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At least 631 records · Page 35

Achieving Reversible H2/H+ Interconversion at Room Temperature with Enzyme-Inspired Molecular Complexes: A Mechanistic Study

Inspired by the contribution of the protein scaffold to the efficiency with which enzymes function, we report the first molecular complex that is reversible for electrocatalytic H2 production/oxidation at room temperature in methanol. [Ni(PCy2NPhe2)2]2+ (CyPhe; PR2NR’2 = 1,5-diaza-3,7-diphosphacyclooctane, Cy=cyclohexyl, Phe=phenylalanine), shows reversible behavior in acidic methanol with peripheral phenylalanine groups providing key contributions to the catalytic behavior. The importance of the aromatic rings is implicated in achieving reversibility, based on the lack of reversibility of similar complexes, [Ni(PCy2NAmino Acid2)2]2+, containing arginine (CyArg) or glycine (CyGly). A complex with an added OH group on the ring, (CyTyr; Tyr=Tyrosine), also shows similar behavior. NMR studies reveal a significantly slower rate of chair-boat isomerization for the CyPhe relative to other derivatives, suggesting that the aromatic groups provide structural control by interacting with each other, an observation supported by molecular dynamics studies. NMR studies also show extremely fast proton movement, with a proton pathway from the Ni-H through the pendant amine to the –COOH group. Further, studies of acomplex without the –COOH group, [Ni(PCy2NTym2)2]2+ (CyTym; Tym=Tyramine), are not reversible and have slow proton movement from the pendant amine, demonstrating the essential nature of the –COOH group in achieving reversibility. Finally, methanol is demonstrated to play a critical contributing role. The influence of multiple factors on reversibility for this synthetic catalyst is a demonstration of the intricate interplay between the first, second, and outer coordination spheres and resembles the complexity observed in metalloenzymes.

Environmental Molecular Sciences Laboratory↗

Molecular Level Understanding of How Oxygen and Carbon Monoxide Improve NOx Storage in Palladium/SSZ-13 Passive NOx Adsorbers: The Role of NO+ and Pd(II)(CO)(NO) Species

Addition of molecular oxygen to NO-containing stream improves NOx storage of the Pd/H-SSZ-13. Model Pd/SSZ-13 with high dispersion of Pd ions (0.1 and 1 wt% Pd) was synthesized. The material was characterized with FTIR and cryo-STEM. Adsorption of NO leads to the formation of Pd(II)-NO and Pd(I)-NO complexes as well as NO+ species that replace residual H+ (extra framework) sites. These nitrosyl species are characterized by notable thermal stability, with resistance to decomposition under high vacuum at 200 ºC. Addition of O2 to NO slightly increases the amount of Pd(II)-NO complex with ?NO at ~1865 cm-1 whereas the low frequency ?NO band at 1805 cm-1, assigned to Pd(I)-NO, decreases in intensity. Simultaneously, polydentate nitrate species appear in small amounts, contributing to the high temperature NOx release stage during a PNA cycle. The concentration of NO+ (characterized by the broad IR band centered at 2170 cm-1), in the presence of O2, increases in intensity profoundly and contributes to the increased capacity of Pd/SSZ-13 to store NOx and release it at temperatures >140 ºC. In the presence of H2O/O2, Pd/SSZ-13 does not perform satisfactorily as PNA, but the addition of CO to the stream improves the PNA storage capacity and shifts the NOx release peak temperature to >320 ºC where SCR catalysts are the most effective. With the aid of FTIR spectroscopy, we reveal the selective formation of a mixed carbonyl-nitrosyl complex Pd(II)(NO)(CO) in the presence of CO. Due to shielding of the Pd(II) ion from excess water and selective formation of stable coordinately saturated Pd(NO)(CO) complexes, the PNA performance is improved by CO. Therefore, we demonstrate that beside NO species adsorbed on Pd, nitrosyl ions (NO+) in extra framework positions of chabazite are important for PNA storage. Furthermore, the important role of CO in promoting PNA performance is elucidated, thus highlighting the utility of the combined spectroscopic approach (in addition to materials performance testing) to derive structure/PNA performance relationships and identify new avenues to improve the PNA performance.

