Solvent Acts as the Referee in a Match-Up Between Charged and Preorganized Receptors.

The prevalence of anion-cation contacts in biomolecular recognition under aqueous conditions suggests that ionic interactions should dominate the binding of anions in solvents across both high and low polarities. Investigations of this idea using titrations in low polarity solvents are impaired by interferences from ion pairing that prevent a clear picture of binding. To address this limitation and test the impact of ion-ion interactions across multiple solvents, we quantified chloride binding to a cationic receptor after accounting for ion pairing. In these studies, we created a chelate receptor using aryl-triazole CH donors and a quinolinium unit that directs its cationic methyl inside the binding pocket. In low-polarity dichloromethane, the 1 : 1 complex (log K1 : 1 ~ 7.3) is more stable than neutral chelates, but fortuitously comparable to a preorganized macrocycle (log K1 : 1 ~ 6.9). Polar acetonitrile and DMSO diminish stabilities of the charged receptor (log K1 : 1 ~ 3.7 and 1.9) but surprisingly 100-fold more than the macrocycle. While both receptors lose stability by dielectric screening of electrostatic stability, the cationic receptor also pays additional costs of organization. Thus even though the charged receptor has stronger binding in apolar solvents, the uncharged receptor has more anion affinity in polar solvents.

Photochemical Dearomative Cycloadditions of Quinolines and Alkenes: Scope and Mechanism Studies.

Photochemical dearomative cycloaddition has emerged as a useful strategy to rapidly generate molecular complexity. Within this context, stereo- and regiocontrolled intermolecular para-cycloadditions are rare. Herein, a method to achieve photochemical cycloaddition of quinolines and alkenes is shown. Emphasis is placed on generating sterically congested products and reaction of highly substituted alkenes and allenes. In addition, the mechanistic details of the process are studied, which revealed a reversible radical addition and a selectivity-determining radical recombination. The regio- and stereochemical outcome of the reaction is also rationalized.

Chain Entropy Beats Hydrogen Bonds to Unfold and Thread Dialcohol Phosphates inside Cyanostar Macrocycles To Form [3]Pseudorotaxanes.

The recognition of substituted phosphates underpins many processes including DNA binding, enantioselective catalysis, and recently template-directed rotaxane synthesis. Beyond ATP and a few commercial substrates, however, little is known about how substituents effect organophosphate recognition. Here, we examined alcohol substituents and their impact on recognition by cyanostar macrocycles. The organophosphates were disubstituted by alcohols of various chain lengths, dipropanol, dihexanol, and didecanol phosphate, each accessed using modular solid-phases syntheses. Based on the known size-selective binding of phosphates by π-stacked dimers of cyanostars, threaded [3]pseudorotaxanes were anticipated. While seen with butyl substituents, pseudorotaxane formation was disrupted by competitive OH···O- hydrogen bonding between both terminal hydroxyls and the anionic phosphate unit. Crystallography also showed formation of a backfolded propanol conformation resulting in an 8-membered ring and a perched cyanostar assembly. Motivated by established entropic penalties accompanying ring formation, we reinstated [3]pseudorotaxanes by extending the size of the substituent to hexanol and decanol. Chain entropy overcomes the enthalpically favored OH···O- contacts to favor random-coil conformations required for seamless, high-fidelity threading of dihexanol and didecanol phosphates inside cyanostars. These studies highlight how chain length and functional groups on phosphate's substituents can be powerful design tools to regulate binding and control assembly formation during phosphate recognition.

Broadband Tunable Mid-infrared Plasmon Resonances in Cadmium Oxide Nanocrystals Induced by Size-Dependent Nonstoichiometry.

A central theme of nanocrystal (NC) research involves synthesis of dimension-controlled NCs and studyof size-dependent scaling laws governing their optical, electrical, magnetic, and thermodynamic properties. Here, we describe the synthesis of monodisperse CdO NCs that exhibit high quality-factor (up to 5.5) mid-infrared (MIR) localized surface plasmon resonances (LSPR) and elucidate the inverse scaling relationship between carrier concentration and NC size. The LSPR wavelength is readily tunable between 2.4 and ∼6.0 µm by controlling the size of CdO NCs. Structural and spectroscopic characterization provide strong evidence that free electrons primarily originate from self-doping due to NC surface-induced nonstoichiometry. The ability to probe and to control NC stoichiometry and intrinsic defects will pave the way toward predictive synthesis of doped NCs with desirable LSPR characteristics.

