Sustainable Fertilizers: Publication Landscape on Wastes as Nutrient Sources, Wastewater Treatment Processes for Nutrient Recovery, Biorefineries, and Green Ammonia Synthesis.

The ability of modern agriculture to meet future food demand imposed by accelerating growth of the world's population is a major challenge, and fertilizers play a key role by replacing nutrients in agricultural soil. Given the need for fertilizers, their cost in nonrenewable resources and energy, and the consequences of the greenhouse gas emissions required to make them, people have begun to explore ways to make fertilizer manufacturing and use more sustainable. Using data from the CAS Content Collection, this review examines and analyzes the academic and patent literature on sustainable fertilizers from 2001 to 2021. The breakdown of journal and patent literature publication over time on this topic, country or region of publications, the substances included in published research, among other things allow us to understand the general progress in the field as well as the classes of materials and concepts driving innovation. We hope that this bibliometric analysis and literary review will assist researchers in relevant industries to discover and implement ways to supplement conventional fertilizers and nutrient sources while improving the efficiency and sustainability of waste management and ammonia production.

Materials Research Directions Toward a Green Hydrogen Economy: A Review.

A constellation of technologies has been researched with an eye toward enabling a hydrogen economy. Within the research fields of hydrogen production, storage, and utilization in fuel cells, various classes of materials have been developed that target higher efficiencies and utility. This Review examines recent progress in these research fields from the years 2011-2021, exploring the most commonly occurring concepts and the materials directions important to each field. Particular attention has been given to catalyst materials that enable the green production of hydrogen from water, chemical and physical storage systems, and materials used in technical capacities within fuel cells. The quantification of publication and materials trends provides a picture of the current state of development within each node of the hydrogen economy.

CIDNP and EPR study of phototransformation of lappaconitine derivatives in solution.

Chemically induced dynamic nuclear polarization (CIDNP) and electron paramagnetic resonance (EPR) techniques have been used to study the paramagnetic species formed during the photolysis of the alkaloid lappaconitine and its synthetic analogues in solution. Lappaconitine is a photosensitive antiarrhythmic and hypertension drug, whose major photoproduct (N-acetyl anthranilic acid) is also a potent photosensitizer. Both these compounds are lipophilic and might bind efficiently to cell membranes thereby causing phototoxic damage. Photolysis of natural lappaconitine (I) as well as its N(20) des-ethyl derivatives (N-Bz (II), N-Me (III), N-H (IV), and N(O)-Et (V)) results in cleavage of the ester bond with the formation of N-acetyl anthranilic acid (VIII) and corresponding enamine. The lappaconitine derivative V shows maximum photostability which correlates with reference data about its low toxicity. It was shown that the primary reaction step is electron transfer from the amino group to the anthranilic fragment of lappaconitine resulting in an intermediate biradical. The final products are formed via fragmentation of the neutral lappaconitine radicals.

Enhancement of the photocatalytic activity of TiO2 nanoparticles by water-soluble complexes of carotenoids.

Photoirradiation of TiO(2) nanoparticles by visible light in the presence of the water-soluble natural polysaccharide arabinogalactan complexes of the hydrocarbon carotenoid ß-carotene leads to enhanced yield of the reactive hydroxyl (OH) radicals. The electron paramagnetic resonance (EPR) spin-trapping technique using α-phenyl-N-tert-butyl nitrone (PBN) as the spin-trap has been applied to detect this intermediate by trapping the methyl and methoxy radicals generated upon reaction of the hydroxyl radical with dimethylsulfoxide (DMSO). The free radicals formed in this system proceed via oxygen reduction and not via the reaction of holes on the TiO(2) surface. As compared with pure carotenoids, carotenoid-arabinogalactan complexes exhibit an enhanced quantum yield of free radicals and stability toward photodegradation. The observed enhancement of the photocatalytic efficiency for carotenoid complexes, as measured by the quantum yield of the desired spin adducts, arises specifically from the decrease in the rate constant for the back electron transfer to the carotenoid radical cation. These results are important for a variety of TiO(2) applications, namely, in photodynamic therapy, and in the design of artificial light-harvesting, photoredox, and catalytic devices.

