Solvent-Driven Dynamics: Crafting Tailored Transformations of Cu(II)-Based MOFs.

Metal-organic frameworks (MOFs), a sort of crystalline porous coordination polymers composed of metal ions and organic linkers, have been intensively studied for their ability to take up nonpolar gas-phase molecules such as ethane and ethylene. In this context, interpenetrated MOFs, where multiple framework nets are entwined, have been considered promising materials for capturing nonpolar molecules due to their relatively higher stability and smaller micropores. This study explores a solvent-assisted reversible strategy to interpenetrate and deinterpenetrate a Cu(II)-based MOF, namely, MOF-143 (noninterpenetrated form) and MOF-14 (doubly interpenetrated forms). Interpenetration was achieved using protic solvents with small molecular sizes such as water, methanol, and ethanol, while deinterpenetration was accomplished with a Lewis-basic solvent, pyridine. Additionally, this study investigates the adsorptive separation of ethane and ethylene, which is a significant application in the chemical industry. The results showed that interpenetrated MOF-14 exhibited higher ethane and ethylene uptakes compared to the noninterpenetrated MOF-143 due to narrower micropores. Furthermore, we demonstrate that pristine MOF-14 displayed higher ethane selectivity than transformed MOF-14 from MOF-143 by identifying the "fraction of micropore volume" as a key factor influencing ethane uptake. These findings highlight the potential of controlled transformations between interpenetrated and noninterpenetrated MOFs, anticipating that larger MOF crystals with narrower micropores and higher crystallinity will be more suitable for selective gas capture and separation applications.

Engineering Catalysis within a Saturated In(III)-Based MOF Possessing Dynamic Ligand-Metal Bonding.

Metal-organic frameworks have developed into a formidable heterogeneous catalysis platform in recent years. It is well established that thermolysis of coordinated solvents from MOF nodes can render highly reactive, coordinatively unsaturated metal complexes which are stabilized via site isolation and serve as active sites in catalysis. Such approaches are limited to frameworks featuring solvated transition-metal complexes and must be stable toward the formation of "permanent" open metal sites. Herein, we exploit the hemilability of metal-carboxylate bonds to generate transient open metal sites in an In(III) MOF, pertinent to In-centered catalysis. The transient open metal sites catalyze the Strecker reaction over multiple cycles without loss of activity or crystallinity. We employ computational and spectroscopic methods to confirm the formation of open metal sites via transient dissociation of In(III)-carboxylate bonds. Furthermore, the amount of transient open metal sites within the material and thus the catalytic performance can be temperature-modulated.

The AUTOTAC chemical biology platform for targeted protein degradation via the autophagy-lysosome system.

Targeted protein degradation allows targeting undruggable proteins for therapeutic applications as well as eliminating proteins of interest for research purposes. While several degraders that harness the proteasome or the lysosome have been developed, a technology that simultaneously degrades targets and accelerates cellular autophagic flux is still missing. In this study, we develop a general chemical tool and platform technology termed AUTOphagy-TArgeting Chimera (AUTOTAC), which employs bifunctional molecules composed of target-binding ligands linked to autophagy-targeting ligands. AUTOTACs bind the ZZ domain of the otherwise dormant autophagy receptor p62/Sequestosome-1/SQSTM1, which is activated into oligomeric bodies in complex with targets for their sequestration and degradation. We use AUTOTACs to degrade various oncoproteins and degradation-resistant aggregates in neurodegeneration at nanomolar DC50 values in vitro and in vivo. AUTOTAC provides a platform for selective proteolysis in basic research and drug development.

Crystalline hydrogen bonding of water molecules confined in a metal-organic framework.

Hydrogen bonding (H-bonding) of water molecules confined in nanopores is of particular interest because it is expected to exhibit chemical features different from bulk water molecules due to their interaction with the wall lining the pores. Herein, we show a crystalline behavior of H-bonded water molecules residing in the nanocages of a paddlewheel metal-organic framework, providing in situ and ex situ synchrotron single-crystal X-ray diffraction and Raman spectroscopy studies. The crystalline H-bond is demonstrated by proving the vibrational chain connectivity arising between hydrogen bond and paddlewheel Cu-Cu bond in sequentially connected Cu-Cu·····coordinating H2O·····H-bonded H2O and by proving the spatial ordering of H-bonded water molecules at room temperature, where they are anticipated to be disordered. Additionally, we show a substantial distortion of the paddlewheel Cu2+-centers that arises with water coordination simultaneously. Also, we suggest the dynamic coordination bond character of the H-bond of the confined water, by which an H-bond transitions to a coordination-bond at the Cu2+-center instantaneously after dissociating a previously coordinated H2O.