Khivantsev, Konstantin↗

The Synthesis, Characterization and Dehydrogenation of Sigma-Complexes of BN-Cyclohexanes

The coordination chemistry of the 1,2-BN-cyclohexanes 2,2-R 2 -1,2-B,N-C 4 H 10 (R 2 =HH, MeH, Me 2 ) with Ir and Rh metal fragments has been studied. This led to the solution (NMR spectroscopy) and solid-state (X-ray diffraction) characterization of [Ir(PCy 3 ) 2 (H) 2 (η 2 η 2 -H 2 BNR 2 C 4 H 8 )][BAr F 4 ] (NR 2 =NH 2 , NMeH) and [Rh( i Pr 2 PCH 2 CH 2 CH 2 P i Pr 2 )(η 2 η 2 -H 2 BNR 2 C 4 H 8 )][BAr F 4 ] (NR 2 =NH 2 , NMeH, NMe 2 ). For NR 2 =NH 2 subsequent metal-promoted, dehydrocoupling shows the eventual formation of the cyclic tricyclic borazine [BNC 4 H 8 ] 3 , via amino-borane and, tentatively characterized using DFT/GIAO chemical shift calculations, cycloborazane intermediates. For NR 2 =NMeH the final product is the cyclic amino-borane HBNMeC 4 H 8 . The mechanism of dehydrogenation of 2,2-H,Me-1,2-B,N-C 4 H 10 using the {Rh( i Pr 2 PCH 2 CH 2 CH 2 P i Pr 2 )} + catalyst has been probed. Catalytic experiments indicate the rapid formation of a dimeric species, [Rh 2 ( i Pr 2 PCH 2 CH 2 CH 2 P i Pr 2 ) 2 H 5 ][BAr F 4 ]. Using the initial rate method starting from this dimer, a first-order relationship to [amine-borane], but half-order to [Rh] is established, which is suggested to be due to a rapid dimer–monomer equilibrium operating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Double Intramolecular 1,2 C–H Addition of o -Methyl Groups To Form Ruthenium Pincer Double Tuck-In Complexes

Ruthenium pincer complexes have a rich history of coordination and reaction chemistries. In this work, we report our discoveries of previously unreported Ru pincer coordination geometries. We found that mono tuck-in κ 4 -ArPN H PRuLCl complexes react with NaN(SiMe 3 ) 2 producing double tuck-in mer-κ 5 -ArPN H PRuL complexes. Interestingly, when κ 4 -MesPN H PRuCl is dehydrohalogenated, the resulting double tuck-in complex binds N 2 , forming the nitrogen complex κ 5 -MesPN H PRuN 2 . Further, the mer-κ 5 -ArPN H PRuL complexes thermally isomerize to the fac-κ 5 -ArPN H PRuL isomers, which is an uncommon reaction for pincer complexes. The mer-κ 5 -ArPN H PRuL complexes react with CO and CO 2 to form amide κ 4 -ArPN H PRu(CO)L or carbamate κ 5 -ArPN(CO 2 )PRuL complexes, respectively, supporting the hypothesis that the κ 4 -ArPNPRuL amide intermediates are accessible and reactive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The universal suppressor mutation restores membrane budding defects in the HSV-1 nuclear egress complex by stabilizing the oligomeric lattice

