Near-infrared light activated release of nitric oxide from designed photoactive manganese nitrosyls: strategy, design, and potential as NO donors.

Two new manganese complexes derived from the pentadentate ligand N,N-bis(2-pyridylmethyl)amine-N-ethyl-2-quinoline-2-carboxamide, PaPy2QH, where H is dissociable proton), namely, [Mn(PaPy2Q)(NO)]ClO4 (2) and [Mn(PaPy2Q)(OH)]ClO4 (3), have been synthesized and structurally characterized. The Mn(III) complex [Mn(PaPy2Q)(OH)]ClO4 (3), though insensitive to dioxygen, reacts with nitric oxide (NO) to afford the nitrosyl complex [Mn(PaPy2Q)(NO)]ClO4 (2) via reductive nitrosylation. This diamagnetic {Mn-NO}6 nitrosyl exhibits nuNO at 1725 cm-1 and is highly soluble in water, with lambdamax at 500 and 670 nm.

Vinyl sulfones.

Four neutral vinyl sulfones, two of which are paired with phosphonate groups, are described. The compounds are diisopropyl (2-phenylethenylsulfonylmethyl)phosphonate, C(15)H(23)O(5)PS, (I), diisopropyl {[2-(7-methoxy-1,3-benzodioxol-5-yl)ethenylsulfonyl]methylsulfonylmethyl}phosphonate, C(18)H(27)O(10)PS(2), (II), bis(trans-2-phenylethenyl) sulfone, C(16)H(14)O(2)S, (III), and bis(trans-2-phenylethenylsulfonyl)methane, C(17)H(16)O(4)S(2), (IV). Their structures can be considered as highly functionalized mimics of mono-, di- and triphosphates.

New egg-shaped fullerenes: non-isolated pentagon structures of Tm3N@C(s)(51 365)-C84 and Gd3N@C(s)(51 365)-C84.

Although there are 51 568 non-IPR and 24 IPR structures for C84, the egg-shaped endohedral fullerenes Tm3N@C(s)(51 365)-C84 and Gd3N@C(s)(51 365)-C84 utilize the same non-IPR cage structure as found initially for Tb3N@C(s)(51 365)-C84.

Disorder and intermolecular interactions in a family of tetranuclear Ni(II) complexes probed by high-frequency electron paramagnetic resonance.

High-frequency electron paramagnetic resonance (HFEPR) data are presented for four closely related tetranuclear Ni(II) complexes, [Ni(hmp)(MeOH)Cl]4.H2O (1a), [Ni(hmp)(MeOH)Br]4.H2O (1b), [Ni(hmp)(EtOH)Cl]4.

Internal and external factors in the structural organization in cocrystals of the mixed-metal endohedrals (GdSc2N@Ih-C80, Gd2ScN@Ih-C80, and TbSc2N@Ih-C80) and nickel(II) octaethylporphyrin.

Structural characterizations of three new mixed-metal endohedrals, GdSc 2N@ I h -C80, Gd 2ScN@ I h -C80, and TbSc 2@ I h -C80, have been obtained by single-crystal X-ray diffraction on GdSc 2N@ I h -C80 x Ni (II)(OEP) x 2C 6H 6, Gd 2ScN@ I h -C 80 x Ni(II)(OEP) x 2C6H6, and TbSc 2N@ I h -C80 x Ni (II)(OEP) x 2C6H6. All three have I h -C 80 cages and planar MM' 2N units. The central nitride ion is positioned further from the larger Gd3+ or Tb3+ ions and closer to the smaller Sc3+ ions.

Creatininium bis-(pyridine-2,6-dicarboxyl-ato)chromate(III) pyridine-2,6-dicarboxylic acid hexa-hydrate.

The title compound, (C(4)H(8)N(3)O)[Cr(C(7)H(3)NO(4))(2)]·C(7)H(5)NO(4)·6H(2)O, was obtained by the reaction of Cr(NO(3))(3)·9H(2)O with pyridine-2,6-dicarboxylic acid (pydcH(2)) and creatinine (creat) in aqueous solution (molar ratio 1:2:2). The cation is a protonated creatinine (creatH(+)) while the anion is a bis-pydc(2-) Cr(III) complex. The Cr(III) is coordinated by four oxygen and two nitro-gen atoms of two (pydc)(2-) groups and has a disorted octa-hedral coordination environment.

Bis[1-(1-adamantyliminomethyl)-2-naphtholato-κN,O]cobalt(II).

The title compound, [Co(C(21)H(22)NO)(2)], crystallizes with two mol-ecules in the asymmetric unit. The coordination environments of the two Co(II) ions are distorted tetra-hedral. The primary structural difference between the two independent complex mol-ecules lies in the orientations of their adamantyl groups.

