Designer "Quasi-Benzyne": The Spontaneous Reduction of Ortho-Diiodotetrafluorobenzene on Water Microdroplets.

It has been widely shown that water microdroplets have a plethora of unique properties that are highly distinct from those of bulk water, among which an especially intriguing one is the strong reducing power as a result of the electrons spontaneously generated at the air-water interface. In this study, we take advantage of the reducing power of water microdroplets to reduce ortho-diiodotetrafluorobenzene (o-C6F4I2) into a C6F4I2•- radical anion. Photoelectron spectroscopy and density functional theory computations reveal that the excess electron in C6F4I2•- occupies the I-C1-C2-I linkage, which elongates the C-I bonds but surprisingly shortens the C1-C2 bond, making the bond order higher than a double bond, similar to the benzyne molecule, so we named it "quasi-benzyne". The C6F4I2•- anion was further successfully utilized in a Diels-Alder reaction, a typical reaction for benzyne. This study provides a good example of strategically utilizing the spontaneous properties of water microdroplets and generating an especially exotic anion, and we anticipate that microdroplet chemistry can be an avenue rich in opportunities for new catalyst-free organic reactions.

Study of the Reaction of Hydroxylamine with Iridium Atomic and Cluster Anions (n = 1-5).

Elucidating the multifaceted processes of molecular activation and subsequent reactions gives a fundamental view into the development of iridium catalysts as they apply to fuels and propellants, for example, for spacecraft thrusters. Hydroxylamine, a component of the well-known hydroxylammonium nitrate (HAN) ionic liquid, is a safer alternative and mimics the chemistry and performance standards of hydrazine. The activation of hydroxylamine by anionic iridium clusters, Irn- (n = 1-5), depicts a part of the mechanism, where two hydrogen atoms are removed, likely as H2, and Irn(NOH)- clusters remain. The significant photoelectron spectral differences between these products and the bare clusters illustrate the substantial electronic changes imposed by the hydroxylamine fragment on the iridium clusters. In combination with DFT calculations, a preliminary reaction mechanism is proposed, identifying the possible intermediate steps leading to the formation of Ir(NOH)-.

[A Case of Metastatic Endophthalmitis Resulting from Liver Abscess Complicated with Pyogenic Ventriculitis via Optic Nerve].

BACKGROUND: Intracranial extension of infection via the optic nerve is a rare but serious complication of bacterial endophthalmitis. CASE: A 79-year-old women was hospitalized complaining of right eyelid swelling, severe hyperemia and purulent conjunctival discharge in the right eye. Although the fundus was invisible due to cataract, right endophthalmitis of unknown origin was suggested by pus in the anterior chamber and brain computed tomography (CT) findings showing nasal scleral rupture and orbital cellulitis. Systemic examination revealed pyogenic liver abscess and percutaneous drainage of abscess disclosed Klebsiella pneumoniae, which was also isolated from conjunctival discharge. Because diffusion-weighted magnetic resonance imaging (MRI) findings demonstrated right optic neuritis and ventriculitis, enucleation of her right eye was performed based on the diagnosis of pyogenic ventriculitis via the optic nerve. Klebsiella pneumoniae was detected in both stumps of the transected right optic nerve. Despite intensive anti-bacterial treatment, she died of acute respiratory distress syndrome 46 days after hospitalization. CONCLUSION: Severe bacterial endophthalmitis may cause intracranial infection via the optic nerve.

Five-year incidence of angle closure among glaucoma health examination participants.

BACKGROUND AND AIM: To investigate incidence of angle closure (AC) and its associated factors through a community-based longitudinal study over a 5-year period. METHODS: Japanese residents aged 40 years or over who underwent two glaucoma health examinations held in 2005 and 2010 were enrolled. Of the participants of the first glaucoma health examination (first examination), those who satisfied exclusion criteria such as having eyes with angle closure, glaucoma, incisional ocular surgery, or other conditions that could influence the results were eliminated from the second glaucoma health examination (second examination). In addition to routine ophthalmic examination, a scanning peripheral anterior chamber depth analyzer (SPAC) was employed to investigate the anterior chamber configuration. The incidence of angle closure over the 5-year period and its associated factors were investigated. RESULTS: Of the 754 participants of the first examination, 569 participants were invited for the second examination and 331 participants (87 males and 244 females, age: 62.6 ± 12.7 years), or 619 eyes, were analyzed after eliminating eyes matching exclusion criteria. In the 5-year period, the incidence of AC was 5.4 % (95 % CI: 3.5-8.4 %) of participants or 5.5 % (95 % CI: 4.0-7.6 %) of eyes, including eight eyes (1.3 %) with primary angle-closure glaucoma. Eyes that developed AC had a much smaller SPAC grade at the first examination and a greater decrease in SPAC grade than those that did not develop AC, whereas age and sex were not associated. CONCLUSIONS: AC was developed by 5.4 % of senior Japanese residents over the 5-year period. The shallow anterior chamber and the marked decrease in anterior chamber depth were associated with AC development.

