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Objective: To investigate the prognostic significance of thyroid hormone profile in patients hospitalized for decompensated cirrhosis., Subjects and Methods: Prospective cohort study that included 119 subjects. All subjects were evaluated at admission and followed for 90 days. TSH, fT3, fT4 were measured within 24 hours of hospitalization., Results: Higher fT4 and lower fT3 levels were observed among Child-Pugh C patients as compared to Child-Pugh A and B, and in those with acute-on-chronic liver failure (ACLF). Lower fT3/fT4 ratio was observed in those with ascites, infections, ACLF, and in Child-Pugh C. Ninety-day mortality was 26.9% and it was independently associated with higher Model for End-stage Liver Disease (MELD) and TSH, and lower fT3/fT4 ratio in multivariate analysis. A new prognostic model including MELD, TSH and fT3/fT4 ratio was devised. The areas under the receiver operating characteristic curves for MELD, fT3/fT4 ratio, TSH (μIU/mL), and the new model for predicting 90-day mortality were 0.847 ± 0.041, 0.841 ± 0.039, 0.658 ± 0.062, and 0.899 ± 0.031, respectively. The 90-day survival was 31.6% in patients with values of the predictive model ≥ -0.77 and 93.5% for values < -0.77 (P < 0.001)., Conclusions: Thyroid hormone profile was strongly associated with worse outcomes in patients with cirrhosis and might represent promising prognostic tools that can be incorporated in clinical practice., Competing Interests: Disclosure: no potential conflict of interest relevant to this article was reported.

Background and Purpose: Early brain injury is a major determinant of clinical outcome in poor-grade (World Federation of Neurosurgical Societies [WFNS] IV-V) aneurysmal SAH and is radiologically defined by global cerebral edema. Little is known, though, about the effect of global intracranial hemorrhage volume on early brain injury development and clinical outcome., Materials and Methods: Data from the multicentric prospective Poor-Grade Aneurysmal Subarachnoid Hemorrhage (POGASH) Registry of consecutive patients with poor-grade aneurysmal SAH admitted from January 1, 2015, to August 31, 2022, was retrospectively evaluated. Poor grade was defined according to the worst-pretreatment WFNS grade. Global intracranial hemorrhage volume as well as the volumes of intracerebral hemorrhage, intraventricular hemorrhage, and SAH were calculated by means of analytic software in a semiautomated setting. Outcomes included severe global cerebral edema (defined by Subarachnoid Hemorrhage Early Brain Edema Score grades 3-4), in-hospital mortality (mRS 6), and functional independence (mRS 0-2) at follow-up., Results: Among 400 patients (median global intracranial hemorrhage volume of 91 mL; interquartile range, 59-128), severe global cerebral edema was detected in 218/400 (54.5%) patients. One hundred twenty-three (30.8%) patients died during the acute phase of hospitalization. One hundred fifty-five (38.8%) patients achieved mRS 0-2 at a median of 13 (interquartile range, 3-26) months of follow-up. Multivariable analyses showed global intracranial hemorrhage volume as independently associated with severe global cerebral edema (adjusted OR, 1.009; 95% CI, 1.004-1.014; P < .001), mortality (adjusted OR, 1.006; 95% CI, 1.001-1.01; P = .018) and worse clinical outcome (adjusted OR, 0.992; 95% CI, 0.98-0.996; P < .010). The effect of global intracranial hemorrhage volume on clinical-radiologic outcomes changed significantly according to different age groups (younger than 50, 50-70, older than 70 year of age). Volumes of intracerebral hemorrhage, intraventricular hemorrhage, and SAH affected the 3 predefined outcomes differently. Intracerebral hemorrhage volume independently predicted global cerebral edema and long-term outcome, intraventricular hemorrhage volume predicted mortality and long-term outcome, and SAH volume predicted long-term clinical outcome., Conclusions: Global intracranial hemorrhage volume plays a pivotal role in global cerebral edema development and emerged as an independent predictor of both mortality and long-term clinical outcome. Aging emerged as a reducing predictor in the relationship between global intracranial hemorrhage volume and global cerebral edema., (© 2024 by American Journal of Neuroradiology.)

