Soliton instabilities and vortex street formation in a polariton quantum fluid.

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.

Dynamics of long-range ordering in an exciton-polariton condensate.

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.

A molecular box derived from cobaloxime units held together by 4-pyridinylboronic acid residues.

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.

A new organocobalt complex containing a CO-N-C three membered ring.

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.

Origin and distribution of sulphate in surface waters of the Mansfeld mining district (Central Germany)--a sulphur isotope study.

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 use of a computer-assisted image-guided system (InstaTrak) in orbital surgery.

PURPOSE: To assess the usefulness of a computer-assisted image-guided system (CAIGS) as an intraoperative anatomical guide in performing orbital surgery. METHODS: Noncomparative interventional case series of 30 consecutive orbital procedures performed by one surgeon (J.G.C.) using the CAIGS (InstaTrak) for intraoperative anatomical guidance. RESULTS: The series consisted of 8 cases of orbital decompression, 8 cases of orbital fracture, 11 cases of tumor excision, 2 cases of orbital reconstruction for severe enophthalmos, and 1 case of drainage of an orbital abscess. The CAIGS (InstaTrak) was useful in providing adjunctive intraoperative guidance in all 30 orbital cases. CONCLUSION: The CAIGS (InstaTrak) system is a useful adjunctive tool in providing intraoperative anatomic guidance in a consecutive series of varied orbital operations.

Binding of nitrite and its reductive activation to nitric oxide at biomimetic copper centers.

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.

Therapeutic index of pilocarpine, carbachol, and timolol with nasolacrimal occlusion.

We assessed the effect of nasolacrimal occlusion on the therapeutic index of various antiglaucoma medications in healthy volunteers and patients with glaucoma. Nasolacrimal occlusion used with pilocarpine 2% every 12 hours gave the maximal ocular hypotensive response. Carbachol 1.5% every 12 hours with nasolacrimal occlusion gave the maximal response for this drug. For timolol, nasolacrimal occlusion collapsed the dose-response curve and extended the duration of action. A final trial of carbachol added to timolol with nasolacrimal occlusion showed that timolol 0.25% and carbachol 1.5% every 12 hours gave the maximal response for this combination. Our findings suggest that most of the commercially used ocular hypotensive agents can achieve the same maximal effect with lower concentrations and less frequent administration (never exceeding every 12 hours) than are currently recommended should nasolacrimal occlusion be performed. Furthermore, nasolacrimal occlusion should markedly decrease the systemic absorption of topical ocular drugs and lessen the chance of systemic side effects.

Therapeutic index of epinephrine and dipivefrin with nasolacrimal occlusion.

We assessed the effect of nasolacrimal occlusion on the therapeutic index of the adrenoreceptor agonists in healthy volunteers and patients with glaucoma. Nasolacrimal occlusion did not significantly alter the response to 2% epinephrine or to 0.1% dipivefrin in healthy subjects, suggesting that both 2% epinephrine and 0.1% dipivefrin are at the top of the dose-response curve. When 0.5% epinephrine with nasolacrimal occlusion was tested in patients with glaucoma, effects were noticeable at four and eight hours (P less than .05), but not at 12 hours. For 2% epinephrine, there was no significant difference at any measurement time. Epinephrine (1%) with and without nasolacrimal occlusion gave results similar to those of 2% epinephrine, suggesting that 1% epinephrine is also at the top of the dose-response curve. Nasolacrimal occlusion did not increase the ocular hypotensive effect of either of these concentrations. Because dipivefrin, the most widely used formulation in this class, is a prodrug of epinephrine that has a corneal penetration approximately 17 times that of epinephrine, 0.05% dipivefrin, every 12 hours, might be an adequate dosage for maximal effect. Although nasolacrimal occlusion did not alter the drug effect of 0.1% dipivefrin, preventing as much drug as possible from reaching the systemic circulation is desirable.

Sneezing as a cause of acute angle-closure glaucoma.

We report the case of a patient who had an attack of acute angle-closure glaucoma precipitated by sneezing, probably as a result of a sudden increase in venous back pressure. This young woman had a history of allergic sinusitis.

Effect of chronic carbonic anhydrase inhibitor therapy on bone mineral density in white women.

A limited, dual-photon absorptiometry, single-center study of bone mineral density (BMD) was conducted on white female glaucoma subjects who were chronic users of the carbonic anhydrase (CA) inhibitors acetazolamide (Az) or methazolamide (Mz). In postmenopausal subjects long-term (greater than 4 years) CA inhibitor use was associated with a bone-sparing effect as judged by spinal BMD in comparison to controls matched for age, sex, weight, and ethnic group or in comparison to a national normative data base. Short-term (0-2 years) postmenopausal CA inhibitor users and premenopausal subjects using CA inhibitors showed no sparing of spinal BMD. Femoral neck BMD was not affected by CA inhibitor therapy in any of the groups. This study supports a proposed role for carbonic anhydrase in human bone resorption and suggests a possible future utility for carbonic anhydrase inhibitors in prophylaxis or management of primary involutional osteoporosis. Future studies are necessary to verify and expand these findings, assess the effects of CA inhibitors on bone mechanical competence, and further develop CA inhibitors with some specificity for bone.

Automated perimetry, tonometry, and questionnaire in glaucoma screening.

To evaluate the sensitivity and specificity of various portions of the glaucoma screening process, 145 participants underwent complete ophthalmic examinations. A weighted questionnaire was 20% (2 patients) and 36% (5 suspects) sensitive for the glaucoma patients and glaucoma suspects, respectively. Tonometry alone was 20% (2 patients) and 7% (1 suspect) sensitive for glaucoma patients and glaucoma suspects, respectively. Automated perimetry of the central 30 degrees and nasal periphery identified nine (90%) of the glaucoma patients and five (36%) of the glaucoma suspects. The presence of increased intraocular pressure was not by itself very useful, but when perimetry or tonometry was used, 10 (100%) of the glaucoma group was identified. We recommend that automated suprathreshold perimetry and tonometry be performed in glaucoma screening.

Effect of intracameral carbachol on intraocular pressure after cataract extraction.

Thirty-two patients were randomly assigned to a treatment or a control group to determine the dose-response and duration of action of intracameral carbachol on immediate postoperative intraocular pressure after extracapsular cataract extraction using a viscoelastic substance. Patients in the treatment group received 0.5, 0.25, or 0.1 ml of 0.01% intracameral carbachol. Patients in the control group received 0.1 or 0.5 ml of balanced salt solution. Intraocular pressures of all patients were measured preoperatively and at three, six, 12, 24, and 48 hours postoperatively. The control group as a whole showed a 9.5-mm Hg intraocular pressure rise at three hours, a 10.0-mm Hg rise at six hours, a 9.0-mm Hg rise at 12 hours, and a 7.2-mm Hg rise at 24 hours postoperatively. The group treated with 0.5 ml of carbachol maintained stable intraocular pressures through the 48-hour measurement period. The groups treated with 0.25 and 0.1 ml of carbachol maintained stable intraocular pressures through 24 hours postoperatively. The differences in intraocular pressure were statistically significant for all treated groups through the 24-hour measurement.

Tolerability of timolol and betaxolol in patients with chronic open-angle glaucoma.

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).