13C Cross-polarization Magic Angle Spinning Research Articles

Investigating discrepancies between experimental solid-state NMR and GIPAW calculation: N[dbnd]C–N 13C and OH⋯O 1H chemical shifts in pyridinium fumarates and their cocrystals

An NMR crystallography analysis is presented for four solid-state structures of pyridine fumarates and their cocrystals, using crystal structures deposited in the Cambridge Crystallographic Data Centre, CCDC. Experimental one-dimensional one-pulse 1H and 13C cross-polarisation (CP) magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and two-dimensional 14N–1H heteronuclear multiple-quantum coherence MAS NMR spectra are compared with gauge-including projector augmented wave (GIPAW) calculations of the 1H and 13C chemical shifts and the 14N shifts that additionally depend on the quadrupolar interaction. Considering the high ppm (>10 ​ppm) 1H resonances, while there is good agreement (within 0.4 ​ppm) between experiment and GIPAW calculation for the hydrogen-bonded NH moieties, the hydrogen-bonded fumaric acid OH resonances are 1.2–1.9 ​ppm higher in GIPAW calculation as compared to experiment. For the cocrystals of a salt and a salt formed by 2-amino-5-methylpyridinium and 2-amino-6-methylpyridinium ions, a large discrepancy of 4.2 and 5.9 ​ppm between experiment and GIPAW calculation is observed for the quaternary ring carbon 13C resonance that is directly bonded to two nitrogens (in the ring and in the amino group). By comparison, there is excellent agreement (within 0.2 ​ppm) for the quaternary ring carbon 13C resonance directly bonded to the ring nitrogen for the salt and cocrystal of a salt formed by 2,6-lutidinium and 2,5-lutidinium, respectively.

Acetylation of bacterial cellulose using N-methyl-imidazole as a catalyst under solvent-free and N,N-dimethylacetamide/lithium chloride solvent systems

Bacterial cellulose acetate (BCA) at a low degree of substitution (DS) was prepared using acetic anhydride in the presence of N-methylimidazole (NMIM) as a catalyst. The acetylated reaction was studied in both solvent-free (heterogeneous) and N,N-dimethylacetamide/lithium chloride (DMAc/LiCl; homogeneous) systems, where the DS ranges of BCA obtained from heterogeneous (BCA-HE) and homogeneous (BCA-HO) systems were recorded as 0.31 to 0.95 and 0.4 to 1.5, respectively. The DS values could be effectively controlled by adjusting the reaction conditions. Compared to the heterogeneous reaction, the homogeneous reaction could be processed under a mild condition within a short time. The BCA-HE and BCA-HO displayed good water solubility at a DS value less than 0.95 and 1.09, respectively. The structural and the characteristic changes were confirmed by scanning electron microscopy, Fourier transform infrared, X-ray diffraction, 13C cross-polarization magic angle spinning nuclear magnetic resonance, and thermogravimetric analyses. The present study may offer a convenient, mild, and green catalyzed-processing to tailor low DS of cellulose acetate.

Dynamic Covalent Synthesis of Crystalline Porous Graphitic Frameworks

Summary Porous graphitic framework (PGF) is a two-dimensional (2D) material that has emerging energy applications. An archetype contains stacked 2D layers, the structure of which features a fully annulated aromatic skeleton with embedded heteroatoms and periodic pores. Due to the lack of a rational approach in establishing in-plane order under mild synthetic conditions, the structural integrity of PGF has remained elusive and ultimately limited its material performance. Here, we report the discovery of the unusual dynamic character of the C=N bonds in the aromatic pyrazine ring system under basic aqueous conditions, which enables the successful synthesis of a crystalline porous nitrogenous graphitic framework with remarkable in-plane order, as evidenced by powder X-ray diffraction studies and direct visualization using high-resolution transmission electron microscopy. The crystalline framework displays superior performance as a cathode material for lithium-ion batteries, outperforming the amorphous counterparts in terms of capacity and cycle stability.

Synthesis of anionic ionic liquids@TpBd-(SO3)2 for the selective adsorption of cationic dyes with superior capacity.