Background: Scarce data are available regarding rebleeding predictors in poor-grade aneurysmal subarachnoid hemorrhage (aSAH)., Objectives: To investigate predictors and clinical impact of rebleeding in a national multicentric poor-grade aSAH., Methods: Retrospective analysis of prospectively collected data from the multicentric Poor Grade Aneurysmal Subarachnoid Hemorrhage Study Group (POGASH) registry of consecutive patients treated from January 1, 2015, to June 30th, 2021. Grading was defined as pretreatment World Federation of Neurological Surgeons grading scale IV-V. Ultra-early vasospasm (UEV) was defined as luminal narrowing of intracranial arteries not due to intrinsic disease. Rebleeding was defined as clinical deterioration with evidence of increased hemorrhage on subsequent computed tomography scans, fresh blood from the external ventricular drain, or deterioration before neuroradiological evaluation. Outcome was assessed by the modified Rankin Scale., Results: Among 443 consecutive World Federation of Neurological Surgeons grades IV-V patients with aSAH treated within a median of 5 (IQR 4-9) hours since onset, rebleeding occurred in 78 (17.6%). UEV (adjusted odds ratio [OR] 6.8, 95% CI 3.2-14.4; P < .001) and presence of dissecting aneurysm (adjusted OR 3.5, 95% CI 1.3-9.3; P = .011) independently predicted rebleeding while history of hypertension (adjusted OR 0.4, 95% CI 0.2-0.8; P = .011) independently reduced its chances. 143 (32.3) patients died during hospitalization. Rebleeding emerged, among others, as an independent predictor of intrahospital mortality (adjusted OR 2.2, 95% CI 1.2-4.1; P = .009)., Conclusion: UEV and presence of dissecting aneurysms are the strongest predictors of aneurysmal rebleeding. Their presence should be carefully evaluated in the acute management of poor-grade aSAH., (Copyright © Congress of Neurological Surgeons 2023. All rights reserved.)

Multidimensional coherent spectroscopy directly unravels multiply excited states that overlap in a linear spectrum. We report multidimensional coherent optical photocurrent spectroscopy in a semiconductor polariton diode and explore the excitation ladder of cavity polaritons. We measure doubly and triply avoided crossings for pairs and triplets of exciton polaritons, demonstrating the strong coupling between light and dressed doublet and triplet semiconductor excitations. These results demonstrate that multiply excited excitonic states strongly coupled to a microcavity can be described as two coupled quantum-anharmonic ladders.

This study reports the thermal analysis of a novel thermal energy storage based on high temperature phase change material (PCM) used to improve efficiency in waste-to-energy plants. Current waste-to-energy plants efficiency is limited by the steam generation cycle which is carried out with boilers composed by water-walls (i.e. radiant evaporators), evaporators, economizers and superheaters. Although being well established, this technology is subjected to limitations related with high temperature corrosion and fluctuation in steam production due to the non-homogenous composition of solid waste; this leads to increased maintenance costs and limited plants availability and electrical efficiency. The proposed solution in this paper consists of replacing the typical refractory brick installed in the combustion chamber with a PCM-based refractory brick capable of storing a variable heat flux and to release it on demand as a steady heat flux. By means of this technology it is possible to mitigate steam production fluctuation, to increase temperature of superheated steam over current corrosion limits (450°C) without using coated superheaters and to increase the electrical efficiency beyond 34%. In the current paper a detailed thermo-mechanical analysis has been carried out in order to compare the performance of the PCM-based refractory brick against the traditional alumina refractory bricks. The PCM considered in this paper is aluminium (and its alloys) whereas its container consists of high density ceramics (such as Al 2 O 3 , AlN and Si 3 N 4 ); the different coefficient of linear thermal expansion for the different materials requires a detailed thermo-mechanical analysis to be carried out to ascertain the feasibility of the proposed technology., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

We demonstrate the potential of spatial light modulators for the spectral control of a broadband source in digital holographic microscopy. Used in a 'pulse-shaping' geometry, the spatial light modulator provides a versatile control over the bandwidth and wavelength of the light source. The control of these properties enables adaptation to various experimental conditions. As a first application, we show that the source bandwidth can be adapted to the off-axis geometry to provide quantitative phase imaging over the whole field of view. As a second application, we generate sequences of appropriate wavelengths for a hierarchical optical phase unwrapping algorithm, which enables the measurement of the topography of high-aspect ratio structures without phase ambiguity. Examples are given with step heights up to 50 µm.

