In this report, we describe in detail the O(2)-binding chemistry of the metalloporphyrin (F(8)TPP)Fe(II) (1). This complex was synthesized from aqueous dithionite reduction of (F(8)TPP)Fe(III)-Cl (X-ray structure reported: C(55)H(36)ClF(8)FeN(4)O; a = 13.6517(2) A, b = 13.6475(2) A, c = 26.3896(4), alpha = 90 degrees, beta = 89.9776(4) degrees, gamma = 90 degrees; monoclinic, P2(1)/c, Z = 4). Complex 1 crystallizes from toluene/heptane solvent system as a bis(toluene) solvate, (F(8)TPP)Fe(II).(C(7)H(8))(2), with ferrous ion in the porphyrin plane (C(58)H(36)F(8)FeN(4); a = 20.9177(2) A, b = 11.7738(2) A, c = 19.3875(2), alpha = 90 degrees, beta = 108.6999(6) degrees, gamma = 90 degrees; monoclinic, C2/c, Z = 4; Fe-N(4)(av) = 2.002 A; N-Fe-N (all) = 90.0 degrees ). Close metal-arene contacts are also observed at 3.11-3.15 A. Upon oxygenation of 1 at 193 K in coordinating solvents, UV-visible and (2)H and (19)F NMR spectroscopies revealed the presence of a reversibly formed dioxygen adduct, formulated as the heme-superoxo complex (S)(F(8)TPP)Fe(III)-(O(2)(-)) (2) (S = solvent) [(i) tetrahydrofuran (THF) solvent: UV-visible, 416 (Soret), 536 nm; (2)H NMR: delta(pyrrole) 8.9 ppm; (ii) EtCN solvent: UV-visible, 414 (Soret), 536 nm; (iii) acetone solvent: UV-visible, 416 (Soret), 537 nm; (2)H NMR: delta(pyrrole) 8.9 ppm]. Dioxygen-uptake manometry (THF, 193 K) revealed an O(2):1 oxygenation stoichiometry of 1.02:1, consistent with the heme-superoxo formulation of 2. Stopped-flow UV-visible spectrophotometry studies of the (F(8)TPP)Fe(II) (1)/O(2) reaction in EtCN and THF solvents were able to provide kinetic and thermodynamic insight into the reversible formation of 2 [(i) EtCN: Delta H degrees = -40 +/- 5 kJ/mol; Delta S degrees = -105 +/- 23 J/(K mol); k(1) = (5.57 +/- 0.04) x 10(3) M(-)(1) s(-)(1) (183 K); Delta H(++) = 38.6 +/- 0.2 kJ/mol; Delta S(++) = 42 +/- 1 J/(K mol); (ii) THF: Delta H* = -37.5 +/- 0.4 kJ/mol; Delta S* = -109 +/- 2 J/(K mol)]. The (F(8)TPP)Fe(II) (1)/O(2) reaction was also examined at reduced temperatures in noncoordinating solvents (toluene, CH(2)Cl(2)), where UV-visible and (2)H and (19)F NMR spectroscopies also revealed the presence of a reversibly formed adduct, formulated as the peroxo-bridged dinuclear complex [(F(8)TPP)Fe(III)](2)-(O(2)(2)(-)) (3) [CH(2)Cl(2): UV-visible, 414 (Soret), 535 nm; (2)H NMR, delta(pyrrole) 17.5 ppm]. Dioxygen-uptake spectrophotometric titrations revealed a stoichiometry of 2 (F(8)TPP)Fe(II) (1) per O(2) upon full formation of 3. Addition of a nitrogenous base, 4-(dimethylamino)pyridine, to a cold solution of 3 in dichloromethane gave rapid formation of the iron(IV)-oxo ferryl species (DMAP)(F(8)TPP)Fe(IV)==O (4), based upon UV-visible [417 (Soret), 541 nm] and (2)H NMR (delta(pyrrole) = 3.5 ppm) spectroscopic characterization. These detailed investigations into the O(2)-adducts and "ferryl" species formed from (F(8)TPP)Fe(II) (1) may be potentially important for a full understanding of our ongoing heme-copper oxidase model studies, which employ 1 or similar "...

We report the rare case of an acute intracranial subdural hematoma caused by a CSF leak following lumbar surgery. This report illustrates the potential morbidity associated with CSF leaks occurring after spinal surgery.