Electrosynthesis of a Biaurone by Controlled Dimerization of Flavone: Mechanistic Insight and Large-Scale Application.

The electrochemistry of flavone (1) has been carefully investigated at glassy carbon cathodes in dimethylformamide containing 0.10 M tetra-n-butylammonium tetrafluoroborate as supporting electrolyte. In this medium, a cyclic voltammogram for a reduction of 1 exhibits a reversible cathodic process (Epc = -1.58 V and Epa = -1.47 V vs SHE) that is followed by an irreversible cathodic peak (Epc = -2.17 V vs SHE). When water (5.0 M) is introduced into the medium, the first peak for 1 becomes irreversible (Epc = -1.56 V vs SHE), and the second (irreversible) peak shifts to -2.07 V vs SHE. Bulk electrolyses of 1 at -1.60 V vs SHE afford flavanone, 2'-hydroxychalcone, 2'-hydroxy-3-phenylpropionate, and two new compounds, namely (Z)-1,6-bis(2-hydroxyphenyl)-3,4-diphenylhex-3-ene-1,6-dione (D1) and (Z)-2,2'-(1,2-diphenylethene-1,2-bis(benzofuran-3(2H))-one) (D2), obtained in significant amounts, that were characterized by means of 1H and 13C NMR spectrometry as well as single-crystal X-ray diffraction. Along with the above findings, we have proposed a mechanism for the electroreduction of 1, which has been further corroborated by our quantum mechanical study.

Hydrosilylation of an Iron(IV) Nitride Complex.

The nitride ligand in iron(IV) complex PhB(MesIm)3Fe≡N reacts with excess H3SiPh to afford PhB(MesIm)3Fe(µ-H)3(SiHPh) as the major product, which has been structurally and spectroscopically characterized. Bulkier silane HaSiPh2 provides iron(II) amido complex PhB(MesIm)3FeN(H)(SiHPh2) as the initial product of the reaction, with excess H2SiPh2 affording diamagnetic PhB(MesIm)3Fe(µ-H)3(SiPh2) as the major product. Unobserved iron(II) hydride PhB(MesIm)3Fe-H is implicated as an intermediate in this reaction, as suggested by the results of the reaction between iron(II) amido PhB(MesIm)3FeN(H)tBu and H3SiPh, which provides PhB(MesIm)3Fe(H)(µ-H)2(Si(NHtBu)Ph) as the sole product.

Multi-state amine sensing by electron transfers in a BODIPY probe.

Amines are ubiquitous in the chemical industry and are present in a wide range of biological processes, motivating the development of amine-sensitive sensors. There are many turn-on amine sensors, however there are no examples of turn-on sensors that utilize the amine's ability to react by single electron transfer (SET). We investigated a new turn-on amine probe with a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) fluorophore. BODIPY fluorescence is first preprogrammed into an off state by internal photoinduced electron transfer (PET) to an electron-deficient quinolinium ring, resulting in fluorescence quenching. At low concentrations of aliphatic amine (0 to 10 mM), this PET pathway is shut down by external SET from the amine to the photoexcited charge-transfer state of the probe and the fluorescence is turned on. At high concentrations of amine (50 mM to 1 M), we observed collisional quenching of the BODIPY fluorescence. The probe is selective for aliphatic amines over aromatic amines, and aliphatic thiols or alcohols. The three molecular processes modulate the BODIPY fluorescence in a multi-mechanistic way with two of them producing a direct response to amine concentrations. The totality of the three molecular processes produced the first example of a multi-state and dose-responsive amine sensor.

Lone-Pair-Induced Topicity Observed in Macrobicyclic Tetra-thia Lactams and Cryptands: Synthesis, Spectral Identification, and Computational Assessment.

The synthesis of a rigid macrobicyclic N,S lactam L1 and a topologically favored in/in N,S cryptand L2 are reported with X-ray structure analysis, dynamic correlation NMR spectroscopy, and computational analysis. Lactam L1 exhibits two distinct rotameric conformations (plus their enantiomeric counterparts) at 25 °C, as confirmed via NMR spectroscopy and computational analysis. Coalescence of the resonances of L1 was observed at 115 °C, allowing for complete nuclei to frequency correlation. Combining computational investigations with experimental data, topological equilibria and relative energies/strain relating to the perturbation of the pore were determined. Due to the increased conformational strain of the N2S2 template, the nitrogen lone pairs in L2 elicit a unique transannular interaction, resulting in a thermodynamically favored in/in nephroidal racemate. The combination of preferred topology, steric relief, and electronic localization of L2 induces a chiral environment imparted through the amine with a computed inversion barrier of 10.3 kcal mol-1.