We study an asymmetric double InGaAs quantum well using optical two-dimensional coherent spectroscopy. The collection of zero-quantum, one-quantum, and two-quantum two-dimensional spectra provides a unique and comprehensive picture of the double well coherent optical response. Coherent and incoherent contributions to the coupling between the two quantum well excitons are clearly separated. An excellent agreement with density matrix calculations reveals that coherent interwell coupling originates from many-body interactions.

Multidimensional Coherent Optical Photocurrent Spectroscopy (MD-COPS) is implemented using unstabilized interferometers. Photocurrent from a semiconductor sample is generated using a sequence of four excitation pulses in a collinear geometry. Each pulse is frequency shifted by a unique radio frequency through acousto-optical modulation; the Four-Wave Mixing (FWM) signal is then selected in the frequency domain. The interference of an auxiliary continuous wave laser, which is sent through the same interferometers as the excitation pulses, is used to synthesize reference frequencies for lock-in detection of the photocurrent FWM signal. This scheme enables the partial compensation of mechanical fluctuations in the setup, achieving sufficient phase stability without the need for active stabilization. The method intrinsically provides both the real and imaginary parts of the FWM signal as a function of inter-pulse delays. This signal is subsequently Fourier transformed to create a multi-dimensional spectrum. Measurements made on the excitonic resonance in a double InGaAs quantum well embedded in a p-i-n diode demonstrate the technique.

Exciton polaritons have been shown to be an optimal system in order to investigate the properties of bosonic quantum fluids. We report here on the observation of dark solitons in the wake of engineered circular obstacles and their decay into streets of quantized vortices. Our experiments provide a time-resolved access to the polariton phase and density, which allows for a quantitative study of instabilities of freely evolving polaritons. The decay of solitons is quantified and identified as an effect of disorder-induced transverse perturbations in the dissipative polariton gas.

We report on time-resolved measurements of the first order spatial coherence in an exciton-polariton Bose-Einstein condensate. Long-range spatial coherence is found to set in right at the onset of stimulated scattering, on a picosecond time scale. The coherence reaches its maximum value after the population and decays slowly, staying up to a few hundred picoseconds. This behavior can be qualitatively reproduced, using a stochastic classical field model describing interaction between the polariton condensate and the exciton reservoir within a disordered potential.

The electronic structure of hydroxocobalamin (OHCbl) has been calculated by a density functional method, using the orthogonalized linear combination of the atomic orbitals method (OLCAO). The X-ray crystal structure has been determined from synchrotron X-ray diffraction data and the geometry determined was used in the calculations. Comparison with the recently reported electronic structures of cyanocobalamin (CNCbl), methylcobalamin (MeCbl) and adenosylcobalamin (AdoCbl) shows that Mulliken charges (Q*) and bond orders (BO) vary only on the axial fragment.

Crystallization and crystal structure analysis of chlorohydrates of either tri- or tetracationic copper porphyrins, namely copper(5,10,15-tris(N-methyl-pyridinium-4-yl)-20-pyridine-porphyrinato) (1) and copper(5,10,15,20-tetrakis(N-methyl-pyridinium-4-yl)-porphyrinato), respectively, have been performed. Two crystalline forms, 2 and 3, of the latter have been obtained under different preparation conditions. A novel kind of slipped stack chains of these cationic porphyrins has been detected. The pronounced saddle conformation of the porphyrin reveals pi-like interactions between the peripheral pyrrole Cb-Cb- "double bond" and the metal center. DFT calculations on the isolated porphyrins clearly show the HOMO orbitals with the correct topology to yield a bonding interaction among the stacked porphyrin units. To our knowledge, a slipped stack chain of positively charged porphyrins has never been previously reported, if the arrangement of faced units of monocationic metalloporphyrins or phthalocyanins is excluded.