Influence of sulfur oxidation state and steric bulk upon trifluoromethyl ketone (TFK) binding kinetics to carboxylesterases and fatty acid amide hydrolase (FAAH).

Carboxylesterases metabolize numerous exogenous and endogenous ester-containing compounds including the chemotherapeutic agent CPT-11, anti-influenza viral agent oseltamivir, and many agrochemicals. Trifluoromethyl ketone (TFK)-containing compounds with a sulfur atom beta to the ketone moiety are some of the most potent carboxylesterase and amidase inhibitors identified to date. This study examined the effects of alkyl chain length (i.

Cannabinoid-induced tolerance is associated with a CB1 receptor G protein coupling switch that is prevented by ultra-low dose rimonabant.

The analgesic effect of opioids is enhanced, and tolerance is attenuated, by ultra-low doses (nanomolar to picomolar) of an opioid antagonist, an effect that is mediated by preventing the receptor from coupling to Gs proteins. Recently, we demonstrated a cannabinoid-opioid interaction at the ultra-low dose level, suggesting that the effect might not be specific to opioid receptors. The purpose of this study was to examine, both behaviorally and mechanistically, whether the cannabinoid CB1 receptor was also sensitive to ultra-low dose effects.

Intact preference conditioning in acute intoxication despite deficient declarative knowledge and working memory.

Background: The impact of alcohol on implicit, emotional learning is not well understood, partly because family history, drug use, and task demands influence these processes. The conditioned pattern preference (CPP) task provides a more ecologically valid means to investigate implicit cognition in the lab because it has low demand awareness and relies on learning to associate nonverbal cues with reward.

Methods: This study examined the effects of acute alcohol intoxication on implicit learning using the CPP task in 83 intoxicated and 69 sober young adults.

Adventures in crystallization. Crystalline salts containing one, two, or even three chemically distinct cations obtained from solutions of [(cyclohexyl isocyanide)(4)Rh(I)]+.

By judicious selection of crystallization conditions, it has been possible to obtain the salts of a common building block, [(RNC)4Rh(I)]+, in single-crystal form suitable for X-ray diffraction. Salts that contain a single type of cation include deep green [(C6H11NC)12Rh(I)3](SbF6)3, deep green [(C6H11NC)12Rh(I)3](AsF6)3, and straw yellow [(C6H11NC)8Rh(II)2Cl2](BF4)2 (in addition to the previously isolated trimeric deep green [(i-PrNC)12RhI3]Cl3 x 4.5 H2O, monomeric, [(C6H11NC)4 Rh(I)](BPh4), and [(i-PrNC)4Rh(I)](BPh4) (both yellow), and red, dimeric [(C6H11NC)8Rh(I)2]Cl2 x 0.

Synthesis and characterization of the homologous M-M bonded series Ar'MMAr' (M = Zn, Cd, or Hg; Ar' = C6H3-2,6-(C6H3-2,6-Pr(i)2)2) and related arylmetal halides and hydride species.

The synthesis and structural characterization of the first homologous, molecular M-M bonded series for the group 12 metals are reported. The compounds Ar'MMAr' (M = Zn, Cd, or Hg; Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) were synthesized by reduction of the corresponding arylmetal halides by alkali metal/graphite (Zn or Hg) or sodium hydride (Cd). These compounds possess almost linear C-M-M-C core structures with two-coordinate metals.

Sc3N@C78: encapsulated cluster regiocontrol of adduct docking on an ellipsoidal metallofullerene sphere.

The first N-tritylpyrrolidino derivatives of D(3h) (78:5) Sc(3)N@C(78) were successfully synthesized and isolated. The addition sites for the two nearly equivalent kinetic monoadducts 1a and 1b are across two different 6,6 junction sites on the Sc(3)N@C(78) cage that are offset from the horizontal plane defined by the Sc(3)N cluster. The adducts were characterized by NMR experiments, DFT calculations and X-ray crystallographic analysis of Sc(3)N@C(78) derivative 1a.

"Open rather than closed" malonate methano-fullerene derivatives. The formation of methanofulleroid adducts of Y3N@C80.

Cycloaddition of bromomalonates to Y3N@C80 unexpectedly gave rise to fulleroid derivatives with unusually high stability. Complete characterization of these derivatives is described including X-ray crystallography, 1H NMR, 13C NMR, HMQC, UV-visible, HPLC, MALDI-MS, and electrochemistry. Density functional theory calculations are also presented, which provide a rationale for the formation of the fulleroid and reveal the underlying thermodynamic basis for their stability.

Synthesis and structural characterization of cross-linked histidine-phenol Cu(ii) complexes as cytochrome c oxidase active site models.

Tridentate cross-linked histidine-phenol Cu(ii) ether and ester complexes, chemical analogs of the active site of several heme-copper oxidases, have been synthesized and crystallized.