SQUARE GRID DEFORMATION ANALYSIS OF THE MACULA AND POSTOPERATIVE METAMORPHOPSIA AFTER MACULAR HOLE SURGERY.

PURPOSE: To investigate the correlation between postoperative metamorphopsia and macular deformation after macular hole surgery. METHODS: This study included 28 eyes of 28 patients who underwent vitrectomy and internal limiting membrane removal for an idiopathic macular hole. The retinal vasculatures were compared between preoperative and postoperative photographs, and postoperative deformation of the macula was assessed as deformation of the square grid. The displacement of each node was measured, and deformation of the grid was calculated as differences in the coordinates of the adjacent nodes. These parameters were analyzed to find correlation with metamorphopsia measured using the M-charts after 6 postoperative months. RESULTS: The average deformations in the vertical and horizontal lines of the grid were 94.29 µm and 49.72 µm, respectively. Perifoveal deformation was significantly greater than parafoveal deformation (P = 0.001∼0.019). The multiple regression analysis demonstrated that the vertical M-score correlated with superior perifoveal deformation of the vertical line on the fovea (P = 0.036), and the horizontal M-score correlated with temporal perifoveal deformation of the horizontal line on the fovea (P = 0.032). CONCLUSION: The parafoveal tissue was displaced with the fovea concurrently after internal limiting membrane removal in macular hole surgery causing perifoveal deformation, which correlated with postoperative metamorphopsia.

Comparison of refractive deviations after phacovitrectomy according to the intraocular lens insertion method.

PURPOSE: This study aimed to compare refractive deviations between in-the-bag insertion, trans-scleral ciliary sulcus fixation, ciliary sulcus insertion, and ciliary sulcus insertion with optic capture after phacovitrectomy. STUDY DESIGN: Single-unit, single-surgeon, retrospective study. METHODS: Consecutive patients who underwent phacovitrectomy and intraocular lens (IOL) out-of-the-bag insertion simultaneously were retrospectively reviewed. Patients who underwent phacovitrectomy with IOL in-the-bag insertion were also included for comparison with those who underwent phacovitrectomy with out-of-the-bag insertion. Patients were classified into four groups based on the IOL insertion method. The average difference from the target spherical equivalent (SE) to postoperative SE was defined as the refractive deviation. Refractive deviations of the groups were compared. RESULTS: The refractive deviation for the in-the-bag insertion (43 eyes) was -0.18 ± 0.50 Df, -0.84 ± 0.81 D for the trans-scleral ciliary sulcus fixation (43 eyes), -0.93 ± 0.68 D for the ciliary sulcus insertion (25 eyes), and -0.27 ± 0.50 D for the ciliary sulcus insertion with optic capture group (24 eyes). The trans-scleral ciliary sulcus fixation and ciliary sulcus insertion groups had significantly different deviations than the in-the-bag group (p < 0.001). There was no significant difference between the ciliary sulcus insertion with optic capture and the in-the-bag insertion groups (p = 0.100). CONCLUSION: Refractive deviation was significantly different between the eyes that underwent trans-scleral ciliary sulcus fixation or ciliary sulcus insertion and the eyes that underwent in-the-bag insertion. However, there was no significant deviation among the eyes that underwent ciliary sulcus insertion with optic capture.

Fortified Barrier Laser On The Vitreous Base In Vitrectomy For Rhegmatogenous Retinal Detachment.

PURPOSE: To investigate the efficacy of fortified barrier laser (FBL) on the vitreous base in vitrectomy for rhegmatogenous retinal detachment (RRD). PATIENTS AND METHODS: This was a retrospective study of patients who underwent vitrectomy for RRD without proliferative vitreoretinopathy. Barrier laser was applied as 3-4 rows surrounding the break at the end of fluid-air exchange. For the FBL, 3-4 rows of laser burn were additionally made about 0.5 clock-hour long adjacent to the break along the posterior border of the vitreous base. The primary outcome was single surgery success rate (SSSR) between two groups: FBL and conventional barrier laser (CBL) groups. RESULTS: Overall, 118 eyes were included; 50 eyes in the FBL group and 68 eyes in the CBL group. SSSR was 100% (50/50) in the FBL group and 91.2% (62/68) in the CBL group with a significant difference (p=0.038). Four eyes of the recurrent cases in the CBL group were related to reopening of the break. All eyes achieved reattachment, and no differences were found in postoperative visual acuity at 6 months. CONCLUSION: FBL on the vitreous base was efficacious in improving the anatomical success rate of vitrectomy.