The reaction of a cis beta folded organocobalt derivative with a salen-type ligand, 1, isolated as racemic compound of Delta and Lambda enantiomers, with enantiomerically pure alpha-l amino acids is reported. The reaction between racemic 1 and l-tyrosine afforded a mixture of the two diastereoisomers Delta-2 and Lambda-2, which could be separated by fractional crystallization owing to the lower solubility of Delta-2. The absolute configuration of the two diastereomers was unequivocally assigned from the X-ray structure, using the known absolute configuration of the asymmetric carbon of the amino acid as internal reference. The reaction of racemic 1 with trans-4-hydroxy-l-proline afforded only the diastereoisomer with a Delta configuration of the tetradentate ligand, as proved by X-ray diffractometric analysis. For both l-tyrosine and trans-4-hydroxy-l-proline, the amino acid initially coordinates both to the Delta and to the Lambda enantiomers of 1, leading to an about equimolar mixture of diastereoisomers. In the case of l-tyrosine the diastereoisomers have about the same energy, so that the successive isomerization is negligible. In the case of trans-4-hydroxy-l-proline, Delta-3 is much more stable than Lambda-3, and the isomerization reaction Lambda-3 --> Delta-3 goes practically to completion.

[reaction: see text] The stereoselective synthesis of a novel proline-containing dipeptide isostere is described. Starting from l-valine, three new contiguous stereocenters are generated by asymmetric induction and epoxide chemistry, while the pyrrolidine ring of proline is introduced in the final step via intramolecular ring opening of the amino acid derived epoxyamine. Proline-containing peptidomimetics are potentially attractive as selective inhibitors of proline-specific enzymes, such as PPIases and retroviral proteases, and as analogues of bioactive peptides.

The electronic structure of adenosylcobalamin (B12 coenzyme, AdoCbl) has been calculated by a density functional method, using the orthogonalized linear combination of the atomic orbital method (OLCAO). Since a fixed accurately determined geometry was needed in such calculations, the crystal structure of adenosylcobalamin has been redone and refined to R = 0.065, using synchrotron diffraction data. Comparison with the recently reported electronic structures of cyano- (CNCbl) and methylcobalamin (MeCbl) shows that the net charges and bond orders vary only on the axial donors. The values in the three cobalamins suggest that the Co-C bond in MeCbl has a strength similar to that in AdoCbl, but it is significantly weaker that that in CNCbl. Present results are compared with those previously reported for the analogous corrin derivatives; i.e., simplified cobalamins with the side chains a-f replaced by H atoms. Despite a qualitative agreement, a discrepancy in the calculated HOMO-LUMO gap is found.

The reduction of [Co(III)(tmsalen)py(2)](+)ClO(4)(-), where tmsalen = 4,4',7,7'-tetramethylsalen, with NaBH(4)/PdCl(2) in alkaline methanolic solution, followed by the oxidative addition of CH(2)ClI, leads to the expected trans organometallic dimeric species 1, [CH(2)ClCo(tmsalen)](2), provided that the product is recovered from the reaction mixture immediately after the completion of the reaction. If 1 is left for longer time in contact with the reaction mixture, the intramolecular reaction of the axial chloromethyl group with the equatorial chelate leads to the formation of the monocationic complex 2, containing a seven-membered ring. In this complex the novel tetradentate ligand coordinates Co in a cis fashion, the other two positions being occupied by one py and one water molecule. The resulting complex is chiral, even if the reaction product is a racemic compound. The unidentate ligands of 2 have been exchanged quantitatively for N-MeIm, and the resulting complex 3 still maintains the beta cis geometry. Therefore, 2 may be considered the precursor of a new class of organocobalt derivatives with a folded tetradentate ligand and two adjacent exchangeable sites. On the basis of the geometry of the tetradentate Schiff bases in complexes, where they adopt a planar geometry, it was suggested that there is a significant electron density delocalization involving the metal center over the two chemically equivalent moieties of Co(chel). Comparison of the geometry of the planar salicylaldiminate (sal) moiety with that of the cyclized methoxy-iminate one (imi) in 2 and 3 strongly supports that the delocalization, still present in sal, is essentially either lost or strongly reduced in imi.