The discharge of industrial printing and dyeing wastewater is one of the main reasons for the increasing water shortage and deterioration. The treatment of dyestuff wastewater is an issue and needs to be urgently solved. In this work, anionic ionic liquid functional covalent organic materials (COMs) were firstly synthesized and used for the selective adsorption of cationic dyes. First, a series of sulfonic acid group (SO3H)-functionalized anionic TpPa-SO3, TpBd-(SO3)2, and TpCR-(SO3)2 were prepared, respectively, and then imidazole was grafted onto TpBd-(SO3)2 to obtain ImI@TpBd-(SO3)2. The full characterization using X-ray diffraction, FT-IR spectroscopy, 13C cross-polarization magic-angle spinning NMR spectroscopy, zeta-potentials, BET surface and pore analysis indicated that these COMs and ImI@TpBd-(SO3)2 exhibited different morphologies, porosities, and potentials. The effects of the type of dye, adsorption time, initial dye concentration, and pH on the adsorption of dyes on ImI@TpBd-(SO3)2 were systematically investigated, respectively. The results revealed that ImI@TpBd-(SO3)2 possessed good adsorption performance for nine different cationic dyes with adsorption capacities in the range from 2865.3 mg g−1 for methylene blue (MB) to 597.9 mg g−1 for basic orange 2 (BO), but little adsorption for anionic and neutral dyes, revealing charge selectivity. The adsorption ratio of ImI@TpBd-(SO3)2 for MB was as high as 74.0% at 10 min by using 1.0 mg material, owing to the post modification of TpBd-(SO3)2 with imidazole. The adsorption of MB on ImI@TpBd-(SO3)2 was pH dependent. The adsorption isotherm and kinetics fitted well with the Freundlich and pseudo second-order kinetic model, respectively. Finally, the very outstanding advantages of superior selective adsorption, desorption, convenient preparation, and low density of ImI@TpBd-(SO3)2 predicted its research and application potential in dye wastewater recovery.

CP MAS kinetics in soft matter: Spin diffusion, local disorder and thermal equilibration in poly(2-hydroxyethyl methacrylate)

The 1H–13C cross-polarization magic angle spinning kinetics was studied in poly(2-hydroxyethyl methacrylate) (pHEMA), i.e. a soft material with high degrees of internal freedom and molecular disorder, having the purpose to track the influence of increasing local incoherent contributions to the effects of coherent nature in the open quantum spin systems. The experimental CP MAS kinetic curves were analyzed in the frame of the models of isotropic and anisotropic spin diffusion with thermal equilibration. The rates of spin diffusion and spin-lattice relaxation as well as the profiles of distribution of dipolar coupling, the parameters accounting the effective size of spin clusters and the local order parameters were determined. The intensities of the peaks of periodic quasi-equilibrium origin gradually decrease with increasing disorder, i.e. going from most ordered to more disordered sites in the polymer. Assuming that the thermal motion induced by the temperature gradients is much faster than the equilibration driven by spin diffusion due the difference in spin temperatures, it was deduced that the thermal equilibration in pHEMA occurs in the time scale of 10−4 s. This is one order of magnitude faster than the spectral spin diffusion, which occurs between spins having different resonance frequencies. The thermal equilibration in the case of remote spin clusters was described by the ‘stretched exponent’ decay. This led to the fractal dimension Dp ≈ 1.65 for both carbon sites (quaternary and carbonyl). The obtained Dp value corresponds to the aggregates, which images are very similar to those for pHEMA and some other related polymer structures are usually conceived.

Suppression of glycogen synthase expression reduces glycogen and lipid storage during mosquito overwintering diapause

