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PURPOSE: Corneal cross-linking (CXL) is the standard of care in patients with keratoconus but presents unique challenges in children and developmentally delayed patients. We present our clinical decision-making algorithm, CXL surgical technique, and outcomes in these groups. METHODS: A retrospective chart review was undertaken at a tertiary referral center of all patients who underwent CXL for keratoconus at University of Pittsburgh Medical Center (UPMC) Children's Hospital of Pittsburgh between October 1, 2017, and April 1, 2021. Demographic information along with preoperative, intraoperative, and postoperative ophthalmic examination findings were collected. The main outcome measures were indications of CXL, postoperative complications, and visual acuity (VA). RESULTS: Forty-eight eyes of 34 patients [21 patients (30 eyes) with developmental delay (DD) and 13 patients (18 eyes) with no DD (NDD)] underwent epithelium-off, standard CXL. General anesthesia was used for CXL in all patients except for 3 with NDD. A temporary central tarsorrhaphy was performed in all patients with DD and 7 patients with NDD. The remaining got a bandage contact lens. There were no immediate postoperative complications. A trend toward improvement in VA was noted postoperatively. The mean logMAR VA (with habitual correction) was 0.67 preoperatively and 0.57 postoperatively (P = 0.3) in DD and 0.52 and 0.36, respectively (P = 0.13), in NDD. CONCLUSIONS: This retrospective review presents a technique for assessment and treatment of keratoconus in children and those with DD. Our technique ensures timely diagnosis and provides a safe method for CXL in these groups. Temporary central tarsorrhaphy is a well-tolerated option to reduce postoperative pain.

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Phonon modes and their association with the electronic states have been investigated for the metallic EuCu2As2system. In this work, we present the Raman spectra of this pnictide system which clearly shows the presence of seven well defined peaks above 100 cm-1that is consistent with the locally non-centrosymmetricP4/nmmcrystal structure, contrary to that what is expected from the accepted symmorphicI4/mmmstructure. Lattice dynamics calculations using theP4/nmmsymmetry attest that there is a commendable agreement between the calculated phonon spectra at the Γ point and the observed Raman mode frequencies, with the most intense peak at∼232 cm-1being ascribed to the A1gmode. Temperature dependent Raman measurements show that there is a significant deviation from the expected anharmonic behaviour around 165 K for the A1gmode, with anomalies being observed for several other modes as well, although to a lesser extent. Attempts are made to rationalize the observed anomalous behavior related to the hardening of the phonon modes, with parallels being drawn from metal dichalcogenide and allied systems. Similarities in the evolution of the Raman peak frequencies with temperature seem to suggest a strong signature of a subtle electronic density wave instability below 165 K in this compound.

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Ferroic orders and their associated structural phase transitions are paramount in the understanding of a multitude of unconventional condensed matter phenomena. On this note, our investigation focuses on the polymorphic ferroelectric (FE) phase transitions of Copper(II) hydroxide, Cu(OH)2, considering an antiferromagnetic ground state. By employing the first-principles studies and group theory analysis, we have provided a systematic theoretical investigation of vibrational properties in the hypotheticalCmcmhigh-symmetry phase to unveil the symmetry-allowed ferroic phases. We identified a non-polar to polar (Cmc21) phase transition, in which the displacive transformation is primarily responsible for the phase change induced by twoB1u(i.e.Γ2-) phonon modes within the centrosymmetric phase. We also observed the existence of two polar structures with the same space group and different degrees of polarization (i.e.Ps= 3.06µC·cm-2andPs= 42.41µC·cm-2), emerging from the high symmetry non-polar structure. According to the structural analysis the FE order, of a geometric nature, is driven by theΓ2-mode in which the O- and H-sites displacements lead the polar distortion with a minor contribution from the Cu-sites. Interestingly, the 3d9:Cu2+Jahn-Teller distortion coupled with the orientational shifts of O-H atoms enhances the polarization.

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Pyrazoles have recently received significant attention due to their unique and potential applications in the medical field, agriculture and are also known to be highly stable explosives. The present work describes the terahertz time-domain spectroscopy (THz-TDS) based study of 4-Amino 3,5 Dinitro Pyrazole(ADNP) in between the 0.1 and 3.0 THz ranges. A Toptica-Teraflash fibre-coupled handheld terahertz system has been employed in reflection mode configuration. We ascertained complex refractive index, absorption coefficients, and complex dielectric constants from 0.1 THz to 3.0 THz. The value of the refractive index and absorption coefficients are found to be 1.8 and 10---180 cm -1, respectively. Also, we have analyzed the structural, vibrational, and optical properties of ADNP using the plane-wave pseudopotential method based on Density Functional Theory (DFT) calculations. We have observed six low-frequency optical phonon modes, located at 0.36, 1.20, 1.52, 1.77, 2.40, and 2.75 THz, respectively, exhibiting a redshift compared to the values predicted by the DFT calculations. The possible reasoning for the above might be due to the anharmonicity that is not considered in the DFT calculations. The theoretical calculations align with the experimental results and deliver direction for further investigations and the futuristic application of ADNP.

