The Stability of G6PD Is Affected by Mutations with Different Clinical Phenotypes

Glucose-6-phosphate dehydrogenase (G6PD) deficiency is the most common enzyme deficiency worldwide, causing a wide spectrum of conditions with severity classified from the mildest (Class IV) to the most severe (Class I). To correlate mutation sites in the G6PD with the resulting phenotypes, we studied four naturally occurring G6PD variants: Yucatan, Nashville, Valladolid and Mexico City. For this purpose, we developed a successful over-expression method that constitutes an easier and more precise method for obtaining and characterizing these enzymes. The k_cat (catalytic constant) of all the studied variants was lower than in the wild-type. The structural rigidity might be the cause and the most evident consequence of the mutations is their impact on protein stability and folding, as can be observed from the protein yield, the T₅₀ (temperature where 50% of its original activity is retained) values, and differences on hydrophobic regions. The mutations corresponding to more severe phenotypes are related to the structural NADP⁺ region. This was clearly observed for the Classes III and II variants, which became more thermostable with increasing NADP⁺, whereas the Class I variants remained thermolabile. The mutations produce repulsive electric charges that, in the case of the Yucatan variant, promote increased disorder of the C-terminus and consequently affect the binding of NADP⁺, leading to enzyme instability.     

tert-Butyl Hydroperoxide (tBHP)-Induced Lipid Peroxidation and Embryonic Defects Resemble Glucose-6-Phosphate Dehydrogenase (G6PD) Deficiency in C. elegans

G6PD is required for embryonic development in animals, as severe G6PD deficiency is lethal to mice, zebrafish and nematode. Lipid peroxidation is linked to membrane-associated embryonic defects in Caenorhabditis elegans (C. elegans). However, the direct link between lipid peroxidation and embryonic lethality has not been established. The aim of this study was to delineate the role of lipid peroxidation in gspd-1-knockdown (ortholog of g6pd) C. elegans during reproduction. tert-butyl hydroperoxide (tBHP) was used as an exogenous inducer. Short-term tBHP administration reduced brood size and enhanced germ cell death in C. elegans. The altered phenotypes caused by tBHP resembled GSPD-1 deficiency in C. elegans. Mechanistically, tBHP-induced malondialdehyde (MDA) production and stimulated calcium-independent phospholipase A₂ (iPLA) activity, leading to disturbed oogenesis and embryogenesis. The current study provides strong evidence to support the notion that enhanced lipid peroxidation in G6PD deficiency promotes death of germ cells and impairs embryogenesis in C. elegans.     

Non-isothermal nitridation kinetics of Ti6Al4V in Al2O3-based refractories

To establish a kinetic model of nitridation of Ti6Al4V in Al₂O₃-based refractories, the non-isothermal nitridation of Ti6Al4V–Al₂O₃ composite refractories at various heating rates was investigated using a thermogravimetric (TG) analyzer for large samples. The activation energy (E) and kinetic model (G(α)) for the nitridation of Ti6Al4V were determined using the isoconversional and master plots methods, respectively. The nucleation and growth of nitriding products of the TiN solid solution was the controlling step in the nitridation of Ti6Al4V in Al₂O₃-based refractories. The Avrami-Erofeev kinetic model, depicted by the G(α) = [-ln (1-α)]⁴ equation, is the most rational kinetic model. The values of E and A for the nitridation of Ti6Al4V were calculated to be 214.99 kJ/mol and 1.46 × 10⁷ (S^?1), respectively.     

Cobalt(II) and nickel(II) complexes bearing mono(imino)pyridyl and bis(imino)pyridyl ligands: preparation,structure and ethylene polymerization/oligomerization behaviors

