major triclinic phase with pyz-occupied hexagonal channels, formulated as fac-Mo(CO)3(pyz)3/2·1/2pyz (Mo-hex), and a minor dense cubic phase, formulated as fac-Mo(CO)3(pyz)3/2 (Mo-cub). In the present work, an open reflux method in toluene has been optimized for the large-scale synthesis of the pure Mo-cub phase. The crystalline solids Mo-hex and Mo-cub were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), FT-IR and FT-Raman spectroscopies, and 13C{1H} cross-polarization (CP) magic-angle spinning (MAS) NMR spectroscopy. The release of CO from the MOFs was studied by the deoxy-myoglobin (deoxy-Mb)/carbonmonoxy-myoglobin (MbCO) UV-vis assay. Mo-hex and Mo-cub release CO upon contact with a physiological buffer in the dark, delivering 0.35 and 0.22 equiv (based on Mo), respectively, after 24 h, with half-lives of 3-4 h. Both materials display high photostability such that the CO-releasing kinetics is not affected by irradiation of the materials with UV light. These materials are attractive as potential CORMAs due to the slow release of a high CO payload. In the solid-state and under open air, Mo-cub underwent almost complete decarbonylation over a period of 4 days, corresponding to a theoretical CO release of 10 mmol per gram of material.

Potentially Health-Promoting Spaghetti-Type Pastas Based on Doubly Modified Corn Starch: Starch Oxidation via Wet Chemistry Followed by Organocatalytic Butyrylation Using Reactive Extrusion.

Extruded spaghetti-type pasta systems were obtained separately either from native or oxidized starch prepared via wet chemistry with the aim of evaluating the effect of oxidation modification of starch. In addition to this, the butyrylation reaction (butyrate (Bu) esterification-short-chain fatty acid) using native or oxidized starch was analyzed under reactive extrusion (REx) conditions with and without the addition of a green food-grade organocatalyst (l(+)-tartaric acid) with the purpose of developing potentially health-promoting spaghetti-type pasta systems in terms of increasing its resistant starch (RS) values. These would be due to obtaining organocatalytic butyrylated starch or not, or the manufacture of a doubly modified starch (oxidized-butyrylated-starch oxidation followed by organocatalytic butyrylation) or not. To this end, six pasta systems were developed and characterized by solid-state 13C cross-polarization magic angle spinning nuclear magnetic resonance (CP MAS NMR) spectroscopy, degree of substitution (DS), attenuated total reflectance Fourier transform infrared (ATR/FTIR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), pancreatic digestion, free Bu content analysis and in vitro starch digestibility. The results obtained here suggest that starch oxidation hydrolytically degrades starch chains, making them more susceptible to enzymatic degradation by α-amylase. However, the oxidized starch-based pasta systems, once esterified by Bu mainly on the amylose molecules (doubly modified pasta systems) increased their RS values, and this was more pronounced with the addition of the organocatalyst (maximum RS value = ~8%). Interestingly, despite the checked chemical changes that took place on the molecular structure of starch upon butyrylation or oxidation reactions in corn starch-based spaghetti-type pasta systems, and their incidence on starch digestibility, the orthorhombic crystalline structure (A-type starch) of starch remained unchanged.

Synthesis, characterization, and application of starch-based adhesives modified with itaconic acid and N-hydroxyethyl acrylamide

A renewable, biodegradable, formaldehyde-free starch-based adhesive was prepared by grafting itaconic acid (IA) and N-hydroxyethyl acrylamide (HEAA) onto corn starch. The adhesive exhibits excellent performance for particleboard and low viscosity (251 mPas, 62 s measured by flow cup viscometer) using 8% addition of IA (w/w, dry starch basis), and 10% addition of HEAA (w/w, dry starch basis). The thickness swelling of the particleboard was decreased to 10%. When unmodified starch-based adhesive was used, the particleboard soaked in water disintegrated completely. The data obtained from the Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), confocal Raman microscopy (CRM), and 13C cross-polarization magic-angle spinning (CPMAS) showed that IA wrapped and covered the surface of starch granules. HEAA is unevenly distributed on the surface of starch as a cross-linked backbone. After the hot-pressing process, IA and HEAA are self-cross-linked and inter-cross-linked, respectively, to form a complex network structure, which can inhibit the disintegration caused by excessive expansion during the soaking process of the board, thus improving the water resistance of the starch adhesive.