Results of the accurate crystal structure determination of NO(2)Cbl.2LiCl (1), NO(2)Cbl.NaCl (2), NCSCbl (3) and NCSeCbl (4), based on synchrotron diffraction data collected at 100 K, are described. The nitro group in (1) was found to be disordered with two orientations that differ by a rotation of approximately 60 degrees about the Co-NO(2) bond, whereas in (2) the nitro group has only one orientation. The first X-ray structural determination of a cobalamin with a Co-Se bond is reported. Comparison of the axial distances indicates that SeCN has a bond length of 2.384 (3) A and that the trans influence on the Co-N bond is only slightly greater than that of SCN. The crystals of the thiocyanate cobalamin contain both the S- and N-bonded coordination isomers in a 3:2 ratio. The structural features of the Co-S bond in cobalamins are discussed. The crystal chemistry of cobalamins is discussed in terms of packing of roughly spherical molecules. The unit-cell parameters can be used to group the cobalamins' crystal structures in different arrays intermediate between distorted hexagonal close packing and primitive hexagonal arrangements. The structural features of cobalamins, and of cobaloximes that have the same axial fragment as the cobalamins, are reviewed and discussed in terms of the cis influence of the equatorial ligand.

The guest-induced synthesis of a molecular box from methylaquacobaloxime and 1,4-phenylenebisboronic acid, with pyrazine (pz) as guest, is described. The resulting supramolecular species was characterized by X-ray structural analysis, 1H and 13C NMR spectroscopy, and low-resolution electrospray ionization (ES) mass spectrometry. The assembly was monitored by a time dependent 1H NMR experiment, which showed that the guest thermodynamically drives the assembly of the host. The effectiveness of pyrazine in this role arises from its having both the correct geometry and a sufficiently low pKa value. Several other ditopic ligands were tested, but none led to formation of an analogous product. However, a second supramolecular species was formed in the case of ethylenediamine (en). X-ray structural analysis and 1H and 13C spectroscopy revealed that this is closely related to the first, with a phenyl side removed and the pz bridge substituted by the en bridge.

The complex mer-[Co(III)(L(1)Npy)(2)](+) (1') where the L(1)Npy(-) is the tridentate 3-[(2-pyridyl)methylimino]butan-2-one oximate ligand, gives alkyl-cobalt derivatives after reduction with NaBH(4)/Pd(2+) to the Co(I) and alkylation. The formation of the cobalt-carbon bond is accompanied by the reduction to the amino form of one or both imino ligands (depending on the experimental conditions) initially present in 1'. In one series of experiments, complexes of the type fac-[RCo(III)(L(1)Npy)(H-L(1)NHpy)](+) (R = Me, i-Pr, CH(2)Cl, CH(2)Br, CH(2)CF(3), and Bz) were obtained, in which only one of the two ligands was reduced to the amino form (H-L(1)NHpy). The saturation of one azomethine group causes the products to assume a fac configuration and induces the formation of one asymmetric carbon and one asymmetric nitrogen center in the chelating system. When an excess of reducing agent is used, both azomethine groups may be saturated, causing the introduction of one pair of chiral carbons and one pair of chiral nitrogens. Two isomers of the methyl derivative [MeCo(III)(L(1)NHpy)(H-L(1)NHpy)](+) were isolated. The X-ray analysis reveals that these isomers differ from one another in configuration of the C and N chiral centers. Possible reaction mechanisms leading to these different types of complexes are proposed.

Treatment of R = -CH(2)X (X = halogen) derivatives of the type [RCo(III)(LNH-py)(HLNH-py)](+), where HLNH-py = 2-(2-pyridyl-ethyl)amino-3-butanone oxime and LNH-py its conjugated base with diluted NaOH, afforded a new complex containing a three-membered ring by a pathway involving the intramolecular nucleophilic addition of an equatorial nitrogen donor to the axial carbon. The X-ray analysis reveals a highly distorted structure. The C-Co-N angle is acute (42.8 degrees ) with the distortion of the coordination sphere concentrated in the Co-C axial and Co-N bonds, which move away from the pseudo-octahedral positions in the CH(2)X parent complex to form the C-N bond of the metallocycle. Kinetic studies of the formation of this novel complex starting from [(XCH(2)Co(III)(LNH-py)(HLNH-py)](+) (X = Cl,Br,I) showed that the metallocycle formation rates increase in the order Cl < Br < I. Kinetic data are consistent with a mechanism involving an intermediate species resulting from the deprotonation of an amine equatorial nitrogen in a rapid preequilibrium, followed by the slow step of the ring closure.