BACKGROUND: Ethylene oligomerization is the major industrial process to produce linear α‐olefins. Recently much work has been devoted to late transition metal catalysts used in this process, especially those with 2,6‐bis(imino)pyridyl dihalide ligands. Considering that most work has focused on simple modification to the substituents in imino‐aryl rings based on the symmetric bis(imino)pyridyl framework, here we expand this work to the asymmetric mono(imino)pyridyl ligands. RESULTS: The preparation, structure and ethylene polymerization/oligomerization behavior of series of mono(imino) pyridyl–MCl₂ and bis(imino)pyridyl–MX_n complexes are presented. The systematic studies were focused on the relationship between the catalytic behavior of these complexes for ethylene polymerization/oligomerization and reaction conditions, ligand structures, metal centers and counter‐anions. The influence of the coordination environment on catalyst behavior is also discussed. CONCLUSION: For mono(imino)pyridyl–Co(II) and ? Ni(II) catalysts bearing the Cl^? counter‐anion, good activities ranging from 0.513 × 10⁵ to 1.58 × 10⁵ g polyethylene (mol metal)^?1 h^?1 atm^?1 are afforded, and the most active catalysts are those with methyl in both ortho‐ and para‐positions of the imine N‐aryl ring. For bis(imino)pyridyl–Co(II) and ? Ni(II) catalysts bearing the SO₄^2? and NO₃^? counter‐anions, the low activities for ethylene oligomerization are in sharp contrast to those of their chloride analogues. Copyright © 2009 Society of Chemical Industry     

Cationic copolymerization of 1 ,3-pentadiene-with isoprene

The cationic copolymerization of 1,3-pentadiene (PD) with isoprene (IP) initiated by AICl₃, was carried out in toluene. The microstructure of the copolymer chain was characterized by IR and ¹H NMR. IP is incorporated in the copolymer chain mainly in cyclic segments. The PD–IP copolymer has a much higher cyclic content than the PD homopolymer, which shows that the cyclization reaction during PD polymerization is enhanced by the addition of IP. In addition, the reactivity ratios for IP(M₁) and PD(M₂) determined by the Kelen–Tudos method from low-conversion data are r₁ = 1.22 and r₂ = 1.09.     

Tunable Emission Phosphor Ca4Y6O(SiO4)6:Ce3+, Eu2+: Luminescence and Energy Transfer

A series of Ca_4–yY_6–xO(SiO₄)₆: xCe³⁺, yEu²⁺ samples are synthesized by a high‐temperature solid‐state method. Under 356 nm excitation, Ca₄Y₆O(SiO₄)₆:Ce³⁺ presents a strong blue emission band at 426 nm which are assigned to 4f⁰5d¹→4f¹ transition of Ce³⁺ ion. Ca₄Y₆O(SiO₄)₆:Eu²⁺ shows green emission under 380 nm radiation excitation, and the peak locates at 527 nm which is mainly due to transitions of Eu²⁺ from 4f⁷ ground state to 4f⁶5d¹ excited state. Under 356 nm excitation, a remarkable energy transfer from Ce³⁺ to Eu²⁺ exists in Ca₄Y₆O(SiO₄)₆, and the result reveals that the mechanism of energy transfer is a resonant type via a nonradiative dipole–dipole interaction. The hues of Ca₄Y₆O(SiO₄)₆:Ce³⁺, Eu²⁺ can be adjusted by the energy transfer from Ce³⁺ to Eu²⁺ ions, and a white emission can be achieved by tuning the ratio of Ce³⁺ to Eu²⁺. The results mean that Ce³⁺ may be the effective sensitizer for Eu²⁺‐doped Ca₄Y₆O(SiO₄)₆.     

Developing High Field MRI Contrast Agents by Tuning the Rotational Dynamics: Bisaqua GdAAZTA-based Dendrimers

Monomeric and dimeric AAZTA-based bifunctional chelators (AAZTA=6-amino-6-methylperhydro-1,4-diazepine tetraacetic acid) were attached to different generations (G0, G1 and G2) of ethylenediamine-cored PAMAM dendrimers (PAMAM=polyamidoamine) to obtain a series of six dendrimeric systems with 4 to 32 chelates at the periphery. These Gd^III-loaded dendrimers have molecular weight ranging from 3.5 to 25 kDa, thus allowing a systematic investigation on the changes in relaxivity (r₁) with the variation of the rotational dynamics following the increase in molecular size. Variable-temperature ¹⁷O NMR (on the dimeric building block Gd₂ L2 ) and ¹H Nuclear Magnetic Relaxation Dispersion measurements at different temperatures indicate that the water exchange lifetime (τ_M∼90 ns) of the two inner sphere water molecules does not represent a limiting factor to the relaxivity of the systems. The r₁ values at 1.5 T (60 MHz) and 298 K increases from 10.2 mM⁻¹ s⁻¹ for the monomer Gd L1 to 31.4 mM⁻¹ s⁻¹ for the dendrimer Gd₃₂ G2-32 (+308 %). However, the relaxivity (per Gd) does not show a linear dependence on the molecular mass, but rather the enhancement tends to attenuate markedly for larger systems. This effect has been attributed to the growing decrease in correlation between local rotational motions and global molecular tumbling.     