Nuclear egress is an essential process in herpesvirus replication whereby nascent capsids translocate from the nucleus to the cytoplasm. This initial step of nuclear egress–budding at the inner nuclear membrane–is coordinated by the nuclear egress complex (NEC). Composed of the viral proteins UL31 and UL34, NEC deforms the membrane around the capsid as the latter buds into the perinuclear space. NEC oligomerization into a hexagonal membrane-bound lattice is essential for budding because NEC mutants designed to perturb lattice interfaces reduce its budding ability. Previously, we identified an NEC suppressor mutation capable of restoring budding to a mutant with a weakened hexagonal lattice. Using an established in-vitro budding assay and HSV-1 infected cell experiments, we show that the suppressor mutation can restore budding to a broad range of budding-deficient NEC mutants thereby acting as a universal suppressor. Cryogenic electron tomography of the suppressor NEC mutant lattice revealed a hexagonal lattice reminiscent of wild-type NEC lattice instead of an alternative lattice. Further investigation using x-ray crystallography showed that the suppressor mutation promoted the formation of new contacts between the NEC hexamers that, ostensibly, stabilized the hexagonal lattice. This stabilization strategy is powerful enough to override the otherwise deleterious effects of mutations that destabilize the NEC lattice by different mechanisms, resulting in a functional NEC hexagonal lattice and restoration of membrane budding.

60 APPLIED LIFE SCIENCES↗

N-heterocyclic carbene platinum-butadiyne Click/iClick complexes. Towards blue-violet phosphorescence

By employing two different methods, namely, Click and iClick, a series of four trans-NHC-Pt(II) triazole-acetylide complexes containing benzyl (3a), methylnaphthalene (3b), methylanthracene (3c), and phenyl (3d) substituents at the terminal triazole ring were synthesized and characterized. The traditional click approach involves first synthesizing a triazole-acetylene and then attaching to the Pt ion. In the iClick approach, the triazole is formed via cycloaddition by combining a trans-platinum butadiyne with the corresponding organic azide. The complexes were interrogated to determine the effects of conjugation and ligand substituent on their photophysical properties. Complex 3a exhibits a photoluminescence lifetime of 4.3 μs at 77 K. Ascribed to emission from conformers differing due to the torsion of the aryl acetylide ligands, employing different excitation wavelengths results in different emission spectra. Complex 3a emits in the violet region with CIE coordinates of (0.159, 0.021) under 290 nm excitation and shifts to CIE coordinates of (0.161, 0.019) under 320 nm excitation. Finally, complex 3d, having a photoluminescence lifetime of 13.1 μs at room temperature, emits in the sky-blue region with CIE coordinates of (0.237, 0.355).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A tetrahedral neptunium(V) complex

Neptunium is an actinide element sourced from anthropogenic production, and, unlike naturally abundant uranium, its coordination chemistry is not well developed in all accessible oxidation states. High-valent neptunium generally requires stabilization from at least one metal–ligand multiple bond, and departing from this structural motif poses a considerable challenge. Here we report a tetrahedral molecular neptunium(V) complex ([Np 5+ (NPC) 4 ][B(ArF 5 ) 4 ], 1-Np) (NPC = [NP t Bu(pyrr) 2 ] − ; t Bu = C(CH 3 ) 3 ; pyrr = pyrrolidinyl (N(C 2 H 4 ) 2 ); B(ArF 5 ) 4 = tetrakis(2,3,4,5,6-pentafluourophenyl)borate). Single-crystal X-ray diffraction, solution-state spectroscopy and density functional theory studies of 1-Np and the product of its proton-coupled electron transfer (PCET) reaction, 2-Np, demonstrate the unique bonding that stabilizes this reactive ion and establishes the thermochemical and kinetic parameters of PCET in a condensed-phase transuranic complex. The isolation of this four-coordinate, neptunium(V) complex reveals a fundamental reaction pathway in transuranic chemistry.

coordination chemistry↗

Synthesis of Anhydrous Acetates for the Components of Nuclear Fuel Recycling in Dialkylimidazolium Acetate Ionic Liquids [plus supplemental information]