The reaction of CH(3)Co(DH)(2)H(2)O with 4-pyridinyl boronic acid in methanol or water affords the dinuclear complexes [MeCo(DH)(DB(OR)(4-Py))](2), with R = Me (2) or H (3), respectively, through reaction of boron with the oxime oxygens of the alkylcobaloxime and coordination of the pyridinyl N to cobalt. The reaction is strongly pH dependent, and the formation of the complexes requires a neutral medium. The complexes have been fully characterized by (1)H and (13)C NMR spectroscopy, ESI-MS spectrometry, and elemental analysis. The X-ray structure shows that in 2, the pyridinyl groups are facing each other and nearly perpendicular both to the plane of the Co B Co1 B1 atoms and to the mean equatorial plane, so that the complex may be considered a molecular box. A dimeric arrangement has already been found in the related [MeCo(DH)(DB(OMe)(3-Py))](2) (1) complex, which forms a distorted molecular rectangle [Dreos, R.; Nardin, G.; Randaccio, L.; Tauzher, G.; Vuano, S. Inorg. Chem. 1997, 36, 2463]. The dimerization is possible in both cases, as the conformational freedom of the B bridge compensates for the different position (3- or 4-) of the pyridinyl N donor.

In the Mansfeld region (Central Germany) copper mining contributed to an enormous pollution of the environment. Metal- and sulphate-bearing sediments and leachates emerge from the former copper smelters and mining waste heaps, spread along local rivers and finally reach the Saale river. A sulphur isotope study on water and stream sediments was performed along the River "Böse Sieben" and from its tributaries to determine the different sulphur sources. Four major sulphur sources exist in the area: metal sulphide mineralisations (Kupferschiefer), met alliferous sulphidic flue dust, slag, and anhydrite and gypsum of Permian and Triassic age. We obtained delta34S(SO4)-values in water samples varying from +4 per thousand to -18 per thousand CDT, clearly reflecting the input of sulphate from different sources. Sulphate from the oxidation of sulphidic mining residues is restricted to the mining area and cannot be traced for more than 5 km downstream. The major source for sulphate is the dissolution of gypsum and anhydrite. The sulphur isotope composition in dissolved and sedimentary adsorbed sulphate differs only slightly from each other. Microbial dissimilatory sulphate reduction can not be excluded in the shallow sediment layers.

The reactivity of nitrite towards the copper(II) and copper(I) centers of a series of complexes with tridentate nitrogen donor ligands has been investigated. The ligands are bis[(1-methylbenzimidazol-2-yl)methyl]amine (1-bb), bis[2-(1-methylbenzimidazol-2-yl)ethyl]amine (2-bb), and bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine (ddah) and carry two terminal benzimidazole (1-bb, 2-bb) or pyrazole (ddah) rings and a central amine donor residue. While 2-bb and ddah form two adjacent six-membered chelate rings on metal coordination, 1-bb forms two smaller rings of five members. The binding affinity of nitrite and azide to the Cu(II) complexes (ClO4- as counterion) has been determined in solution. The association constants for the two ligands are similar, but nitrite is a slightly stronger ligand than azide when it binds as a bidentate donor. The X-ray crystal structure of the nitrite complex [Cu(ddah)(NO2)]ClO4 (final R=0.056) has been determined: triclinic P1space group, a=8.200(2) A, b=9.582(3) A, c=15.541(4) A. It may be described as a perchlorate salt of a "supramolecular" species resulting from the assembly of two complex cations and one sodium perchlorate unit. The copper stereochemistry in the complex is intermediate between SPY and TBP, and nitrite binds to Cu(II) asymmetrically, with Cu-O distances of 2.037(2) and 2.390(3) A and a nearly planar CuO2N cycle. On standing, solutions of [Cu(ddah)(NO2)]ClO4 in methanol produce the dinuclear complex [Cu(ddah)(OMe)]2(ClO4)2, containing dibridging methoxy groups. In fact the crystal structure analysis (final R=0.083) showed that the crystals are built up by dinuclear cations, arranged on a crystallographic symmetry center, and perchlorate anions. Electrochemical analysis shows that binding of nitrite to the Cu(II) complexes of 2-bb and ddah shifts the reduction potential of the Cu(II)/Cu(I) couple towards negative values by about 0.3 V. The thermodynamic parameters of the Cu(II)/Cu(I) electron transfer have also been analyzed. The mechanism of reductive activation of nitrite to nitric oxide by the Cu(I) complexes of 1-bb, 2-bb, and ddah has been studied. The reaction requires two protons per molecule of nitrite and Cu(I). Kinetic experiments show that the reaction is first order in [Cu(I)] and [H+] and exhibits saturation behavior with respect to nitrite concentration. The kinetic data show that [Cu(2-bb)]+ is more efficient than [Cu(1-bb)]+ and [Cu(ddah)]+ in reducing nitrite.