Measuring Ti(III)-carotenoid radical interspin distances in TiMCM-41 by pulsed EPR relaxation enhancement method.

Interspin distances between the Ti(3+) ions and the carotenoid radicals produced inside TiMCM-41 pores by photoinduced electron transfer from 7'-apo-7'-(4-carboxyphenyl)-beta-carotene (coordinated to Ti(3+)), canthaxanthin (formed as a random distribution of isomers), and beta-ionone (model for a short-chain polyene) to Ti(3+) framework sites were determined using the pulsed EPR relaxation enhancement method. To estimate the electron transfer distances, the temperature dependence of relaxation rates was analyzed in both siliceous and metal-substituted siliceous materials. The phase memory times, T(M), of the carotenoid radicals were determined from the best fits of two-pulse ESEEM curves. The spin-lattice relaxation times, T(1), of the Ti(3+) ion were obtained from the inversion recovery experiment with echo detection on a logarithmic time scale in the temperature range of 10-150 K. The relaxation enhancement for the carotenoid radicals in TiMCM-41 as compared to that in MCM-41 is consistent with an interaction between the radical and the fast relaxing Ti(3+) ion. For canthaxanthin and beta-ionone, a dramatic effect on the carotenoid relaxation rate, 1/T(M), occurs at 125 and 40 K, respectively, whereas for carboxy-beta-carotene 1/T(M) increases monotonically with increasing temperature. The interspin distances for canthaxanthin and beta-ionone were estimated from the 1/T(M) - 1/T(M0) difference, which corresponds to the Ti(3+) contribution at the temperature where the maximum enhancement in the relaxation rate occurs. Determination of the interspin distances is based on calculations of the dipolar interaction, taking into consideration the unpaired spin density distribution along the 20-carbon polyene chain, which makes it possible to obtain a fit over a wider temperature interval. A distribution of the interspin distances between the carotenoid radical and the Ti(3+) ion was obtained with the best fit at approximately 10 A for canthaxanthin and beta-ionone and approximately 9 A for 7'-apo-7'-(4-carboxyphenyl)-beta-carotene with an estimated error of +/-3 A. The interspin distances do not depend on 1/T(M) - 1/T(M0) for carboxy-beta-carotene which shows no prominent peak in the relaxation rate over the temperature range measured.

Mass spectrometric and spectroscopic studies of the nutritional supplement chromium(III) nicotinate.

Despite chromium nicotinate's popular use as a chromium nutritional supplement, the structure and composition of chromium nicotinate have only been poorly described. As solid chromium nicotinate is intractable, being insoluble or unstable in common solvents, studies on the solid have been limited, and studies of the solution from which the "compound" precipitates have additionally provided little additional data. The results of mass spectrometric and spectroscopic investigations designed to further elucidate the structure and composition of chromium nicotinate are described. The results demonstrated that the three common methods for producing "chromium nicotinate" all yield different compounds, all of which are polymers of Cr(III), oxygen-bound nicotinate, hydroxide, and water. Implications for interpreting results of nutritional studies of "chromium nicotinate" are discussed.

Water soluble complexes of carotenoids with arabinogalactan.

We present the first example of water soluble complexes of carotenoids. The stability and reactivity of carotenoids in the complexes with natural polysaccharide arabinogalactan were investigated by different physicochemical techniques: optical absorption, HPLC, and pulsed EPR spectroscopy. Compared to pure carotenoids, polysaccharide complexes of carotenoids showed enhanced photostability by a factor of 10 in water solutions. A significant decrease by a factor of 20 in the reactivity toward metal ions (Fe(3+)) and reactive oxygen species in solution was detected. On the other hand, the yield and stability of carotenoid radical cations photoproduced on titanium dioxide (TiO(2)) were greatly increased. EPR measurements demonstrated efficient charge separation on complex-modified TiO(2) nanoparticles (7 nm). Canthaxanthin radical cations are stable for approximately 10 days at room temperature in this system. The results are important for a variety of carotenoid applications, in the design of artificial light-harvesting, photoredox, and catalytic devices.