A series of anhydrous acetate salts with uranium {[C 2 C 1 im][UO 2 (OAc) 3 ] (1), [C 2 C 2 im][UO 2 (OAc) 3 ] (2), and [C 4 C 1 im][UO 2 (OAc) 3 ] (3)}, lanthanides {[C 2 C 2 im] 2 [La(OAc) 5 ] (4) and [C 2 C 1 im] 2 [Nd(OAc) 5 ] (5)}, and strontium {[C 2 C 1 im] n [Sr- (OAc) 3 ] n (6)} (where C 2 C 1 im = 1-ethyl-3-methylimidazolium, C 2 C 2 im = 1,3-diethylimidazolium, C 4 C 1 im = 1-butyl-3-methylimi-dazolium, and OAc = acetate) have been prepared and structurally characterized. Both lanthanides and strontium are common components of the nuclear fuel waste, and their separation from uranium is an important but still challenging task. A new synthetic method with dialkylimidazolium acetate ionic liquids (ILs) as the solvent has been developed for the direct synthesis of homoleptic acetates from the corresponding hydrates and, unexpectedly, hardly soluble f-element oxides. Although the group of characterized compounds shows perfect structural variability, all actinide and lanthanide metal ions form monomeric complex anions where the metal cation coordinates to five ligands including two oxygen atoms in the case of uranium, as is commonly observed for uranyl compounds. Crystallographic analyses revealed that the complex [UO 2 (OAc) 3 ] - anions possess rather standard D 3h symmetry featuring a hexagonal-bipyramidal coordination environment, while the lanthanide anions [Ln(OAc) 5 ] 2- are fully asymmetric and the Ln 3+ cations are 10-coordinated in the form of a distorted bicapped tetragonal antiprism. This is the first report of lanthanide ions coordinated in this fashion. For Sr 2+ , 9-fold coordination through oxygen atoms in the form of a strongly distorted tricapped trigonal prism is observed. Furthermore, the crystallization of anhydrous, homoleptic, anionic acetate complexes from such a large variety of different metal salts appears to be due to the properties of dialkylimidazolium acetate ILs themselves, including enhanced basicity from the high concentration of free anions and their greater affinity for hydrogen-bonding solutes relative to metal cations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

C–IBI: Targeting cumulative coordination within an iterative protocol to derive coarse-grained models of (multi-component) complex fluids

We present a coarse-graining strategy that we test for aqueous mixtures. The method uses pair-wise cumulative coordination as a target function within an iterative Boltzmann inversion (IBI) like protocol. We name this method coordination iterative Boltzmann inversion (C–IBI). While the underlying coarse-grained model is still structure based and, thus, preserves pair-wise solution structure, our method also reproduces solvation thermodynamics of binary and/or ternary mixtures. In addition, we observe much faster convergence within C–IBI compared to IBI. To validate the robustness, we apply C–IBI to study test cases of solvation thermodynamics of aqueous urea and a triglycine solvation in aqueous urea.

74 ATOMIC AND MOLECULAR PHYSICS↗

Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex

We introduce a new family of complexes with the general formula [Run(tda)(py)2]m+ (n = 2, m = 0, 1; n = 3, m = 1, 2+; n = 4, m = 2, 32+), with tda2– being [2,2':6',2''-terpyridine]-6,6''-dicarboxylate, including complex [RuIV(OH)(tda-κ-N3O)(py)2]+, 4H+, which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 32+ under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV–vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), including solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Ru center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H+ can be generated potentiometrically, or voltammetrically, from 32+, and both coexist in solution. While complex 32+ is not catalytically active, the catalytic performance of complex 4H+ is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s–1 at pH 7.0 and 50 000 s–1 at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H+, manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O–O bond formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vibrational properties of heme-nitrosoalkane complexes in comparison with those of their HNO analogs, and reactivity studies towards nitric oxide and Lewis acids