Reductive defluorination of graphite monofluoride by weak, non-nucleophilic reductants reveals low-lying electron-accepting sites.

Graphite monofluoride (GF) can undergo reductive defluorination in the presence of weak, non-nucleophilic reductants. This leads to a new approach to GF-polyaniline composites as cathode materials for significantly improving the discharge capacity of primary lithium batteries. We postulate that the reduction is mediated by residual π-bonds in GF.

Correction to: Total disc replacement versus fusion for lumbar degenerative disc disease: a systematic review of overlapping meta-analyses.

The authors declare that when writing their article [1] they referenced two previously published papers [2, 3]. Several sentences on pages 807, 808, and 813 were similar to sentences from these two previously published articles.

Cyanide Ligand Assembly by Carbon Atom Transfer to an Iron Nitride.

The new iron(IV) nitride complex PhB(iPr2Im)3Fe≡N reacts with 2 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) to provide PhB(iPr2Im)3Fe(CN)(N2)(BAC). This unusual example of a four-electron reaction involves carbon atom transfer from BAC to create a cyanide ligand along with the alkyne iPr2N-C≡C-NiPr2. The iron complex is in equilibrium with an N2-free species. Further reaction with CO leads to formation of a CO analogue, which can be independently prepared using NaCN as the cyanide source, while reaction with B(C6F5)3 provides the cyanoborane derivative.

Total disc replacement versus fusion for lumbar degenerative disc disease: a systematic review of overlapping meta-analyses.

PURPOSE: Although many meta-analyses have been performed to compare total disc replacement (TDR) and fusion for treating lumbar degenerative disc disease (LDDD), their findings are inconsistent. This study aimed to conduct a systematic review of overlapping meta-analyses comparing TDR with fusion for treating LDDD, to assist decision makers in selection among conflicting meta-analyses, and to provide treatment recommendations based on the best available evidence. METHODS: This study was conducted following the Preferred Reporting Items for Systematic Reviews and Meta-Analysis (PRISMA) statement. Multiple databases were comprehensively searched for meta-analyses comparing TDR with fusion for treating LDDD. Meta-analyses only comprising randomised controlled trials (RCTs) were included. Two authors independently assessed meta-analysis quality and extracted data. The Jadad decision algorithm was used to ascertain which meta-analyses represented the best evidence. RESULTS: A total of five meta-analyses were included. All these studies only included RCTs were determined as Level-II evidence. The scores of Assessment of Multiple Systematic Reviews (AMSTAR) ranged from 6 to 9 (median 7). A high-quality Cochrane review was chosen according to the Jadad algorithm. This best available evidence found that statistical significances were observed between TDR and fusion for LDDD regarding disability, pain relief, and pain in the short term, but it was not over clinically important differences. The prevent effects on adjacent segment and facet joint degeneration, as the primary goal of adopting TDR stated by the manufacturers, were not appropriately evaluated. CONCLUSIONS: There is discord in results from meta-analyses that assessed TDR and fusion for LDDD. According to this systematic review of overlapping meta-analyses comparing TDR and fusion for LDDD, the current best available evidence suggests that TDR may be an effective technique for the treatment of selected patients with LDDD, and is at least equal to lumbar fusion in the short term. However, considering that disadvantages may appear after years, spine surgeons should be cautions about performing TDR on a large scale.

Addition of Si-H and B-H bonds and redox reactivity involving low-coordinate nitrido-vanadium complexes.