During diapause in mosquitoes, efficient storage and utilization of energy are crucial for surviving prolonged periods of developmental arrest and for maximizing reproductive success once diapause is terminated and development recommences. In Culex pipiens, glycogen rapidly accumulates during early diapause (7–10 days after adult eclosion) and it is used to maintain energy homeostasis during the first month of diapause. In this study, a gene encoding glycogen synthase, which converts glucose residues into a polymeric chain for storage as glycogen, was characterized. After dsi-RNA directed against glycogen synthase was injected into mosquitoes programmed for diapause (reared under short day lengths), Cx. pipiens were fed 1% d-[13C6]glucose, and the knockdown effects after 7-days were monitored by measuring 13C-labeled carbohydrate accumulation using solid-state NMR. The use of 13C cross-polarization magic-angle spinning spectrum showed a 46% reduction of 13C-labeled glycogen and a 6% reduction in lipid accumulation in glycogen synthase knockdown adult females. In addition, the suppression of glycogen synthase dramatically increased the mortality rate of diapausing Cx. pipiens by 88% at 30-days post injection. These findings indicated that glycogen synthase plays a critical role in regulating glycogen and lipid storages during overwintering diapause, and its function is essential for successful overwintering and survival of Cx. pipiens.

CP MAS kinetics and impedance spectroscopy studies of local disorder in low-dimensional H-bonded proton-conducting materials

The 1H–13C cross-polarization magic angle spinning (CP MAS) kinetics was studied in poly(vinyl phosphonic acid) (pVPA), i.e. material with high degrees of freedom of proton motion along H-bonded chains. It has been shown that the CP kinetic data for the adjacent 1H–13C spin pairs can be described in the frame of the isotropic spin-diffusion approach. The rates of spin diffusion and spin-lattice relaxation as well as the parameters accounting for spin coupling and the effective size of spin clusters have been determined. The local order parameter S ≈ 0.63±0.02, determined as the ratio of the measured dipolar 1H–13C coupling constant and the calculated static dipolar coupling constant, is significantly lower than the values deduced for related sites in other polymers and in series of amino acids. This means that the local disorder of the C–H bonds in pVPA is between those for rather rigid C–H bond configurations having S = 0.8–1.0 and highly disordered –CH3 groups (S ~ 0.4). This effect can be attributed to the presence of the proton transfer path where proton motion is easy to activate. The activation energy for the proton motion Ea = 59±7 kJ/mol was determined from the impedance spectroscopy data analysing the temperature and frequency dependences of the complex dielectric permittivity of pVPA. The rates of proton spin-lattice relaxation and spin diffusion are of the same order and both run in the time scale of milliseconds.

Application of Comprehensive Multiphase NMR To Characterize Organic Matter in Clay and Atmospheric Particulates

The molecular composition of organic matter (OM) and its interaction with minerals play important roles in regulating the fate of carbon and pollutants in soil and in the atmosphere. Clay minerals such as montmorillonite processed with bacteria can imitate the microbial interactions occurring in more complex natural environmental media such as soil and atmospheric particulates. Here, we characterize OMs in multiple phases for bacteria-inoculated montmorillonite clay and atmospheric particulates collected in China. In addition to the traditional 13C cross-polarization magic angle spinning nuclear magnetic resonance (CPMAS NMR) experiments, this study, for the first time, applies both one- and two-dimensional comprehensive multiphase (CMP) NMR to these critical environmental issues. The CMP NMR experimental spectra show that the main OM components in these samples are aliphatics, carbohydrates, and aromatics. These CMP NMR spectra also reveal the biochemical interactions between microbes and clay minerals by identifying the metabolites. CMP NMR can further investigate the states, interfacial/surficial interactions, and dynamics at the molecular/atomic levels since diffusion/relaxation (T2)-edited experiments can distinguish OM with differing sizes and mobilities. Therefore, the mechanism at the atomic/molecular level for environmental biogeochemical interactions can be efficiently probed by CMP NMR experiments. This paper concludes that CMP NMR is a powerful and innovative tool for crucial environmental studies at the molecular/atomic scale, providing not only the composition, phase, and structural identifications but also the interfacial/surficial interaction dynamics involved in environmental geochemical processes.