Theoretical Study on Thermodynamic and Detonation Properties of Polynitrocubanes

We investigated the heat of formation (Δ_fH) of polynitrocubanes using density functional theory B3LYP and HF methods with 6‐31G*, 6‐311+G**, and cc‐pVDZ basis sets. The results indicate that Δ_fH firstly decreases (nitro number m=0–2) and then increases (m=4–8) with each additional nitro group being introduced to the cubane skeleton. Δ_fH of octanitrocubane is predicted to be 808.08 kJ mol⁻¹ at the B3LYP/6‐311+G** level. The Gibbs free energy of formation (Δ_fG) increases by about 40–60 kJ mol⁻¹ with each nitro group being added to the cubane when the substituent number is fewer than 4, then Δ_fG increases by about 100–110 kJ mol⁻¹ with each additional group being attached to the cubic skeleton. Both the detonation velocity and the pressure for polynitrocubanes increase as the number of substituents increases. Detonation velocity and pressure of octanitrocubane are substantially larger than the famous widely used explosive cyclotetramethylenetetranitramine (HMX).     

Ruthenium(II) Complex-Based G-quadruplex DNA Selective Luminescent ‘Light-up’ Probe for RNase H Activity Detection

A bis-heteroleptic ruthenium(II) complex, 1[PF₆]₂ of benzothiazole amide substituted 2,2′-bipyridine ligand ( bmbbipy ) has been synthesized for the selective detection of G-quadruplex (GQ) DNA and luminescence-assay-based RNase H activity monitoring. Compound 1[PF₆]₂ exhibited aggregation-caused quenching (ACQ) in water. Aggregate formation was supported by DLS, UV-vis, and ¹H NMR spectroscopy results, and the morphology of aggregated particles was witnessed by SEM and TEM. 1[PF₆]₂ acted as an efficient GQ DNA-selective luminescent light-up probe over single-stranded and double-stranded DNA. The competency of 1[PF₆]₂ for selective GQ structure detection was established by PL and CD spectroscopy. For 1[PF₆]₂ , the PL light-up is exclusively due to the rigidification of the benzothiazole amide side arm in the presence of GQ-DNA. The interaction between the probe and GQ-DNA was analyzed by molecular docking analysis. The GQ structure detection capability of 1[PF₆]₂ was further applied in the luminescent ‘off-on’ RNase H activity detection. The assay utilized an RNA:DNA hybrid, obtained from 22AG2-RNA and 22AG2-DNA sequences. RNase H solely hydrolyzed the RNA of the RNA:DNA duplex and released G-rich 22AG2-DNA, which was detected via the PL enhancement of 1[PF₆]₂ . The selectivity of RNase H activity detection over various other restriction enzymes was also demonstrated.     

Significantly improving the Cu2+ removal performance of conducting polymer-based adsorbent from aqueous solution through cross-linking modification

Through cross-linking modification of poly(o-phenylenediamine) (PoPD) to increase the adsorption active sites, the Cu²⁺ adsorption capacity of PoPD was improved significantly. According to FT-IR, XRD, SEM and BET results, both PoPD and the cross-linked PoPD had porous or surface-adhesive porous morphology with a typical mesoporous character, the specific surface area of the latter was increased obviously from the former. Both of them showed excellent Cu²⁺ adsorption capabilities with the maximum adsorption q^exp_max of 76.51 and 85.49 mg·g⁻¹, and the corresponding removal ratios of 60.21% and 68.39%, respectively. The adsorption capacity was increased to its 1.54 times with pentaerythritol tris[3-(1-aziridinyl)propionate] (cross-linking agent-III) as cross-linking agent at pH = 5 and 25°C. Because temperature could affect the adsorption behavior of materials and the adsorption process is endothermic with ΔG < 0, the process should be accompanied by spontaneous chemical changes. The XRD, SEM–EDX mapping and XPS results showed that Cu²⁺ was successfully removed from the aqueous solution. Additionally, the adsorption was mainly based on the cation-π interaction and the formation of Cu-N bonds.     