In this study we enumerate the reactivity for two molecular vanadium nitrido complexes of [(nacnac)V≡N(X)] formulation [nacnac = (Ar)NC(Me)CHC(Me)(Ar)(-), Ar = 2,6-(CHMe2)2C6H3); X(-) = OAr (1) and N(4-Me-C6H4)2 (Ntolyl2) (2)]. Density functional theory calculations and reactivity studies indicate the nitride motif to have nucleophilic character, but where the nitrogen atom can serve as a conduit for electron transfer, thus allowing the reduction of the vanadium(V) metal ion with concurrent oxidation of the incoming substrate. Silane, H2SiPh2, readily converts the nitride ligand in 1 into a primary silyl-amide functionality with concomitant two-electron reduction at the vanadium center to form the complex [(nacnac)V{N(H)SiHPh2}(OAr)] (3). Likewise, addition of the B-H bond in pinacolborane to the nitride moiety in 2 results in formation of the boryl-amide complex [(nacnac)V{N(H)B(pinacol)}(Ntolyl2)] (4). In addition to spectroscopic data, complexes 3 and 4 were also elucidated structurally by single-crystal X-ray diffraction analysis. One-electron reduction of 1 with 0.5% Na/Hg on a preparative scale allowed for the isolation and structural determination of an asymmetric bimolecular nitride radical anion complex having formula [Na]2[(nacnac)V(N)(OAr)]2 (5), in addition to room-temperature solution X-band electron paramagnetic resonance spectroscopic studies.

[(F6acac)Pd(µ-HNC6F5)]2, a Large Family of Polymorphs and Solvates with Short F···F Contacts.

Highly fluorinated [(F6acac)Pd(µ-HNC6F5)]2 was prepared by the reaction of palladium bis(hexafluoroacetylacetonate), Pd(F6acac)2, with pentafluoroaniline. This compound generates a large family of crystalline polymorphs and solvates. In this paper, we present a study on the synthesis, solution phase dynamics, and crystal structures of highly fluorinated [(F6acac)Pd(µ-HNC6F5)]2. Pd3(µ-F6acac)2(µ-HNC6F5)4 is produced as a minor byproduct. We also describe the synthesis and structural characterization of trinuclear Pd3(µ-F6acac)3[µ-(CF3)2C=N]3 prepared by the reaction of Pd(F6acac)2 with hexafluoroacetone imine.

Room temperature dehydrogenation of ethane, propane, linear alkanes C4-C8, and some cyclic alkanes by titanium-carbon multiple bonds.

The transient titanium neopentylidyne, [(PNP)Ti≡C(t)Bu] (A; PNP(-)≡N[2-P(i)Pr2-4-methylphenyl]2(-)), dehydrogenates ethane to ethylene at room temperature over 24 h, by sequential 1,2-CH bond addition and ß-hydrogen abstraction to afford [(PNP)Ti(η(2)-H2C═CH2)(CH2(t)Bu)] (1). Intermediate A can also dehydrogenate propane to propene, albeit not cleanly, as well as linear and volatile alkanes C4-C6 to form isolable α-olefin complexes of the type, [(PNP)Ti(η(2)-H2C═CHR)(CH2(t)Bu)] (R = CH3 (2), CH2CH3 (3), (n)Pr (4), and (n)Bu (5)). Complexes 1-5 can be independently prepared from [(PNP)Ti═CH(t)Bu(OTf)] and the corresponding alkylating reagents, LiCH2CHR (R = H, CH3(unstable), CH2CH3, (n)Pr, and (n)Bu). Olefin complexes 1 and 3-5 have all been characterized by a diverse array of multinuclear NMR spectroscopic experiments including (1)H-(31)P HOESY, and in the case of the α-olefin adducts 2-5, formation of mixtures of two diastereomers (each with their corresponding pair of enantiomers) has been unequivocally established. The latter has been spectroscopically elucidated by NMR via C-H coupled and decoupled (1)H-(13)C multiplicity edited gHSQC, (1)H-(31)P HMBC, and dqfCOSY experiments. Heavier linear alkanes (C7 and C8) are also dehydrogenated by A to form [(PNP)Ti(η(2)-H2C═CH(n)Pentyl)(CH2(t)Bu)] (6) and [(PNP)Ti(η(2)-H2C═CH(n)Hexyl)(CH2(t)Bu)] (7), respectively, but these species are unstable but can exchange with ethylene (1 atm) to form 1 and the free α-olefin. Complex 1 exchanges with D2C═CD2 with concomitant release of H2C═CH2. In addition, deuterium incorporation is observed in the neopentyl ligand as a result of this process. Cyclohexane and methylcyclohexane can be also dehydrogenated by transient A, and in the case of cyclohexane, ethylene (1 atm) can trap the [(PNP)Ti(CH2(t)Bu)] fragment to form 1. Dehydrogenation of the alkane is not rate-determining since pentane and pentane-d12 can be dehydrogenated to 4 and 4-d12 with comparable rates (KIE = 1.1(0) at ~29 °C). Computational studies have been applied to understand the formation and bonding pattern of the olefin complexes. Steric repulsion was shown to play an important role in determining the relative stability of several olefin adducts and their conformers. The olefin in 1 can be liberated by use of N2O, organic azides (N3R; R = 1-adamantyl or SiMe3), ketones (O═CPh2; 2 equiv) and the diazoalkane, N2CHtolyl2. For complexes 3-7, oxidation with N2O also liberates the α-olefin.