Carbon compositional analysis of hydrogel contact lenses by solid-state NMR spectroscopy

Contact lenses are worn by over 140 million people each year and tremendous research and development efforts contribute to the identification and selection of hydrogel components and production protocols to yield lenses optimized for chemical and physiological properties, eye health and comfort. The final molecular composition and extent of incorporation of different components in contact lenses is routinely estimated after lens production through the analysis of the soluble components that were not included in the lens, i.e. remaining starting materials. Examination of composition in the actual intact materials is always valued and can reveal details that are missed by only examining the non-incorporated components, for example identifying chemical changes to components in lenses during the production process. Solid-state nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for the direct compositional analysis of insoluble and heterogeneous materials and is also uniquely suited to determining parameters of architecture in contact lenses. We utilized 13C cross-polarization magic angle spinning (CPMAS) NMR to examine and compare the carbon composition of soft contact lenses. 13C NMR spectra of individual polymer components enabled the determination of the approximate molecular carbon contributions of major lens components. Comparisons of the conventional etafilcon A hydrogel (1 Day Acuvue MOIST) lenses and silicone hydrogel lenses (Acuvue Oasys, Dailies Total 1, Clariti 1 Day, Biofinity, and Pure Vision) revealed major spectral differences, with considerable variation even among different silicone hydrogel lenses. The solid-state NMR approach provides a direct spectral reporting of carbon types in the hydrogel lens itself. This approach represents a valuable complementary analysis to benefit contact lens research and development and could be extended to isotopically labeled hydrogel lenses to map proximities and architecture between hydrogel components.

Molecular characterization of particulate organic matter in full scale anaerobic digesters: An NMR spectroscopy study

This study assesses the molecular characteristics of particulate organic matter (POM) in agricultural and food waste digesters and elucidates the molecular properties of the recalcitrant POM fraction, which remains in the digestate after AD process. Molecular properties of POM in influent (substrate) and effluent (digestate) of seven full-scale AD plants (three agricultural waste and four food waste digesters) were characterized and compared using solid-state 13C cross-polarization magic angle spinning (CP-MAS) and solution-state 1H,13C heteronuclear single-quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectroscopy. Comparison of the POM structural compositions of substrate and digestate from each AD plant revealed an enrichment of protein structures relative to the carbohydrates in most cases, implying a preferential degradation of the carbohydrates over proteins and/or increase of microbial biomass upon AD of agricultural and food wastes. Distinctive molecular structures of labile and recalcitrant fractions of POM, subjected to AD, were identified by comparing the NMR spectra of all substrate and digestate POM. Accordingly, the labile POM fraction in food and agricultural solid wastes is characterized by structural entities of lipids and starch-like carbohydrates, whereas recalcitrant POM structures resemble alkyl and aromatic subunits of amino acids, lignin, and polysaccharides with β-glycosidic linkages. This information serves as a basis to further explore optimization approaches for improving AD of the underutilized POM and the fate of organic matter in digestate-amended arable lands.

A comprehensive and comparative study of the internal structure and dynamics of natural [formula omitted]keratin and regenerated[formula omitted]keratin by solid state NMR spectroscopy

Structure and dynamics of natural and regenerated chicken feather β-keratin were investigated by 13C cross-polarization (CP) magic angle spinning (MAS) solid state nuclear magnetic resonance (SSNMR) spectral analysis, 13C and 1H spin-lattice relaxation time measurements, and 13C two dimensional phase adjusted spinning sidebands (2DPASS) MAS SSNMR measurements. Chemical shift anisotropy (CSA) parameters of both natural and regenerated chicken feather β-keratin were extracted by using 2DPASS MAS SSNMR experiment. The beauty of 2DPASS MAS SSNMR experiment is it can correlate the isotropic and anisotropic dimension with the help of shearing transformation and two dimensional Fourier Transformation. Molecular correlation time at each and every magnetically inequivalent carbon site of both natural and regenerated chicken feather β-keratin were also determined. The change in molecular dynamics of structural protein after pretreatment was monitored by 2DPASS MAS SSNMR and 13C relaxation measurement. This type of comprehensive study will provide the information about the interrelation between the structure and dynamics of structural protein and will also shed light in the way of developing methods for conversion of animal by-products to novel product.