Ratiometric fluorescent chemosensor based on the block copolymer of poly(N-isopropylacrylamide)-b-poly(N-vinylcarbazole) containing rhodamine 6G and 1,8-naphthalimide moieties

We have synthesized an amphiphilic block copolymer poly(N-isopropylacrylamide)-b-poly(N-vinylcarbazole) containing 1,8-naphthalimide and spirolactam rhodamine 6G moieties via reversible addition-fragmentation chain transfer radical polymerization. The photoluminescence (PL) spectrum of the poly(N-vinylcarbazole) block well matches the absorption spectrum of the 1,8-naphthalimide moiety and the enhanced emission with a peak at 510 nm from the 1,8-naphthalimide moiety is found in the block copolymer film for excitation at 330 nm. The 560-nm emission from the rhodamine 6G moiety is observed as the block copolymer film sprayed by Britton-Robinson (B-R) buffers or Fe³⁺ aqueous solutions for excitation at 330 and 400 nm. The PL intensity at 560 nm is markedly increased for the pH value of the B-R buffer lower than 3.0 or the Fe³⁺ concentration in water higher than 5 × 10⁻⁴ M. The 560-nm PL intensity is much higher for the block copolymer film photoexcited at 330 nm than that photoexcited at 400 nm due to double-step resonance energy transfer. The PL intensity ratio of 560 to 510 nm (I₅₆₀/I₅₁₀) is dependent on the resonance energy transfer from 1,8-naphthalimide to rhodamine 6G, which is sensitive to the concentrations of H⁺ and Fe³⁺ ions in water.     

Surface modification of nylon‐6 fibers for medical applications

Hydroxyethylmethacrylate (HEMA) is considered to be one of the important vinyl monomers. The ability of polyhydroxyethyl‐methacylate (PHEMA) graft sites to consecutive chemical modification makes the use of nylon‐6 fibers grafted with PHEMA a feasible bed for immobilization of a wide range of biologically active reagents, specially enzymes, drugs, cells, and immunadsorbents. Stemming from the above discussions, in this article, the graft copolymerization of HEMA onto modified nylon‐6 fibers containing Polydiallyldimethylammonium chloride (PDADMAC) in the presence of Cu²⁺–K₂S₂O₈ as a redox initiating system was carried out, with very high rate and almost without homopolymer formation. The factors affecting the grafting reaction (monomer, K₂S₂O₈ and cupric ion concentrations, the amount of PDADMAC as well as the reaction temperature) were studied. Kinetic investigation revealed that the rate of grafting (R_p) of HEMA onto modified nylon‐6 fibers is proportional to [HEMA]¹, [CuSO₄.5H₂O] ^0.7, [PDADMAC]^0.4, and [K₂S₂O₈]^1.4. The overall activation energy was calculated (71 KJ/mol). The fine structure, surface topography, thermal and electrical properties of parent and grafted nylon‐6 fibers were investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3788–3796, 2007     

Triazidotrinitro Benzene: 1,3,5‐(N3)3‐2,4,6‐(NO2)3C6

Triazidotrinitro benzene, 1,3,5‐(N₃)₃‐2,4,6‐(NO₂)₃C₆ ( 1 ) was synthesized by nitration of triazidodinitro benzene, 1,3,5‐(N₃)₃‐2,4‐(NO₂)₂C₆H with either a mixture of fuming nitric and concentrated sulfuric acid (HNO₃/H₂SO₄) or with N₂O₅. Crystals were obtained by the slow evaporation of an acetone/acetic acid mixture at room temperature over a period of 2 weeks and characterized by single crystal X‐ray diffraction: monoclinic, P 2₁/c (no. 14), a=0.54256(4), b=1.8552(1), c=1.2129(1) nm, β=94.91(1)°, V=1.2163(2) nm³, Z=4, ϱ=1.836 g⋅cm⁻³, R_all =0.069. Triazidotrinitro benzene has a remarkably high density (1.84 g⋅cm⁻³). The standard heat of formation of compound 1 was computed at B3LYP/6‐31G(d, p) level of theory to be ΔH°_f=765.8 kJ⋅mol⁻¹ which translates to 2278.0 kJ⋅kg⁻¹. The expected detonation properties of compound 1 were calculated using the semi‐empirical equations suggested by Kamlet and Jacobs: detonation pressure, P=18.4 GPa and detonation velocity, D=8100 m⋅s⁻¹.     