An intussusception caused by a rare transverse colon lipoma: Case report.

INTRODUCTION: Intestinal lipoma is a rare benign tumor with a reported incidence of 0.2 % to 4.4 %. It is seen mainly in patients aged 50 to 70 years. Intestinal lipoma as a pathological lead point of intussusception is rare. There are few reports of colic lipoma in children. PRESENTATION OF CASE: We reported a 7-year-old girl with a 4-year history of intermittent abdominal pain. Ultrasound examination showed a homogeneous hyperechoic mass near the distal transverse colon, which was similar to the surrounding lipid tissue. Histopathological examination confirmed the diagnosis of intestinal lipoma. DISCUSSION: Colonic lipoma is very rare in children. If intussusception occurs repeatedly, or if it occurs in older children, we should consider the presence of pathological lead point. Early diagnosis and immediate surgical intervention are the key factors to a successful outcome. CONCLUSION: In this case we report a pediatric case of intussusception secondary to colonic lipoma, and describe imaging and pathologic signs suggestive of intestinal lipoma.

Biomimetic porous scaffolds containing decellularized small intestinal submucosa and Sr2+/Fe3+co-doped hydroxyapatite accelerate angiogenesis/osteogenesis for bone regeneration.

The design of bone scaffolds is predominately aimed to well reproduce the natural bony environment by imitating the architecture/composition of host bone. Such biomimetic biomaterials are gaining increasing attention and acknowledged quite promising for bone tissue engineering. Herein, novel biomimetic bone scaffolds containing decellularized small intestinal submucosa matrix (SIS-ECM) and Sr2+/Fe3+co-doped hydroxyapatite (SrFeHA) are fabricated for the first time by the sophisticated self-assembled mineralization procedure, followed by cross-linking and lyophilization post-treatments. The results indicate the constructed SIS/SrFeHA scaffolds are characterized by highly porous structures, rough microsurface and improved mechanical strength, as well as efficient releasing of bioactive Sr2+/Fe3+and ECM components. These favorable physico-chemical properties endow SIS/SrFeHA scaffolds with an architectural/componential biomimetic bony environment which appears to be highly beneficial for inducing angiogenesis/osteogenesis bothin vitroandin vivo. In particular, the cellular functionality and bioactivity of endotheliocytes/osteoblasts are significantly enhanced by SIS/SrFeHA scaffolds, and the cranial defects model further verifies the potent ability of SIS/SrFeHA to acceleratein vivovascularization and bone regeneration following implantation. In this view these results highlight the considerable angiogenesis/osteogenesis potential of biomimetic porous SIS/SrFeHA scaffolds for inducing bone regeneration and thus may afford a new promising alternative for bone tissue engineering.

4-Hexylresorcinol inhibits osteoclastogenesis by suppressing the NF-κB signaling pathway and reverses bone loss in ovariectomized mice.

4-Hexylresorcinol (4HR) is a small organic compound that is widely used as an antiseptic and antioxidant. In the present study, its role in osteoclastogenesis was investigated. Bone marrow-derived macrophages from mice were used to examine the role of 4HR in osteogenesis. An ovariectomy (OVX) mouse model was constructed to examine the effect of 4HR in vivo, followed by hematoxylin and eosin and tartrate resistant acid phosphatase staining. In the present study, 4HR effectively suppressed receptor activator of NF-κB ligand-induced osteoclastogenesis in a dose-dependent manner. 4HR was also found to significantly suppress the expression of osteoclast (OC)-specific markers, including tartrate-resistant acid phosphatase, cathepsin K, nuclear factor of activated T-cell cytoplasmic 1 and c-Fos in the presence of RANKL in BMMs. Furthermore, 4HR inhibited osteoclastogenesis by inhibiting the activation of the NF-κB signaling pathway in BMMs. Consistent with the in vitro results, 4HR effectively ameliorated OVX-induced bone loss and markedly reduced OC number in the proximal tibia in vivo. In conclusion, the present results suggested that 4HR inhibited osteoclastogenesis in vitro and rescued bone loss in vivo, suggesting that 4HR may serve as a novel therapeutic agent for osteoporosis treatment.