Solid-state 1H and 13C NMR of corn starch plasticized with glycerol and urea

1H and 13C NMR spectroscopy was used for the study of corn starch plasticized with urea and/or glycerol. The information on the interactions between plasticizers and starch macromolecules as well as the arrangement of starch macromolecules depending on the storage time (from 1 day to 52 weeks), were obtained from the broad-line and magic-angle spinning 1H NMR spectra measured at 22 °C and within the range from 30 to 140 °C and the cross-polarization magic-angle spinning (CP MAS) 13C NMR spectra measured at 30 °C. The 1H chemical shifts for the groups of the plasticizer molecules enabled characterization of the interactions between urea and glycerol molecules in starch plasticized with a mixture of urea and glycerol. With increasing temperature, the signal related to water molecules gradually vanished due to water evaporation, and resolved 1H peaks associated with starch macromolecules were detected above 100 °C. The free water amount in the thermoplastic starch samples was also estimated using MAS 1H NMR spectra. Formation of double helices due to sample ageing was observed through the CP MAS 13C NMR spectra.

Porous Crystalline Olefin-Linked Covalent Organic Frameworks.

The first unsubstituted olefin-linked covalent organic framework, termed COF-701, was made by linking 2,4,6-trimethyl-1,3,5-triazine (TMT) and 4,4'-biphenyldicarbaldehyde (BPDA) through Aldol condensation. Formation of the unsubstituted olefin (-CH═CH-) linkage upon reticulation is confirmed by Fourier transform infrared (FT-IR) spectroscopy and solid-state 13C cross-polarization magic angle spinning (CP-MAS) NMR spectroscopy of the framework and of its 13C-isotope-labeled analogue. COF-701 is found to be porous (1715 m2 g-1) and to retain its composition and crystallinity under both strongly acidic and basic conditions. The high chemical robustness is attributed to the unsubstituted olefin linkages. Immobilization of the strong Lewis acid BF3·OEt2 in the pores of the structure yields BF3⊂COF-701. In the material, the catalytic activity of the guest is retained, as evidenced in a benchmark Diels-Alder reaction.

Integrated analysis of modified Japanese cypress using solid-state NMR spectra and nuclear magnetic relaxation times

Acetylation and resin impregnation of Japanese cypress and subsequent heating of these modified cypresses were examined using an integrated analysis of solid-state NMR spectra and relaxation times. The 1H magic angle spinning NMR showed altered moisture balance after chemical and thermal modifications because of changed hydrophobicity. The 13C cross-polarization/magic angle spinning (CP-MAS) NMR spectra showed that acetylation predominately occurred for carbohydrates while phenol formaldehyde (PF) and melamine formaldehyde (MF) resins permeated all biomass constituents in cypress samples. Spin–lattice relaxation times in the laboratory frame, T1H and T1C, increased with chemical modifications although T1C decreased with the curing of both resins. In contrast, 1H spin–lattice relaxation in the rotation frame, T1ρH, increased with the curing as well as acetylation. The tendencies of relaxation times with curing suggested that faster molecular motions were suppressed in the MHz frequency range, and slower molecular motions were enhanced in the kHz frequency range, which generally matched with the signal changes in the 13C pulse saturation transfer/magic angle spinning NMR spectra. Scanning electron microscope observation showed different adhesion distribution between PF and MF resins, affecting the cellulose signals of 13C CP-MAS NMR and T1H change due to the curing.

121/123Sb Nuclear Quadrupole Resonance Spectroscopy: Characterization of Non-Covalent Pnictogen Bonds and NQR Crystallography.

Pnictogen (or pnicogen) bonding is an attractive interaction between the electrophilic region of group 15 elements (N, P, As, Sb, Bi) and a nucleophile. This interaction for which unique applications in catalysis have recently been uncovered continues to gain popularity. Here, we investigate a series of pnictogen-bonded cocrystals based on SbF3 and SbCl3, prepared via mechanochemical ball milling, with 121/123Sb ( I = 5/2 and 7/2, respectively) nuclear quadrupole resonance (NQR) spectroscopy. Observed NQR frequency shifts upon cocrystallization are on the order of 0.1 to 10 MHz and are clearly diagnostic of the formation of pnictogen bonds to antimony. Further evidence for pnictogen bonding is obtained by complementary 13C cross-polarization magic-angle spinning solid-state NMR experiments. DFT calculations of NMR parameters as well as natural localized molecular orbital analyses support the experimental findings and elucidate the electronic origins of the experimental NQR frequency shifts. This work provides insights into the changes in the antimony quadrupolar coupling constant upon pnictogen bonding: strikingly, the decreases noted here parallel those known for hydrogen bonds, but contrast with the increases reported for halogen bonds. The utility of the observed antimony nuclear quadrupolar coupling constants in constraining structural models of cocrystals for which diffraction-based structures are unavailable, i.e., a rudimentary implementation of NQR crystallography, is established. Overall, this work offers a new approach to understand emerging classes of electrophilic interactions and to contextualize them in the broader landscape of established chemical bonding paradigms.