C-Nitroso compounds (RNO, R = alkyl and aryl) are byproducts of drug metabolism and bind to heme proteins, and their heme-RNO adducts are isoelectronic to ferrous nitroxyl (NO-/HNO) complexes. Importantly, heme-HNO compounds are key intermediates in the reduction of NO to N 2 O and nitrite to ammonium in the nitrogen cycle. Ferrous heme-RNO complexes act as stable analogs of these species, potentially allowing for the investigation of the vibrational and electronic properties of unstable heme-HNO intermediates. In this paper, a series of six-coordinate ferrous heme-RNO complexes (where R = iPr and Ph) were prepared using the TPP 2- and 3,5-Me-BAFP 2- co-ligands, and tetrahydrofuran, pyridine, and 1-methylimidazole as the axial ligands (bound trans to RNO). These complexes were characterized using different spectroscopic methods and X-ray crystallography. The complex [Fe(TPP)(THF)(iPrNO)] was further utilized for nuclear resonance vibrational spectroscopy (NRVS), allowing for the detailed assignment of the Fe–N(R)O vibrations of a heme-RNO complex for the first time. The vibrational properties of these species were then correlated with those of their HNO analogs, using DFT calculations. Our studies support previous findings that RNO ligands in ferrous heme complexes do not elicit a significant trans effect. In addition, the complexes are air-stable, and do not show any reactivity of their RNO ligands towards NO. So although ferrous heme-RNO complexes are suitable structural and electronic models for their HNO analogs, they are unsuitable to model the reactivity of heme-HNO complexes. We further investigated the reaction of our heme-RNO complexes with different Lewis acids. Here, [Fe(TPP)(THF)(iPrNO)] was found to be unreactive towards Lewis acids. In contrast, [Fe(3,5-Me-BAFP)(iPrNO) 2 ] is reactive towards all of the Lewis acids investigated here, but in most cases the iron center is simply oxidized, resulting in the loss of the iPrNO ligand. In the case of the Lewis acid B 2 (pin) 2 , the reduced product [Fe(3,5-Me-BAFP)(iPrNH 2 )(iPrNO)] was identified by X-ray crystallography.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectroscopic, Computational, Antimicrobial, DNA Interaction, In Vitro Anticancer and Molecular Docking Properties of Biochemically Active Cu(II) and Zn(II) Complexes of Pyrimidine-Ligand

Biochemically active Cu(II) and Zn(II) complexes [CuL(ClO{sub 4}){sub 2}(1) and ZnL(ClO{sub 4}){sub 2}(2)] have been synthesized from N,N donor Schiff base ligand L derived from4,6-dichloropyrimdine-5-carboxaldehyde with 4-(2-aminoethyl)morpholine. The L, complexes 1 and 2 have been structurally characterized by elemental analysis, {sup 1}H-NMR, FTIR, MS, UV-Visible and ESR techniques. The results obtained from the spectral studies supports the complexes 1 and 2 are coordinated with L through square planar geometry. DFT calculations results supports, the ligand to metal charge transfer mechanism can occur between L and metal(II) ions. The antimicrobial efficacy results have been recommended that, complexes 1 and 2 are good anti-pathogenic agents than ligand L. The interaction of complexes 1 and 2 with calf thymus (CT) DNA has been studied by electronic absorption, viscometric, fluorometric and cyclic voltammetric measurements. The calculated K{sub b} values for L, complexes 1 and 2 found from absorption titrations was 4.45 × 10{sup 4}, L; 1.92 × 10{sup 5}, 1 and 1.65 × 10{sup 5}, 2. The Ksv values were found to be 3.0 × 10{sup 3}, 3.68 × 10{sup 3}and 3.52 × 10{sup 3} for L, complexes 1 and 2 by using competitive binding with ethidium bromide (EB). These results suggest that, the compounds are interacted with DNA may be electrostatic binding. The molecular docking studies have been carried out to confirm the interaction of compounds with DNA. Consequently, in vitro anticancer activities of L, complexes 1 and 2 against selected cancer (lung cancer A549, liver cancer HepG2 and cervical carcinoma HeLa) and normal (NHDF) cell lines were assessed by MTT assay.