Bcl-xL mutant promotes cartilage differentiation of BMSCs by upregulating TGF-ß/BMP expression levels.

Bcl-xL is a transmembrane molecule in the mitochondria, with apoptosis-related and pro-metabolic functions, that also plays a role in chondrogenesis and differentiation. A Bcl-xL mutant, in which the GRI sequence is replaced by ELN, has no anti-apoptotic effect, while other biological functions of this mutant remain unchanged. The present study investigated the impact of this Bcl-xL mutant on cartilage differentiation and the expression levels of TGF-ß and bone morphogenetic protein (BMP). Human bone marrow mesenchymal stem cells (BMSCs) were transfected with Bcl-xL and Bcl-xL mutant (∆Bcl-xL) overexpression vectors. The cells were divided into four groups: Control (not subjected to any transfection), EV (empty pcDNA3.1-Bcl-xL vector), OV (Bcl-xL overexpression) and ∆OV (∆Bcl-xL overexpression). Saffron and toluidine blue staining was performed to observe cartilage tissue formation. Flow cytometry was conducted to measure BMSC apoptosis. The expression levels of TGF-ß and BMP were evaluated using reverse transcription-quantitative PCR (RT-qPCR) and western blotting. Compared with that in the control group, the expression levels of Bcl-xL in the OV group increased significantly (P<0.05). Western blotting and RT-qPCR results revealed that OV and ∆OV treatment increased the expression levels of TGF-ß and BMP in transfected cells, compared to their expression in the control and EV groups (P<0.05). Saffron and toluidine blue staining results showed that cartilage formation was increased in the ∆OV and ∆OV + Bax-/Bak-groups to similar degrees. Cell apoptosis in the ∆OV group did not change compared with that in the control group. The Bcl-xL mutant promoted cartilage differentiation of BMSCs and upregulated TGF-ß/BMP expression. This enhancement of chondrogenic differentiation was not related to the expression of Bax and Bak. Taken together, these findings provided for improved application of bone tissue engineering technology in the treatment of articular cartilage defects.

Nickel-mediated N-N bond formation and N2O liberation via nitrogen oxyanion reduction.

The syntheses of (DIM)Ni(NO3)2 and (DIM)Ni(NO2)2, where DIM is a 1,4-diazadiene bidentate donor, are reported to enable testing of bis boryl reduced N-heterocycles for their ability to carry out stepwise deoxygenation of coordinated nitrate and nitrite, forming O(Bpin)2. Single deoxygenation of (DIM)Ni(NO2)2 yields the tetrahedral complex (DIM)Ni(NO)(ONO), with a linear nitrosyl and κ1-ONO. Further deoxygenation of (DIM)Ni(NO)(ONO) results in the formation of dimeric [(DIM)Ni(NO)]2, where the dimer is linked through a Ni-Ni bond. The lost reduced nitrogen byproduct is shown to be N2O, indicating N-N bond formation in the course of the reaction. Isotopic labelling studies establish that the N-N bond of N2O is formed in a bimetallic Ni2 intermediate and that the two nitrogen atoms of (DIM)Ni(NO)(ONO) become symmetry equivalent prior to N-N bond formation. The [(DIM)Ni(NO)]2 dimer is susceptible to oxidation by AgX (X = NO3 -, NO2 -, and OTf-) as well as nitric oxide, the latter of which undergoes nitric oxide disproportionation to yield N2O and (DIM)Ni(NO)(ONO). We show that the first step in the deoxygenation of (DIM)Ni(NO)(ONO) to liberate N2O is outer sphere electron transfer, providing insight into the organic reductants employed for deoxygenation. Lastly, we show that at elevated temperatures, deoxygenation is accompanied by loss of DIM to form either pyrazine or bipyridine bridged polymers, with retention of a BpinO- bridging ligand.