Methoxy-Group Control of Helical Pitch in Stereoregular Poly(2-ethynylmethoxynaphthalene) Prepared by Rhodium Complex Catalyst.

The position of the methoxy group in a poly(n-methoxy-2-ethynylnaphthalene) (PnMeO2EN) was found to control the helical pitch of the π-conjugated polymer in the solid state. These PnMeO2ENs were stereoregularly synthesized using an Rh-complex catalyst in ethanol or toluene as the solvent. The helical structure in the solid phase was confirmed by conventional analytical methods, namely diffuse reflective ultraviolet–visible light (UV–Vis) and Raman spectroscopies, X-ray diffraction, and 13C cross-polarization magic angle spinning NMR spectroscopy, together with molecular mechanics calculations, because the as obtained polymers were insoluble in common solvents. The color of poly(6-methoxy-2-ethynylnaphthalene) (P6MeO2EN) (yellow or red) depended on the polymerization solvent, whereas no such dependency was observed for the yellow-colored P7MeO2EN and P8MeO2EN. The helical structures energetically optimized by molecular mechanics indicate that the red- and yellow-colored P6MeO2ENs form contracted and stretched helices, respectively. Due to the relatively unconstrained rotations of the 6-methoxynaphthyl moieties, the methoxy groups in P6MeO2EN are less sterically hindered along the helical axis. On the contrary, P7MeO2EN and P8MeO2EN have stretched helices due to the considerable steric hindrance imparted by their methoxy groups. The thermal cis-to-trans isomerization of P6MeO2EN in the contracted-helix form required a somewhat higher temperature than that of the stretched helix.

Synthesis, structure and NMR study of fluorinated isoxazoles derived from hemi-curcuminoids

The purpose of this work is to prepare a series of isoxazoles bearing phenyl and 4'-hydroxy-styryl substituents at position 3 and 5; besides the phenyl group of the styryl residue bears one or two fluorine substituents. They were prepared to study their structure in the solid state and in solution by X-ray crystallography and solid-state NMR (SSNMR) for the solid state and NMR for the solution. The reaction of hydroxylamine with hemi-curcuminoid β-diketones affords two isomeric isoxazoles we have named series a (3-phenyl) and b (5-phenyl) that have been identified and characterized. Four pairs have been prepared that in three cases bear one or two fluorine atoms. Three X-ray structures have been determined 3a, 3b and 5b; 3a crystallizes without solvent, 3b crystallizes with a water molecule hydrogen-bonded to a phenolic OH, finally 5b crystallizes as a solvate with a methanol molecule hydrogen-bonded to the isoxazole N atom. This hydrogen bond results in larger differences between 15N chemical shifts in DMSO-d6 solution and in the solid state. The splitting of some signals observed in Cross-Polarization Magic Angle Spinning (CPMAS) 13C NMR was assigned to 1JCF dipolar couplings. The combined use of crystallography and SSNMR affords a complete characterization of isomeric isoxazoles, in particular the assignment of an isoxazole to a or to b series is not a trivial matter. In this work, we describe methods for the synthesis of isoxazoles bearing fluorine substituents that are promising structures for drug discovery.

Efficacious Electrochemical Oxygen Evolution from a Novel Co(II) Porphyrin/Pyrene-Based Conjugated Microporous Polymer.