60 APPLIED LIFE SCIENCES↗

Elucidation of roles for vitamin B 12 in regulation of folate, ubiquinone, and methionine metabolism

Significance Using a chemical probe mimic of vitamin B 12 , we reveal a light- and B 12 -dependent DNA regulator, and make the unexpected discovery of B 12 having regulatory involvement in microbial folate, ubiquinone, and methionine processes. These findings suggest a pivotal role for B 12 in the control of cell growth, which may lead to coordination of cell behavior in complex multicellular systems. As key research questions emerge from host-associated and environmental microbiomes, we anticipate that B 12 regulatory control of metabolism will be found to be generalizable, will be critical for coordination of individual microbe and community metabolism, and that organismal interdependencies for B 12 may be pertinent to microbiome organization, stability, and overall function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

U 4+/5+/6+ in a Conserved Pseudotetrahedral Imidophosphorane Coordination Sphere

While several ligand systems support uranium across a range of oxidation states, spanning more than two oxidation states in a conserved coordination geometry is uncommon among structurally authenticated complexes. Imidophosphorane ligands significantly stabilize high-valent lanthanide and actinide complexes. Here, we report a series of homoleptic uranium imidophosphorane complexes, spanning the +4, +5 and +6 oxidation states in a four-coordinate pseudotetrahedral ligand field. The +6 oxidation state is accessible using a mild ferrocenium oxidant, yielding a rare example of U6+ in a pseudotetrahedral coordination environment. As the formal oxidation state increases, the U–N distances gradually contract, consistent with the Shannon ionic radii of U 4+/5+/6+ . Compared to reported complexes, the short U–N distances observed in the U 6+ complex are more comparable to dianionic imido ligands than monoanionic amido ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural Changes to the Gd‐DTPA Complex at Varying Ligand Protonation State

Abstract Diethylenetriaminepentaacetic acid (DTPA) is a chelating agent whose complex with the Gd 3+ ion is used in medical imaging. DTPA is also used in lanthanide‐actinide separation processes. As protonation of the DTPA ligand can facilitate dissociation of the Gd 3+ ion from the Gd‐DTPA complex, this work investigates the coordination structures of the aqueous Gd 3+ ion and its environment when chelated by DTPA in eight different DTPA protonation states. Both classical and ab initio molecular dynamics (MD) simulations are conducted to model the solvated complexes. Extended X‐ray absorption fine structure (EXAFS) measurements of the Gd 3+ aqua ion, and the Gd‐DTPA complex at pH 1 and 11, are compared to EXAFS spectra predicted from the MD simulations to verify the accuracy of the MD structures. The findings of this work provide atomic‐level details into the fluctuating Gd‐DTPA complex environment as the DTPA ligand gradually detaches from the Gd 3+ ion with increased protonation.

Chemistry↗

Coordination and Convening of the 2016 Arctic Science Summit Week

The Arctic Science Summit Week, Arctic Observing Summit, Arctic Council Senior Arctic Officials, Model Arctic Council, and International Arctic Assembly were convened on the campus of the University of Alaska Fairbanks with great productivity and satisfaction of the participants. We were pleased to welcome over 1000 participants from 30 different nations and over 130 different institutions. The organization and execution of these meetings was extensive and complex involving more than 250 coordinators, volunteers and contributors from across Alaska. The participants were enthusiastic in their praise of the content and accomplishments of the meeting, but they were equally happy about the genuine welcome offered to our guests by the people of Alaska. Hosting a complex event such as this summit required an army of supporting services and we were blessed to have volunteers from Fairbanks, North Pole, Anchorage and other communities throughout Alaska helping us meet these needs. This truly was an event hosted by the people of Alaska. The significance of these events cannot be overstated. The US and global communities are finally coming to the realization of the important role that the Arctic plays in international politics, economics, and science. The Arctic has experienced tremendous changes in recent years, offering new opportunities that may be addressed through international collaborations, and serious challenges that must be addressed through active investment, adaptation and national and international coordination. Over 10% of the meeting participants were indigenous peoples, from indigenous organizations or hailed from small remote communities. This is still lower than we had hoped, but it is greater participation than similar meetings have experienced in the past. It is through such engagement that we can attack problems related to the changing environment, stagnant economies, and social ills.

42 ENGINEERING↗