The dicopper(II) complex with the ligand N,N,N',N',N"-pentakis[(1-methyl-2-benzimidazolyl)methyl]dipropylenetriamine (LB5) has been synthesized and structurally characterized. The small size and the quality of the single crystal required that data be collected using synchrotron radiation at 276 K. [Cu(2)(LB5)(H(2)O)(2)][ClO(4)](4): platelet shaped, P&onemacr;, a = 11.028 Å, b = 17.915 Å, c = 20.745 Å, alpha = 107.44 degrees, beta = 101.56 degrees, gamma = 104.89 degrees, V = 3603.7 Å(3), Z = 2; number of unique data, I >/= 2sigma(I) = 3447; number of refined parameters = 428; R = 0.12. The ligand binds the two coppers nonsymmetrically; Cu1 is coordinated through five N donors and Cu2 through the remaining three N donors, while two water molecules complete the coordination sphere. Cu1 has distorted TBP geometry, while Cu2 has distorted SP geometry. Voltammetric experiments show quasireversible reductions at the two copper centers, with redox potential higher for the CuN(3) center (0.40 V) and lower for the CuN(5) center (0.17 V). The complex binds azide in the terminal mode at the CuN(3) center with affinity lower than that exhibited by related dinuclear polyaminobenzimidazole complexes where this ligand is bound in the bridging mode. The catechol oxidase activity of [Cu(2)(LB5)](4+) has been examined in comparison with that exhibited by [Cu(2)(L-55)](4+) (L-55 = alpha,alpha'-bis{bis[(1-methyl-2-benzimidazolyl)methyl]amino}-m-xylene) and [Cu(2)(L-66)](4+) (L-66 = alpha,alpha'-bis{bis[2-(1-methyl-2-benzimidazolyl)ethyl]amino}-m-xylene) by studying the catalytic oxidation of 3,5-di-tert-butylcatechol in methanol/aqueous buffer pH 5.1. Kinetic experiments show that [Cu(2)(L-55)](4+) is the most efficient catalyst (rate constant 140 M(-1) s(-1)), followed by [Cu(2)(LB5)](4+) (60 M(-1) s(-1)), in this oxidation, while [Cu(2)(L-66)](4+) undergoes an extremely fast stoichiometric phase followed by a slow and substrate-concentration-independent catalytic phase. The catalytic activity of [Cu(2)(L-66)](4+), however, is strongly promoted by hydrogen peroxide, because this oxidant allows a fast reoxidation of the dicopper(I) complex during turnover. The activity of [Cu(2)(LB5)](4+) is also promoted by hydrogen peroxide, while that of [Cu(2)(L-55)](4+) is little affected. The phenol monooxygenase activity of [Cu(2)(LB5)](2+) has been compared with that of [Cu(2)(L-55)](2+) and [Cu(2)(L-66)](2+) by studying the ortho hydroxylation of methyl 4-hydroxybenzoate to give methyl 3,4-dihydroxybenzoate. The LB5 complex is much more selective than the other complexes since its reaction produces only catechol, while the main product obtained with the other complexes is an addition product containing a phenol residue condensed at ring position 2 of the catechol.

Twenty-four patients with bilateral chronic open-angle glaucoma received three treatments: (1) artificial tears (control) in both eyes, (2) artificial tears in one eye and one drop of timolol (0.05%) in the other, and (3) artificial tears in one eye and one drop of betaxolol (0.05%) in the other. Twelve patients always received the test medication in the left eye and 12 in the right eye. The patients were examined and questioned about ocular symptoms at the time of drug administration and at 1, 5, 30, and 60 minutes. Irritation was noted in five treated eyes after artificial tears, in three after timolol, and in 11 after betaxolol. The incidence of irritation after initial treatment was significantly lower than expected for timolol than for artificial tears or betaxolol (P less than 0.01).