INCIDENCE OF AND RISK FACTORS FOR DISSOCIATED OPTIC NERVE FIBER LAYER AFTER EPIRETINAL MEMBRANE SURGERY.

PURPOSE: To investigate the incidence of and risk factors for a dissociated optic nerve fiber layer (DONFL) after epiretinal membrane surgery. METHODS: Two hundred and ninety-six primary pars plana vitrectomy operations for epiretinal membrane that were eligible for inclusion in the study. All patients received a complete ophthalmologic examination and color fundus photography, optical coherence tomography preoperatively and postoperatively. DONFL group and non-DONFL group was compared. Univariate and multivariate analyses were performed to establish the risk factors for DONFL. RESULTS: A DONFL developed in 30 of the 296 eyes (incidence, 10.1%). Internal limiting membrane (ILM) peeling was performed in 29 of 30 eyes (96.7%) in the DONFL group and 126 of 266 eyes (47.4%) in the control group (P < 0.001). Intravitreal gas tamponade was performed in 21 eyes (70.0%) in the DONFL group and 133 eyes (50.0%) in the control group (P = 0.038). The ILM peeling (odds ratio, 32.22 [4.33-240.0]; P = 0.001) and intravitreal gas tamponade (odds ratio, 2.33 [1.03-5.28]; P = 0.042) were significantly associated with DONFL. CONCLUSION: It was found that ILM peeling and intravitreal gas tamponade were correlated with postoperative DONFL. The ILM peeling with intravitreal gas tamponade was more strongly correlated with postoperative DONFL formation than was ILM peeling alone.

Comparison of Ocular Pulse Amplitude-Lowering Effects of Tafluprost and Latanoprost by Dynamic Contour Tonometry.

PURPOSE: A prospective study was performed to compare the ocular pulse amplitude (OPA)-lowering effects of tafluprost and latanoprost, used in the treatment of glaucoma, using dynamic contour tonometry. METHODS: The study population consisted of patients with normal-tension glaucoma (NTG) (n = 27) or primary open-angle glaucoma (POAG) (n = 14) treated with tafluprost and latanoprost. All patients were newly diagnosed with NTG and POAG and had undergone no previous treatment. Intraocular pressure (IOP) was measured by Goldmann applanation tonometry (GAT), OPA was measured by dynamic contour tonometry, and corrected OPA (cOPA) was calculated before and after 1 week, 1-3 months of treatment. RESULTS: Initial IOP and OPA were 17.12 ± 3.75, 2.30 ± 0.56 mmHg and 17.53 ± 2.87, 2.65 ± 0.94 mmHg in the tafluprost and latanoprost groups, respectively. After 3 months of treatment, IOP and OPA were 13.00 ± 2.04 mmHg (24.1%) and 1.51 ± 0.30 mmHg (34.3%), respectively, in the tafluprost group. These values were 15.40 ± 2.32 mmHg (12.2%) and 2.08 ± 0.83 mmHg (21.5%), respectively, in the latanoprost group. Therefore, tafluprost significantly reduced IOP (P = 0.01), but OPA-lowering effects did not differ significantly between the 2 groups (P = 0.17). However, the cOPA-lowering effect of tafluprost (1.27 mmHg, 55.2%) was significantly greater than that of latanoprost (0.84 mmHg, 31.7%) after 3 months of treatment (P < 0.001). CONCLUSIONS: Tafluprost and latanoprost, used to treat glaucoma, have marked OPA-lowering effects as well as IOP-lowering effects. Moreover, tafluprost has a greater effect than latanoprost. Therefore, it can be used for patients in need of IOP reduction and at risk of glaucoma progression.

FLUCTUATION OF INFUSION PRESSURE DURING MICROINCISION VITRECTOMY USING THE CONSTELLATION VISION SYSTEM.

PURPOSE: To measure fluctuations in infusion pressure and intraocular pressure (IOP) during vitrectomy performed using a flow-based IOP control system. METHODS: Using 3 vitrectomized porcine eyes, the authors simultaneously measured infusion pressure and IOP during vitreous cutting and aspiration and after extraction of operative instruments in 23-gauge and 25-gauge system. The measurements were performed with the "IOP control" setting turned on or off. The efficacy of valved cannula and a built-in "IOP control limit" module in attenuation of infusion pressure fluctuation was evaluated. RESULTS: At set pressure of 30 mmHg and 60 mmHg, the mean infusion pressure levels were 43.7 mmHg and 78.7 mmHg in the vitreous cutting mode, 67.4 mmHg and 101.2 mmHg in the aspiration mode, and 72.8 mmHg and 115.8 mmHg after extraction of the operative instrument, respectively, when the 23-gauge system was used. Use of valved cannulas effectively attenuated fluctuations in both infusion pressure and IOP. When the IOP control limit setting was "on," the compensatory infusion pressure increase was markedly limited and similar to the set pressure level when the IOP control limit was set at Level 2. Similar results were obtained when a 25-gauge system was used. CONCLUSION: Infusion pressure increased markedly during vitrectomy using a flow-based IOP control system.