Systemic arterial stiffness in glaucoma patients.

PURPOSE: To investigate systemic arterial stiffness in glaucoma patients. SUBJECTS AND METHODS: One hundred and forty glaucoma patients and 121 control subjects were enrolled in the study. Among these subjects, 51 glaucoma patients [normal-tension glaucoma (NTG), 31; primary open angle glaucoma or ocular hypertension (POAG/OH): 20] and 61 control subjects without glaucoma, who presented with no risk factors for arteriosclerosis, were extracted for further analysis of systemic arterial stiffness by glaucoma type. Subjects presenting with risk factors for arteriosclerosis were classified into group A, and those presenting with no risk factors were classified into group B. Brachial-ankle pulse wave velocity (baPWV), a marker of systemic arterial stiffness, was determined with a volume-plethysmographic apparatus. The correlation between baPWV and mean deviation obtained from Humphrey Field Analyzer program 30-2 test was compared between 13 each of age-matched and sex-matched NTG and POAG/OH patients. RESULTS: There was a significant difference in baPWV between groups A and B [P<0.0001; 1748+/-393 cm/s (group A) and 1467+/-282 cm/s (group B)]. The baPWVs of control, NTG patients, and POAG/OH patients with no risk factors showed no significant difference. baPWV was positively correlated with age in all the 3 groups, but there were no significant differences among the 3 groups. baPWV tended to be negatively correlated with mean deviation in NTG patients (r2=0.25, P=0.08); in contrast, no correlation was observed in POAG/OH patients. CONCLUSION: Systemic arterial stiffness seems not to be strongly associated with glaucoma.

Efficacy and Safety of Switching Prostaglandin Analog Monotherapy to Tafluprost/Timolol Fixed-Combination Therapy.

PURPOSE: To assess the efficacy and safety of switching from prostaglandin analog (PGA) monotherapy to tafluprost/timolol fixed-combination (Taf/Tim) therapy. SUBJECTS AND METHODS: Patients with primary open-angle glaucoma, normal-tension glaucoma, or ocular hypertension who had received PGA monotherapy for at least 3 months were enrolled. Patients were examined at 1, 2, and 3 months after changing therapies. Subsequently, the patients were returned to PGA monotherapy. The examined parameters included intraocular pressure (IOP) and adverse events. A questionnaire survey was conducted after the switch to Taf/Tim therapy. RESULTS: Forty patients with a mean age of 66.5 ± 10.3 years were enrolled; 39 of these patients completed the study protocol. Switching to Taf/Tim significantly reduced the IOP from 18.2 ± 2.6 mmHg at baseline to 14.8 ± 2.5 mmHg at 1 month, 15.2 ± 2.8 mmHg at 2 months, and 14.9 ± 2.5 mmHg at 3 months (P < 0.001). Switching back to the original PGA monotherapy returned the IOP values to baseline levels. Taf/Tim reduced the pulse rate insignificantly. No significant differences were observed in blood pressure, conjunctival hyperemia, or corneal adverse events. A questionnaire showed that the introduction of Taf/Tim did not significantly influence symptoms. CONCLUSIONS: Compared with PGA monotherapy, Taf/Tim fixed-combination therapy significantly reduced IOP without severe adverse events.

Hyperoxidation of ether-linked phospholipids accelerates neutrophil extracellular trap formation.

Because neutrophil extracellular trap (NET) formation is involved in the pathology of a wide variety of diseases, NET-regulating compounds are expected to be useful for the therapies of these diseases. In this study, we identified sulfasalazine (SSZ) as a potent enhancer of NET formation both in vitro and in vivo. Although SSZ did not increase the amount of ROS generated, it accelerated the generation of ether-linked oxidized phospholipids, such as PE (18;1e/15-HETE) and PC (16;0e/13-HODE). Trolox, but not 2-ME, effectively suppressed lipid oxidation and NET formation that were induced by SSZ. SSZ is known as a potent inducer of ferroptosis in cancer cells by inhibiting xCT, a component of the cystine transporter. However, we found that SSZ accelerated NET formation in an xCT-independent manner. Structure-activity relationship studies revealed that the sulfapyridine moiety of SSZ plays a central role in enhancing NET formation. Furthermore, we found that two additional sulfonamide and sulfone derivatives possess NET-inducing activity by accelerating lipid oxidation. These results indicate that the hyperoxidation of ether-linked phospholipids is a key mechanism for accelerating NET formation.