Structure and Binding of Peptide‐Dendrimer Ligands to Vitamin B12

The third‐generation peptide‐dendrimer B1 (AcES)₈(BEA)₄(K‐Amb‐Y)₂BCD‐NH₂ (B=branching (S)‐2,3‐diaminopropanoic acid, K=branching lysine, Amb=4‐aminomethyl‐benzoic acid) is the first synthetic model for cobalamin‐binding proteins and binds cobalamin strongly (K_a=5.0×10⁶ M ^?1) and rapidly (k₂=346 M ^?1 s^?1) by coordination of cobalt to the cysteine residue at the dendrimer core. A structure–activity relationship study is reported concerning the role of negative charges in binding. Substituting glutamates (E) for glutamines (Q) in the outer branches of B1 to form N3 (AcQS)₈(BQA)₄(B‐Amb‐Y)₂BCD‐NH₂ leads to stronger (K_a=12.0×10⁶ M ^?1) but slower (k₂=67 M ^?1 s^?1) cobalamin binding. CD and FTIR spectra show that the dendrimers and their cobalamin complexes exist as random‐coil structures without aggregation in solution. The hydrodynamic radii of the dendrimers determined by diffusion NMR either remains constant or slightly decreases upon binding to cobalamin; this indicates the formation of compact, presumably hydrophobically collapsed complexes.     

Zero thermal expansion in cubic MgZrF6

Isotropic zero thermal expansion (ZTE) is rare but intriguing physical property in materials. Here, we report an isotropic ZTE property in a double ReO₃‐type compound of MgZrF₆, which exhibits a negligible value of coefficient of thermal expansion (α_l = ?7.94 × 10^?7 K^?1 (XRD), α_l = ?4.22 × 10^?7 K^?1 (dilatometry), 300‐675 K). The ZTE mechanism of MgZrF₆ is understood by the joint studies of temperature dependence of crystal structure and lattice dynamics. Interestingly, different magnitudes of atomic displacement parameters (ADPs) for the fluorine atoms in MZrF₆ (M = Ca, Ni, Mg) are found. The strong temperature sensitivity of ADPs demonstrates intensive transverse thermal vibration of fluorine atoms, which contributes essentially to the negative thermal expansion of CaZrF₆. By contrast, for NiZrF₆ with positive thermal expansion, the temperature response of ADPs is weak. Moderate transverse thermal vibration takes place in MgZrF₆, and ZTE appears. Furthermore, lattice dynamics of MgZrF₆ is studied by temperature‐dependent Raman spectroscopy, which reveals the ZTE mechanism. In particular, the F_2g and A_g modes, corresponding to the bending and stretching vibrations of fluorine atoms, respectively, neither soften nor harden over the whole temperature range, which is correlated with the isotropic ZTE property of MgZrF₆.     

Directed evolution of subtilisin E into a highly active and guanidinium chloride- and sodium dodecylsulfate-tolerant protease

Proteases have niche applications in diagnostic kits that use cell lysis and thereby require high resistance towards chaotropic salts and detergents, such as guanidinium chloride (GdmCl) and sodium dodecylsulfate (SDS). Subtilisin E, a well‐studied serine protease, was selected to be re‐engineered by directed evolution into a “chaophilic” protease that would be resistance to GdmCl and SDS, for application in diagnostic kits. In three iterative rounds of directed evolution, variant SeSaM1–5 (S62I/A153V/G166S/I205V) was generated, with improved activity (330 %) and increased half life in 1 M GdmCl (<2 min to 4.7 h) or in 0.5 % SDS (<2 min to 2.7 h). Saturation mutagenesis at each site in the wild‐type subtilisin E revealed that positions 62 and 166 were mainly responsible for increased activity and stability. A double mutant, M2 (S62I/G166M), generated by combination of the best single mutations showed significantly improved kinetic constants; in 2 M GdmCl the K_m value decreased (29‐fold) from 7.31 to 0.25 mM , and the k_cat values increased (fourfold) from 15 to 61 s^?1. The catalytic efficiency, k_cat/K_m, improved dramatically (GdmCl: 247 mM ^?1 s^?1 (118‐fold); SDS, 179 mM ^?1 s^?1 (13‐fold)). In addition, the SeSaM1–5 variant showed higher stability in 2.0 % SDS when compared to the wild‐type (t_1/2 54.8 min (>27‐fold)). Finally, molecular dynamics simulations of the wild‐type subtilisin E showed that Gdm⁺ ions could directly interact with active site residues, thereby probably limiting access of the substrate to the catalytic centre.     