Oxygen evolution reaction (OER) is energetically challenging from the platform of making many photovoltaic devices such as metal-air batteries and water splitting systems because of its poor kinetics even when precious metals are used. Herein, a Co(II)-porphyrin/pyrene-comprised conjugated microporous polymer Co-MPPy-1 has been developed which shows efficient OER in alkaline medium. The material was characterized by Fourier transform infrared, solid-state 13C cross-polarization magic angle spinning nuclear magnetic resonance, N2 volumetric adsorption/desorption analysis, scanning electron microscopy, ultra high resolution-transmission electron microscopy, X-ray photoelectron spectroscopy, and other physical studies. Co-MPPy-1 showed Brunauer-Emmett-Teller surface area of ∼501 m2 g-1. Co-MPPy-1 achieved a current density of 1 and 10 mA/cm-2 at 340 and 420 mV, respectively. The turnover frequency calculated for the OER is 0.43 s-1. The heterogeneity of this electrocatalyst was tested by chronoamperometric measurement and 1000 cycle recyclability test with retainment of the excellent electrochemical catalytic activity. This can be attributed to the presence of high density of Co(II) porphyrin unit and efficient charge transport in the π-conductive conjugated polymeric backbone.

Insight into Deactivation Behavior and Determination of Generation Time of the Hydroxyapatite Catalyst in the Dehydration of Lactic Acid to Acrylic Acid

For the purpose of industrial applications, deactivation behavior of the hydroxyapatite catalyst was studied in the dehydration of lactic acid to acrylic acid. The hydroxyapatite catalyst shows stable acrylic acid selectivity with 140 h on stream. Obvious increases in acetaldehyde and lactide selectivities were observed from 140 to 250 h, which resulted in a decrease of sharp acrylic acid selectivity. The fresh and used hydroxyapatite catalysts were further characterized by techniques including N2 adsorption–desorption, X-ray diffraction, transmission electron microscopy, 13C cross-polarization magic-angle spinning nuclear magnetic resonance, thermal gravity analysis, and temperature-programmed desorption of CO2 and NH3. These results indicate that the mechanism of coke deactivation consists of two steps. One is the formation of aliphatic carbon by the deposition of low carbon products with 140 h; the other is the formation of aromatic coke by the condensation of lactide. Also, the best generated time of 140 h was determined.

Pristine and Carboxyl-Functionalized Tetraphenylethylene-Based Ladder Networks for Gas Separation and Volatile Organic Vapor Adsorption.

A novel tetraphenylethylene-based ladder network (MP1) made by polycondensation reaction from 4,4′,4″,4‴-(ethene-1,1,2,2-tetrayl)tetrakis(benzene-1,2-diol) and 2,3,5,6-tetrafluoroterephthalonitrile and its COOH-functionalized analogue (MP2) were synthesized for the first time. Their structures were confirmed by solid-state nuclear magnetic resonance (13C cross-polarization magic angle spinning), Fourier transform infrared spectroscopy, and elementary analysis. MP1 exhibited a high Brunauer–Emmett–Teller surface area (1020 m2 g–1), whereas the COOH-functionalized MP2 showed a much smaller surface area (150 m2 g–1) but displayed a more uniform pore size distribution. Because of the high density of nitrile groups in the network polymers of intrinsic microporosity (PIMs) and strong interaction with quadrupole CO2 molecules, MP1 exhibited a high CO2 adsorption capacity of 4.2 mmol g–1 at 273 K, combined with an isosteric heat of adsorption (Qst) of 29.6 kJ mol–1. The COOH-functionalized MP2 showed higher Qst of 34.2 kJ mol–1 coupled with a modest CO2 adsorption capacity of 2.2 mmol g–1. Both network PIMs displayed high theoretical ideal adsorbed solution theory CO2/N2 selectivities (51 and 94 at 273 K vs 34 and 84 at 298 K for MP1 and MP2, respectively). The high selectivities of MP1 and MP2 were confirmed by experimental column breakthrough experiments with CO2/N2 selectivity values of 23 and 45, respectively. Besides the promising CO2 capture and CO2/N2 selectivity properties, MP1 also demonstrated high sorption capacity for toxic volatile organic vapors. At 298 K and a relative pressure of 0.95, benzene and toluene sorption uptakes reached 765 and 1041 mg g–1, respectively. Moreover, MP1 also demonstrated some potential for adsorptive separation of xylene isomers with adsorptive selectivity of 1.75 for m-xylene/o-xylene.