Change in visual acuity and associated risk factors after trabeculectomy with adjunctive mitomycin C.

PURPOSE: To report the 5-year incidence of visual impairment after mitomycin C-augmented trabeculectomy (MMC trabeculectomy) and the risk factors for visual impairment. METHODS: This is a multicentre prospective observational cohort study. Among glaucoma patients registered in the Collaborative Bleb-related Infection Incidence and Treatment Study performed in Japan, the patients with eyes meeting the following qualifications were included: eyes with primary open-angle glaucoma; eyes with primary angle-closure glaucoma; eyes with exfoliative glaucoma; eyes with ≥3/60 in blindness analysis; and eyes with ≥20/60 in low-vision analysis and visual acuity loss analysis. The patients were followed at 6-month intervals for 5 years. The entry data and follow-up data were analysed to determine the incidence of blindness (<3/60), low vision (≥3/60 and <20/60) and visual acuity loss (≥0.2 logMAR) during the follow-up period. Risk factors for visual impairment were also analysed. RESULTS: A total of 694 eyes of 694 or 559 eyes of 559 glaucoma patients were subjected to the blindness analysis or the low-vision and visual acuity loss analysis, respectively. Visual acuity significantly deteriorated (p < 0.0001): 12.2% (95%CI: 9.8-14.7%) of the patients became blind; 12.1% (95%CI: 9.4-14.9%) were judged to have low vision at the final examination; 28.3% (95%CI: 24.5-32.0%) were judged to have visual acuity loss. Glaucoma subtypes, poor preoperative visual function and postoperative complications are the main risk factors for visual impairment. CONCLUSIONS: Visual acuity was significantly reduced after MMC trabeculectomy in 5 years, and we identified several risk factors associated with this complication.

Predicting glaucomatous sensitivity loss using perimetric color saturation test.

PURPOSE: To predict future glaucomatous sensitivity loss using a perimetric color saturation test (PCST) that measures the color saturation discrimination threshold for six hues (red, yellow, green, green-blue, blue, and purple) at 9 degrees in horizontal and 3 degrees in vertical extrafoveal points. METHODS: This new test was carried out on 31 patients (31 eyes) with early glaucoma or ocular hypertension. The sensitivity loss at the four points approximately 9.5 degrees apart from the fixation point was prospectively evaluated annually for 3 years using the Humphrey Field Analyzer (HFA) program central 30-2. The initial results of PCST and the total deviation (TD) in the follow-up HFA results were compared. RESULTS: Twenty-seven patients (27 eyes) were followed up for 3 years. The color saturation threshold for six hues was correlated with the TD of HFA results at 108 points in the 27 eyes. The TD was -4 dB or better at the baseline measurement in 91 out of the 108 points. The averaged TD in the second and the third year in the follow-up period decreased below -4 dB in 10 of these 91 points, which were categorized as progression points in relation to the 81 nonprogression points. In the initial PCST, only the saturation threshold for purple was higher in the progression points when compared with the nonprogression points (P=.0004, Mann-Whitney U-test). CONCLUSION: Future sensitivity loss is most likely at the points where the threshold of color saturation discrimination is increased for purple in eyes with early glaucoma or ocular hypertension.

A prospective study of iridial pigmentation and eyelash changes due to ophthalmic treatment with latanoprost.

PURPOSE: To conduct a 12-month prospective study on the occurrence of latanoprost-induced iridial pigmentation and eyelash change in Japanese patients with glaucoma METHODS: Seventy-five patients (75 eyes) were enrolled in the study. Photographs of the iris and eyelashes were taken under identical conditions before and after treatment. Three glaucoma specialists assessed the iridial pigmentation/eyelash change independently with no knowledge of patient data. The effects of age, sex, concomitant medication, and type of glaucoma on iridial pigmentation/eyelash change were investigated, and intraocular pressure (IOP) reduction and iridocorneal angle pigmentation before and after latanoprost treatment were compared between patients with iridial pigmentation/eyelash change and patients without these changes. RESULTS: The incidence of iridial pigmentation was 6.3% at 1 month, 15.7% at 3 months, 37.8% at 6 months, and 56.5% at 12 months. The incidence of eyelash change was 0% at 1 month, 33.8% at 3 months, 44.4% at 6 months, and 46.2% at 12 months. Latanoprost did not affect IOP reduction or iridocorneal angle pigmentation. No significant relationship between iridial pigmentation and eyelash change was observed. None of the investigated parameters except age affected the iridial pigmentation/eyelash change. CONCLUSION: Iridial pigmentation and eyelash change occurred at a high frequency in long-term treatment with latanoprost in Japanese glaucoma patients.