Peptide mass fingerprinting- and 2-DE/MS-based analysis of the biodegradation potential for monocyclic aromatic hydrocarbons in Pseudomonas sp.

The combined analysis of peptide mass fingerprinting and 2-DE/MS using the induced and selected protein spots following growth of Pseudomonas sp. DU102 on benzoate or p-hydroxybenzoate revealed not only alpha- and beta-subunits of protocatechuate 3,4-dioxygenase but also catechol 1,2-dioxygenase responsible for ortho-pathway through ring-cleavage of aromatic compounds. Toluate 1,2-dioxygenase and p-hydroxybenzoate hydroxylase were also identified. Purification of intradiol dioxygenases such as catechol 1,2-dioxygenase and protocatechuate 3,4-dioxygenase from the benzoate or p-hydroxybenzoate culture makes it possible to trace the biodegradation pathway of strain DU102 for monocyclic aromatic hydrocarbons. Interestingly, vanillin-induced protocatechuate 3,4-dioxygenase was identical in amino acid sequences with protocatechuate 3,4-dioxygenase from p-hydroxybenzoate.

Juvenile xanthogranuloma as an isolated corneoscleral limbal mass: a case report.

A case of a juvenile xanthogranuloma of the corneoscleral limbus was encountered in a 5-year-old oriental boy, who presented with a 5-month history of a lump in the right eye. The lesion extended from the inferior limbus. This yellow-orange mass was vascular and firmly fixed to the underlying tissue. The lesion was diagnosed preoperatively as an atypical dermolipoma and an uneventful excisional biopsy was performed. The pathologic diagnosis showed the characteristic picture of a juvenile xanthogranuloma with numerous Touton giant cells. Dermoid and lipodermoid tumors, as a corneoscleral limbal mass, are the most frequently encountered in childhood. A juvenile xanthogranuloma is a rare and usually benign skin disease with an unknown cause, which occurs in infants and young children. However, it can occur also as a corneoscleral limbal mass in young children.

N-phenethyl-2-phenylacetamide isolated from Xenorhabdus nematophilus induces apoptosis through caspase activation and calpain-mediated Bax cleavage in U937 cells.

The present study was designed to assess the mechanism of N-phenethyl-2-phenylacetamide (NPPA), one of three new compounds isolated from Xenorhabdus nematophilus, on the induction of apoptosis in U937 cells. NPPA displayed strong inhibitory effects on cell proliferation and viability of U937 cells and induced apoptosis. Investigation of the mechanism of NPPA-induced apoptosis revealed that treatment with NPPA produced morphological features of apoptosis and DNA fragmentation. This was associated with caspase-3 activation and cleavage of poly(ADP-ribose) polymerase. U937 cells treated with NPPA demonstrated cytochrome c accumulation in the cytosol during apoptosis induction. Pretreatment of cells with the pan-caspase inhibitor (z-VAD-fmk) prevented NPPA-induced apoptosis. These results suggested that NPPA induces apoptosis through cytochrome c-dependent caspase-3 activation in U937 cells. In late stage of apoptosis, 18 kDa fragment of Bax was generated with the down-regulation of the expressions of XIAP following NPPA treatment, suggesting that the modulation of Bax and XIAP proteins plays some roles in NPPA-mediated apoptosis. Pretreatments of z-VAD-fmk and the calpain inhibitor, calpeptin, inhibited Bax cleavage. Pretreatment of z-VAD-fmk restored the expression level of XIAP, but pretreatment of calpeptin did not. These results suggest that the elevated caspase activities cleave XIAP in this experiment. And Bcl-2 over-expression attenuates NPPA-induced apoptosis by inhibiting caspase-3 activation, and subsequently inhibits calpain autolysis and Bax cleavage. These results suggested that Bax cleavage is mediated by calpain, and calpain activation may be caspase-dependent. Taken together, the apoptotic effects of NPPA may be related, in part to the caspase-3 activation, the down-regulation of XIAP, and Bax cleavage mediated by caspase-dependent calpain activation.