Horseradish‐Peroxidase‐Catalyzed Tyrosine Click Reaction

The efficiency of protein chemical modification on tyrosine residues with N‐methylluminol derivatives was drastically improved by using horseradish peroxidase (HRP). In the previous method, based on the use of hemin and H₂O₂, oxidative side reactions such as cysteine oxidation were problematic for functionalization of proteins selectively on tyrosine residues. Oxidative activation of N‐methylluminol derivatives with a minimum amount of H₂O₂ prevented the occurrence of oxidative side reactions under HRP‐catalyzed conditions. As probes for HRP‐catalyzed protein modification, N‐methylluminol derivatives showed much higher efficiency than tyramide without inducing oligomerization of probe molecules. Tyrosine modification also proceeded in the presence of β‐nicotinamide adenine dinucleotide (NADH, H₂O₂‐free conditions).     

Preparation and thermal decomposition of 5Mg(OH)2·MgSO4·2H2O nanowhiskers

Magnesium hydroxide sulfate hydrate (MHSH) nanowhiskers were prepared using magnesium chloride, ammonia and magnesium sulfate as raw materials by hydrothermal synthesis without any additional template. X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and thermal analysis (TG-DTA) were employed to characterize the composition and structural features of the MHSH nanowhiskers. It is shown that the thermal decomposition of nanowhiskers followed a three-step scheme. Based on DTA data, the reaction order, activation energy and pre-exponential factor for each step were calculated using a non-isothermal Kissinger method. It is also indicated from Satava method that the first step of the thermal decomposition of nanowhiskers is an A₂ nucleus formation and growth mechanism with integral form of G(a) = [−ln(1 − a)]^1/2. The second step is an A_u branching nuclei mechanism with integral form of G(a) = ln[a/(1 − a)], and the final step is a P_1/2 nucleation mechanism with integral form of G(a) = a^1/2.     

Cationic copolymerization of 1,3-pentadiene with 1,3-cyclopentadiene

Copolymerizations of 1,3-pentadiene (PD) with 1,3-cyclopentadiene (CPD) initiated by aluminium trichloride were carried out in toluene. The addition of CPD in the PD polymerization system does not affect the molecular weight but greatly increases the softening point of the polymer due to the introduction of cyclic structures. The Gardner color scale of the polymer is also raised by introduction of unsaturated rings of CPD. The copolymerization gives a complete conversion but generates insoluble crosslinked gels at high CPD content due to the high crosslinking reactivity of CPD. The integral intensities of unsaturated protons from PD and CPD segments of the copolymer chain on the ¹H-NMR spectrum give a perfect correlation with the copolymer compositions. The low-conversion experiments were carried out with small amounts of CPD in order to determine the reactivity ratio in this copolymerization system (M₁ = PD and M₂ = CPD). The result of r₁ = k₁₁/k₁₂ = 0.46 demonstrates that CPD has a higher reactivity than PD toward PD growing carbocations, and hence the copolymer shows a higher CPD proportion than the corresponding comonomer. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1883–1887, 1997     

Synthesis, crystal structures, and electronic spectra of (1,8-naphthyridine)Re(CO)3Cl and [(1,8-naphthyridine)Cu(DPEPhos)]PF6

Two 1,8-naphthyridine (nap) metal complexes (nap)Re^I(CO)₃Cl (1) and [(nap)Cu^I(DPEPhos)]PF₆ (2) were synthesized and characterized by NMR-, emission, and absorption spectroscopy, elemental analysis, mass spectrometry, and X-ray structural analysis. In both complexes, the nap ligand coordinates with both N atoms to the metal centre in a bidentate manner. 1 and 2 exhibit a broad phosphorescence in solid state at T = 300 K, which is completely quenched in solution at r.t. In addition, the gas-phase structures of both complexes were optimized at the B3LYP/6-31G(d,p) level of theory.