[Reliable parameters for assessing the birefringence of retinal nerve fiber layer under various conditions of corneal birefringence].

PURPOSE: To find a reliable parameter for the assessment of parafoveal nerve fiber layer using scanning laser polarimetry. METHODS: The retinal nerve fiber layer was imaged using a Nerve Fiber Analyzer II (NFA II) along the parafoveal circle with a 90-pixel diameter in 4 dilated eyes of 4 normal subjects. The average thickness was measured in the superior(S), temporal(T), inferior(I), and nasal(N) quadrants. The image was obtained by means of a laser beam passing through 4 different locations in the cornea: the center, 2 mm temporal from the center, 2 mm lower temporal from the center, and 2 mm lower from the center. RESULTS: The circumference profile of the nerve fiber layer around the fovea showed a biphasic pattern similar to that obtained around the optic disc. However, the peaks of the pattern varied according to the corneal location through which the laser beam passed. Accordingly, the average thickness of the nerve fiber layer in each quadrant showed great fluctuation when using a displaced laser beam. The coefficient of variance was large (0.265-0.313) for the nerve fiber layer thickness itself; however, it was far less for the ratio of the nerve fiber layer thickness in the opposite direction, such as temporal-to-nasal (0.082) or superior-to-inferior (0.089). CONCLUSIONS: Although the measurement of the retinal nerve fiber thickness itself depends largely on the location in the birefringent cornea through which the laser beam passes, the ratios of nerve fiber layer thickness such as temporal-to-nasal or superior-to-inferior are reliable and show less fluctuation in the measured values.

Reappraisal of spontaneous closure rate of idiopathic full-thickness macular holes.

We retrospectively reviewed the records of 142 eyes of 138 patients with idiopathic full-thickness macular hole. Spontaneous closure of idiopathic full-thickness macular hole was observed in five eyes (3.5%) of four patients before the planned vitrectomy. In the era when surgical treatment was not available for macular hole, the rate of spontaneous closure of idiopathic full-thickness macular hole was reported as 6.2%. Among several case reports on spontaneous closure of idiopathic full-thickness macular hole based on the optical coherence tomography images only one study reported the rate of spontaneous closure as 2.7%. According to the previous reports and our results, small idiopathic full-thickness macular holes may close spontaneously in a few percent of all macular hole cases. The rate of spontaneous closure may be affected by the waiting time before vitrectomy.

Comparison of the anterior ocular segment measurements using swept-source optical coherent tomography and a scanning peripheral anterior chamber depth analyzer.

PURPOSE: To compare the anterior ocular segment measurements of two non-contact devices, i.e., anterior segment swept-source optical coherence tomography (SS-OCT) and the scanning peripheral anterior chamber depth analyzer (SPAC), in patients with glaucoma. PATIENTS AND METHODS: This was a cross-sectional study of glaucoma patients visiting the Yamanashi University Hospital. The consistency and correlation of various parameters were studied between the SS-OCT and SPAC measurements, including the central corneal thickness (CCT), the central anterior chamber depth (ACD), the trabecular-iris angle (TIA), the angle opening distance (AOD), the area of the recessed angle (ARA), and the trabecular-iris space area (TISA) from the SS-OCT measurements, and the CCT, central ACD, SPAC grade, and SPAC-evaluated anterior chamber angle (ACA) from the SPAC measurements. RESULTS: Seventy right eyes of 70 patients (27 men, 43 women) with glaucoma were enrolled in the study. The mean patient age was 65.9 ± 14.5 years. The CCT measurements by SS-OCT and the SPAC were 528.3 ± 32.0 and 516.1 ± 28.5 µm, respectively (P < 0.001). The central ACD measurements by SS-OCT and the SPAC were 2.39 ± 0.44 and 2.73 ± 0.50 mm, respectively (P < 0.001). The two devices showed a significant correlation in terms of the CCT measurements (R (2) = 0.667, P < 0.0001) and the central ACD measurements (R (2) = 0.86, P < 0.0001), but SS-OCT give a significantly shallower central ACD measurement and a thinner CCT measurement compared with the SPAC. AOD, TIA, TISA, and the ARA were all significantly correlated with the SPAC grade and the ACA. Consistency between the two devices was reduced among eyes with primary angle closure. CONCLUSIONS: Based on our results, the SS-OCT and SPAC measurements of the anterior segment were significantly correlated, but the values cannot be considered to be directly interchangeable.