Pulsed electron nuclear double resonance studies of carotenoid oxidation in Cu(II)-substituted MCM-41 molecular sieves.

Carotenoid (Car) radical intermediates formed upon catalytic or photooxidation of lutein (I), 7'-apo-7',7'-dicyano-beta-carotene (II), and lycopene (III) inside Cu(II)-MCM-41 molecular sieves were studied by pulsed electron nuclear double resonance (ENDOR) spectroscopies. The Davies and Mims ENDOR spectra (15-20 K) were simulated using the hyperfine coupling constants predicted by density functional theory (DFT) calculations. The DFT calculations revealed that upon chemical oxidation, carotenoid radical cations (Car*+) are formed, whereas carotenoid neutral radicals (#Car*) are produced by proton loss (indicated by #) from the radical cation. This loss is to first order independent of polarity or hydrogen bonding for carotenoids I, II, or III inside Cu(II)-MCM-41 molecular sieves.

Pulsed EPR and DFT characterization of radicals produced by photo-oxidation of zeaxanthin and violaxanthin on silica-alumina.

Pulsed electron nuclear double resonance (ENDOR) and two-dimensional (2D)-hyperfine sublevel correlation spectroscopy (HYSCORE) studies in combination with density functional theory (DFT) calculations revealed that photo-oxidation of natural zeaxanthin (ex Lycium halimifolium) and violaxanthin (ex Viola tricolor) on silica-alumina produces the carotenoid radical cations (Car*+) and also the neutral carotenoid radicals (#Car*) as a result of proton loss (indicated by #) from the C4(4') methylene position or one of the methyl groups at position C5(5'), C9(9'), or C13(13'), except for violaxanthin where the epoxide at positions C5(5')-C6(6') raises the energy barrier for proton loss, and the neutral radicals #Car*(4) and #Car*(5) are not observed. DFT calculations predict the largest isotropic beta-methyl proton hyperfine couplings to be 8 to 10 MHz for Car*+, in agreement with previously reported hyperfine couplings for carotenoid pi-conjugated radicals with unpaired spin density delocalized over the whole molecule. Anisotropic alpha-proton hyperfine coupling tensors determined from the HYSCORE analysis were assigned on the basis of DFT calculations with the B3LYP exchange-correlation functional and found to arise not only from the carotenoid radical cation but also from carotenoid neutral radicals, in agreement with the analysis of the pulsed ENDOR data. The formation of the neutral radical of zeaxanthin should provide another effective nonphotochemical quencher of the excited state of chlorophyll for photoprotection in the presence of excess light.

Ligand redox effects in the synthesis, electronic structure, and reactivity of an alkyl-alkyl cross-coupling catalyst.

The ability of the terpyridine ligand to stabilize alkyl complexes of nickel has been central in obtaining a fundamental understanding of the key processes involved in alkyl-alkyl cross-coupling reactions. Here, mechanistic studies using isotopically labeled (TMEDA)NiMe(2) (TMEDA = N,N,N',N'-tetramethylethylenediamine) have shown that an important catalyst in alkyl-alkyl cross-coupling reactions, (tpy')NiMe (2b, tpy' = 4,4',4' '-tri-tert-butylterpyridine), is not produced via a mechanism that involves the formation of methyl radicals. Instead, it is proposed that (terpyridine)NiMe complexes arise via a comproportionation reaction between a Ni(II)-dimethyl species and a Ni(0) fragment in solution upon addition of a terpyridine ligand to (TMEDA)NiMe(2). EPR and DFT studies on the paramagnetic (terpyridine)NiMe (2a) both suggest that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand. Thus, an important consequence of these results is that alkyl halide reduction by (terpyridine)NiR(alkyl) complexes appears to be substantially ligand based. A comprehensive survey investigating the catalytic reactivity of related ligand derivatives suggests that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors.