Carbon monoxide readily binds to heme and copper proteins, acting as a competitive inhibitor of dioxygen. As such, CO serves as a probe of protein metal active sites. In our ongoing efforts to mimic the active site of cytochrome c oxidase, reactivity toward carbon monoxide offers a unique opportunity to gain insight into the binding and spectroscopic characteristics of synthetic model compounds. In this paper, we report the synthesis and characterization of CO-adducts of ((5/6)L)Fe(II), [((5/6)L)Fe(II)...Cu(I)](B(C(6)F(5))(4)), and [(TMPA)Cu(I)(CH(3)CN)](B(C(6)F(5))(4)), where TMPA = tris(2-pyridylmethyl)amine and (5/6)L = a tetraarylporphyrinate tethered in either the 5-position ((5)L) or 6-position ((6)L) to a TMPA copper binding moiety. Reaction of ((5/6)L)Fe(II) [in THF (293 K): UV-vis 424 (Soret), 543-544 nm; (1)H NMR delta(pyrrole) 52-59 ppm (4 peaks); (2)H NMR (from ((5)L-d(8))Fe(II)) delta(pyrrole) 53.3, 54.5, 55.8, 56.4 ppm] with CO in solution at RT yielded ((5/6)L)Fe(II)-CO [in THF (293 K): UV-vis 413-414 (Soret), 532-533 nm; IR nu(CO)(Fe) 1976-1978 cm(-1); (1)H NMR delta(pyrrole) 8.8 ppm; (2)H NMR (from ((5)L-d(8))Fe(II)-CO) delta(pyrrole) 8.9 ppm; (13)C NMR delta((CO)Fe) 206.8-207.1 ppm (2 peaks)]. Experiments repeated in acetonitrile, acetone, toluene, and dichloromethane showed similar spectroscopic data. Binding of CO resulted in a change from five-coordinate, high-spin Fe(II) to six-coordinate, low-spin Fe(II), as evidenced by the upfield shift of the pyrrole resonances to the diamagnetic region ((1)H and (2)H NMR spectra). Addition of CO to [((5/6)L)Fe(II)...Cu(I)](B(C(6)F(5))(4)) [in THF (293 K): UV-vis ((6)L only) 424 (Soret), 546 nm; (1)H NMR delta(pyrrole) 54-59 ppm (multiple peaks); (2)H NMR (from [((5)L-d(8))Fe(II).Cu(I)](B(C(6)F(5))(4))) delta(pyrrole) 53.4 ppm (br)] gave the bis-carbonyl adduct [((5/6)L)Fe(II)-CO...Cu(I)-CO](B(C(6)F(5))(4)) [in THF (293 K): UV-vis ((6)L only) 413 (Soret), 532 nm; IR nu(CO)(Fe) 1971-1973 cm(-1), nu(CO)(Cu) 2091-2093 cm(-1), approximately 2070(sh) cm(-1); (1)H NMR delta(pyrrole) 8.7-8.9 ppm; (2)H NMR (from [((5)L-d(8))Fe(II)-CO...Cu(I)-CO](B(C(6)F(5))(4))) delta(pyrrole) 8.9 ppm; (13)C NMR delta((CO)Fe) 206.8-208.1 ppm (2 peaks), delta((CO)Cu) 172.4 ((5)L), 178.2 ((6)L) ppm]. Experiments in acetonitrile, acetone, and toluene exhibited spectral features similar to those reported. The [((5/6)L)Fe(II)-CO.Cu(I)-CO](B(C(6)F(5))(4)) compounds yielded (CO)(Fe) spectra analogous to those seen for ((5/6)L)Fe(II)-CO and (CO)(Cu) spectra similar to those seen for [(TMPA)Cu(I)-CO](B(C(6)F(5))(4)) [in THF (293 K): IR nu(CO)(Cu) 2091 cm(-1), approximately 2070(sh) cm(-1); (13)C NMR delta((CO)Cu) 180.3 ppm]. Additional IR studies were performed in which the [((5)L)Fe(II)-CO...Cu(I)-CO](B(C(6)F(5))(4)) in solution was bubbled with argon in an attempt to generate the iron-only mono-carbonyl [((5)L)Fe(II)-CO.Cu(I)](B(C(6)F(5))(4)) species; in coordinating solvent or with axial base present, decreases in characteristic IR-band intensities revealed complete loss of CO from co...