Asymmetric dinuclear copper(I) complexes of bis-(2-(2-pyridyl)ethyl)-2-(N-toluenesulfonylamino)ethylamine with short copper-copper distances.

Addition of two equivalents of CuCl to deprotonated bis-(2-(2-pyridyl)ethyl)-2-(N-toluenesulfonylamino)ethylamine (PETAEA) and its derivatives yielded new types of dinuclear Cu(I) complexes, Cu(mu-PETAEA)CuCl, Cu(mu-PEMAEA)CuCl, and Cu(mu-PENAEA)CuCl (PEMAEA is the 4-methoxyphenyl derivative of PETAEA and PENAEA is the 4-nitrophenyl derivative), exhibiting a four coordinate N(4)Cu center, a two coordinate NCuCl center, and a metal-metal distance within the range of 2.6572(8) to 2.6903(3) A.

Incorporation of a designed ruthenium nitrosyl in PolyHEMA hydrogel and light-activated delivery of NO to myoglobin.

A ruthenium nitrosyl with 4-vinylpyridine (4-vpy) as one ligand, namely, [Ru(Me2bpb)(NO)(4-vpy)](BF4) (1), has been synthesized and structurally characterized. This diamagnetic {Ru-NO}6 nitrosyl is photoactive and readily releases NO upon exposure to low-intensity (5-10 mW) UV light (quantum yield at 300 nm = 0.18).

A study of piperidinium structure-directing agents in the synthesis of silica molecular sieves under fluoride-based conditions.

This study is a continuation of our efforts to understand the interplay in the self-assembly chemistry for formation of molecular sieves from guest organocations and inorganic silicon oxide. In this particular study we focus on the competitive interplay of the organocations and the synthesis cofactor fluoride anion. The anions play a key role in structure determination, as a function of net solution concentration.

Repeated exposure to stress across the childhood-adolescent period alters rats' anxiety- and depression-like behaviors in adulthood: The importance of stressor type and gender.

This research tests the hypothesis that specific forms of adversity in early life map onto behavioral signs analogous to depression versus anxiety in later life. Male and female rats were exposed to either severe sporadic stress or chronic mild stress during the childhood-adolescent period, and their behavior was tested in adulthood. Males in the severe sporadic stress group showed exaggerated anxiety-related behaviors, as indicated by increases in shock-probe burying and escape-like responses (jumps) from the open arms of the elevated plus-maze.

Synthesis and characterization of low-coordinate divalent aryl transition-metal halide analogues of grignard reagents: precursors for reduction to metal-metal-bonded complexes.

The synthesis and characterization of the series of divalent first-row aryl transition-metal(II) halide compounds [Cr(mu-Cl)Ar']2 (1) and (Li(OEt2)Ar'MI2]2 (M=Mn (2), Fe (3), and Co (4); Ar'=C6H3-2,6-(C6H3-2,6-iPr2)2) are described. 1-4 were prepared by the addition of one equiv of Ar'Li to the respective transition-metal dihalides. They were characterized by UV-vis spectroscopy, magnetic measurements, and by X-ray crystallography.

Synthesis, characterization, and electrochemical studies of beta,beta'-fused metallocenoporphyrins.

Beta,beta'-Fused monoruthenocenylporphyrins, Cp*Ru(III)[1,2-[M(II)-5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)-porphyrinato]-3-methyl-cyclopentadienide] (M = Ni (20), Cu (21), Zn (22)), and bisferrocenoporphyrins, Fe(II) bis[1,2-[M(II)-5,10,15,20-tetraphenylporphyrinato]-3-methyl-cyclopentadienide] (M = Ni (24), Cu (25), Zn (26)), were synthesized and characterized. A novel synthetic approach to beta,beta'-fused porphyrins through Pd(0)-catalyzed [3 + 2] cycloaddition was implemented in this work. UV-vis spectra of these compounds show largely broadened and red-shifted bands (relative to their precursors) indicating potential electronic communication between the attached organometallic moiety and the porphyrin core.

Ruthenium nitrosyls derived from polypyridine ligands with carboxamide or imine nitrogen donor(s): isoelectronic complexes with different NO photolability.

As part of our search for photoactive ruthenium nitrosyls, a set of {RuNO}6 nitrosyls has been synthesized and structurally characterized. In this set, the first nitrosyl [(SBPy3)Ru(NO)](BF4)3 (1) is derived from a polypyridine Schiff base ligand SBPy3, while the remaining three nitrosyls are derived from analogous polypyridine ligands containing either one ([(PaPy3)Ru(NO)](BF4)2 (2)) or two ([(Py3P)Ru(NO)]BF4 (3) and [(Py3P)Ru(NO)(Cl)] (4)) carboxamide group(s). The coordination structures of 1 and 2 are very similar except that in 2, a carboxamido nitrogen is coordinated to the ruthenium center in place of an imine nitrogen in case of 1.