Mutation of the putative hydrogen-bond donor to P700 of photosystem I.

The primary electron donor of photosystem I (PS1), called P(700), is a heterodimer of chlorophyll (Chl) a and a'. The crystal structure of photosystem I reveals that the chlorophyll a' (P(A)) could be hydrogen-bonded to the protein via a threonine residue, while the chlorophyll a (P(B)) does not have such a hydrogen bond. To investigate the influence of this hydrogen bond on P(700), PsaA-Thr739 was converted to alanine to remove the H-bond to the 13(1)-keto group of the chlorophyll a' in Chlamydomonas reinhardtii. The PsaA-T739A mutant was capable of assembling active PS1. Furthermore the mutant PS1 contained approximately one chlorophyll a' molecule per reaction center, indicating that P(700) was still a Chl a/a' heterodimer in the mutant. However, the mutation induced several band shifts in the visible P(700)(+) - P(700) absorbance difference spectrum. Redox titration of P(700) revealed a 60 mV decrease in the P(700)/P(700)(+) midpoint potential of the mutant, consistent with loss of a H-bond. Fourier transform infrared (FTIR) spectroscopy indicates that the ground state of P(700) is somewhat modified by mutation of ThrA739 to alanine. Comparison of FTIR difference band shifts upon P(700)(+) formation in WT and mutant PS1 suggests that the mutation modifies the charge distribution over the pigments in the P(700)(+) state, with approximately 14-18% of the positive charge on P(B) in WT being relocated onto P(A) in the mutant. (1)H-electron-nuclear double resonance (ENDOR) analysis of the P(700)(+) cation radical was also consistent with a slight redistribution of spin from the P(B) chlorophyll to P(A), as well as some redistribution of spin within the P(B) chlorophyll. High-field electron paramagnetic resonance (EPR) spectroscopy at 330-GHz was used to resolve the g-tensor of P(700)(+), but no significant differences from wild-type were observed, except for a slight decrease of anisotropy. The mutation did, however, provoke changes in the zero-field splitting parameters of the triplet state of P(700) ((3)P(700)), as determined by EPR. Interestingly, the mutation-induced change in asymmetry of P(700) did not cause an observable change in the directionality of electron transfer within PS1.

Carotenoid radical cations and dications: EPR, optical, and electrochemical studies.

Investigations of the structure and properties of paramagnetic carotenoid radical cations and diamagnetic carotenoid dications using electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy in conjunction with electrochemical, optical, and HPLC measurements, and molecular orbital calculations are described. These methods were applied to determine how the carotenoid radical cations and dications can be formed, their electron-transfer properties and stability in various media, and the mechanism by which carotenoid radical cations can isomerize.

Inclusion complexes of carotenoids with cyclodextrins: 1H NMR, EPR, and optical studies.

Direct evidence of carotenoid/cyclodextrin inclusion complex formation was obtained for the water-soluble sodium salt of beta-caroten-8'-oic acid (IV) by using 1H NMR and UV-Vis absorption spectroscopy. It was shown that this carotenoid forms a stable 1:1 inclusion complex with beta-cyclodextrin (stability constant K11 approximately 1500 M(-1)). All other carotenoids under study in the presence of cyclodextrins (CDs) form large aggregates in aqueous solution as demonstrated by very broad absorption spectra and considerable change in color. By using the EPR spin trapping technique, the scavenging ability of IV toward OOH radicals was compared in DMSO and in the aqueous CD solution. A considerable decrease in PBN/OOH spin adduct yield was detected in the presence of uncomplexed IV because of a competing reaction of the carotenoid with OOH radical. No such decrease occurred in the presence of the IV/CD complex. Moreover, a small increase in spin adduct yield (pro-oxidant effect) is most likely due to the reaction of the carotenoid with Fe3+ to regenerate Fe2+, which in turn regenerates the OOH radical. Our data show that CD protects the carotenoid from reactive oxygen species. On the other hand, complexation with CD results in considerable decrease in antioxidant ability of the carotenoid.