We present here the synthesis, characterization, and flash photolysis study of [(F(8)TPP)Fe(II)(CO)(THF)] (1) [F(8)TPP = tetrakis(2,6-difluorophenyl)porphyrinate(2-)]. Complex 1 crystallizes from THF/heptane solvent system as a tris-THF solvate, [(F(8)TPP)Fe(II)(CO)(THF)].3THF (1.3THF), with ferrous ion in the porphyrin plane (C(61)H(52)F(8)FeN(4)O(5); a = 11.7908(2) A, b = 20.4453(2) A, c = 39.9423(3), alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees; orthorhombic, P2(1)2(1)2(1), Z = 8; Fe-N(4)(av) = 2.00 A; N-Fe-N (all) = 90.0 degrees ). This complex (as 1.THF) has also been characterized by (1)H NMR [six-coordinate, low-spin heme; CD(3)CN, RT, delta 8.82 (s, pyrrole-H, 8H), 7.89 (s, para-phenyl-H, 8H), 7.46 (s, meta-phenyl-H, 4H), 3.58 (s, THF, 8H), 1.73 (s, THF, 8H)], (2)H NMR (pyrrole-deuterated analogue) [(F(8)TPP-d(8))Fe(II)(CO)(THF)] [THF, RT, delta 8.78 ppm (s, pyrrole-D)], (13)C NMR (on (13)CO-enriched adduct) [THF-d(8), RT, delta 206.5 ppm; CD(2)Cl(2), RT, delta 206.1 ppm], UV-vis [THF, RT, lambda(max), 411 (Soret), 525 nm], and IR [293 K, solution, nu(CO) 1979 cm(-)(1) (THF), 1976 cm(-)(1) (acetone), 1982 cm(-)(1) (CH(3)CN)] spectroscopies. In order to more fully understand the intricacies of solvent-ligand binding (as compared to CO rebinding to the photolyzed heme), we have also synthesized the bis-THF adduct [(F(8)TPP)Fe(II)(THF)(2)]. Complex 2 also crystallizes from THF/heptane solvent system as a bis-THF solvate, [(F(8)TPP)Fe(II)(THF)(2)].2THF (2.2THF), with ferrous iron in the porphyrin plane (C(60)H(52)F(8)FeN(4)O(4); a = 21.3216(3) A, b = 12.1191(2) A, c = 21.0125(2) A, alpha = 90 degrees, beta = 105.3658(5) degrees, gamma = 90 degrees; monoclinic, C2/c, Z = 4; Fe-N(4)(av) = 2.07 A; N-Fe-N (all) = 90.0 degrees ). Further characterization of 2 includes UV-vis [THF, lambda(max), 421 (Soret), 542 nm] and (1)H NMR [six-coordinate, high spin heme; THF-d(8), RT, delta 56.7 (s, pyrrole-H, 8H), 8.38 (s, para-phenyl-H, 8H), 7.15 (s, meta-phenyl-H, 4H)] spectroscopies. Flash photolysis studies employing 1 were able to resolve the CO rebinding kinetics in both THF and cyclohexane solvents. In CO saturated THF [[CO] approximately 5 mM] and at [1] congruent with 5 microM, the conversion of [(F(8)TPP)Fe(II)(THF)(2)] (produced after photolytic displacement of CO) to [(F(8)TPP)Fe(II)(CO)(THF)] was monoexponential, with k(obs) = 1.6 (+/-0.2) x 10(4) s(-)(1). Reduction in [CO] by vigorous Ar purging gave k(obs) congruent with 10(3) s(-)(1) in cyclohexane. The study presented in this report lays the foundation for applying fast-time scale studies based on CO flash photolysis to the more complicated heterobimetallic heme/Cu systems.

Object Parallel advancements in image guidance technology and minimal access techniques continue to push the frontiers of minimally invasive spine surgery (MISS). While traditional intraoperative imaging remains widely used, newer platforms, such as 3D-fluoroscopy, cone-beam CT, and intraoperative CT/MRI, have enabled safer, more accurate instrumentation placement with less radiation exposure to the surgeon. The goal of this work is to provide a review of the current uses of advanced image guidance in MISS. Methods The authors searched PubMed for relevant articles concerning MISS, with particular attention to the use of image-guidance platforms. Pertinent studies published in English were further compiled and characterized into relevant analyses of MISS of the cervical, thoracic, and lumbosacral regions. Results Fifty-two studies were included for review. These describe the use of the iso-C system for 3D navigation during C1–2 transarticular screw placement, the use of endoscopic techniques in the cervical spine, and the role of navigation guidance at the occipital-cervical junction. The authors discuss the evolving literature concerning neuronavigation during pedicle screw placement in the thoracic and lumbar spine in the setting of infection, trauma, and deformity surgery and review the use of image guidance in transsacral approaches. Conclusions Refinements in image-guidance technologies and minimal access techniques have converged on spinal pathology, affording patients the ability to undergo safe, accurate operations without the associated morbidities of conventional approaches. While percutaneous transpedicular screw placement is among the most common procedures to benefit from navigation, other areas of spine surgery can benefit from advances in neuronavigation and further growth in the field of image-guided MISS is anticipated.

Preoperative CT evaluation is important in choosing PS length, diameter, trajectory, and entry point due to variation based on spinal level, patient sex, and side of placement. These data are valuable for resident and fellow training to guide the safe use of thoracic PSs.

Delayed treatment of SAH with controlled-release DETA-NO polymers prevented experimental posthemorrhagic vasospasm in the rabbit. This inhibition was dose-dependent. This further confirms the role of NO in the pathogenesis of vasospasm.

For C3-C6 laminectomy, instrumentation to C7 significantly decreased flexion/extension ROM and intradiscal pressure at C6-C7 without significantly increasing either measure at C2-C3 or C7-T1 relative to C3-C6 fixation. In the setting of a C3-C7 laminectomy, when instrumenting to either C2 or T2, consideration should be given to including both levels within these constructs.