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PURPOSE: Ocular surface lipodermoids with corneal involvement may require surgical intervention; if deep, ocular surface reconstruction with lamellar corneal tissue or amniotic membrane may be needed. We describe a staged technique using autologous ipsilateral simple limbal epithelial transplantation. METHODS: After verifying sparing of Descemet membrane, the conjunctival portion of the lipodermoid was debulked in the first stage. Six weeks later, the corneal portion was excised, followed by autologous ipsilateral simple limbal epithelial transplantation to promote rapid reepithelialization of the residual stromal bed. Temporary tarsorrhaphy was used for patient comfort and to expedite ocular surface healing. RESULTS: Three eyes of 3 children with grade III large ocular surface lipodermoids that encroached the visual axis and hindered proper eyelid closure underwent surgery without complications. In all cases, the visual axis was cleared and eyelid closure was improved. At the last follow-up (mean 35.7 months, median 36.0 months), the bed of the original dermoid showed minimal haze in 1 case, while 2 eyes developed small pseudopterygium; best spectacle-corrected visual acuity improved from 20/200 to 20/70 in the first case, from fix and follow to 20/50 in the second case, and remained fix and follow in the last case, but this child had congenital hydrocephalus with severe developmental delay. CONCLUSIONS: This surgical technique is a promising option for children with grade III large ocular surface lipodermoids given its effectiveness in clearing the visual axis and in improving eyelid closure. Moreover, it does not require lamellar corneal transplantation or intervention to the fellow eye.

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Keratoconus (KC) is a complex multifactorial corneal ectatic disorder, with disease onset commonly in the second-third decades significantly affecting quantity, quality of vision, and quality of life. Several pathways and factors such as eye rubbing, inflammatory, oxidative, metabolic, genetic, and hormonal among others have been studied in the last two decades. However, the management of KC is still based on a few "one-size fits all" approaches and is predominantly guided by topo/tomographic parameters. Consideration of the several novel factors which have the potential to be biomarkers in addressing several unanswered questions in the disease process could help in the better predictive ability of progression or vision loss and customization of treatment options. This article delves into the understanding of these novel factors or biomarkers based on the pathogenesis of KC and features a special focus on their potential clinical applications and their future role in personalized medicine.

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Structural phase transitions drive several unconventional phenomena including some illustrious ferroic attributes which are relevant for technological advancements. On this note, we have investigated the ferroelastic structural transition of perovskite-type trigonal Ba2ZnTeO6 across Tc ∼ 150 K. With the help of Raman spectroscopy and density-functional theory (DFT)-based calculations, we report new intriguing observations associated with the phase transition in Ba2ZnTeO6. We observed the presence of a central peak (quasi-elastic Rayleigh profile), huge softening in the soft mode, hysteretic phonon behavior, and signatures of coexistent phases. The existence of a central peak in Ba2ZnTeO6 is manifested by a sharp rise in the intensity of the Rayleigh profile concomitant with the huge damping (or softening) of the soft mode (at ∼31 cm-1) near Tc, shedding light on the lattice dynamics during the phase transition. This is further corroborated by our phonon calculations that show that the soft mode (Eg) in the high-symmetry structure involving TeO6 octahedral rotation (with Ba and Zn translation) condenses into Ag and Bg modes in the C2/m low-symmetry phase. While most of the phonon bands split below Tc confirming the phase transition, we observed thermal hysteretic behavior of phonon modes, which signifies the first-order nature of the transition and the presence of coexisting phases as corroborated by our temperature-dependent X-ray diffraction and specific heat measurements.

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Pythium insidiosum (PI) is an oomycete, a protist belonging to the clade Stramenopila. PI causes vision-threatening keratitis closely mimicking fungal keratitis (FK), hence it is also labeled as "parafungus". PI keratitis was initially confined to Thailand, USA, China, and Australia, but with growing clinical awareness and improvement in diagnostic modalities, the last decade saw a massive upsurge in numbers with the majority of reports coming from India. In the early 1990s, pythiosis was classified as vascular, cutaneous, gastrointestinal, systemic, and ocular. Clinically, morphologically, and microbiologically, PI keratitis closely resembles severe FK and requires a high index of clinical suspicion for diagnosis. The clinical features such as reticular dot infiltrate, tentacular projections, peripheral thinning with guttering, and rapid limbal spread distinguish it from other microorganisms. Routine smearing with Gram and KOH stain reveals perpendicular septate/aseptate hyphae, which closely mimic fungi and make the diagnosis cumbersome. The definitive diagnosis is the presence of dull grey/brown refractile colonies along with zoospore formation upon culture by leaf induction method. However, culture is time-consuming, and currently polymerase chain reaction (PCR) method is the gold standard. The value of other diagnostic modalities such as confocal microscopy and immunohistopathological assays is limited due to cost, non-availability, and limited diagnostic accuracy. PI keratitis is a relatively rare disease without established treatment protocols. Because of its resemblance to fungus, it was earlier treated with antifungals but with an improved understanding of its cell wall structure and absence of ergosterol, this is no longer recommended. Currently, antibacterials have shown promising results. Therapeutic keratoplasty with good margin (1 mm) is mandated for non-resolving cases and corneal perforation. In this review, we have deliberated on the evolution of PI keratitis, covered all the recently available literature, described our current understanding of the diagnosis and treatment, and the potential future diagnostic and management options for PI keratitis.

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OBJECTIVE: To compare corneal biomechanics and intraocular pressure (IOP) in keratoconus and penetrating keratoplasty eyes before and after nonfenestrated scleral lens wear. METHODS: Twenty-three participants were enrolled, and 37 eyes were included in the analysis (11 penetrating keratoplasty and 26 keratoconus). A range of corneal biomechanical parameters and IOP were measured using the CORVIS ST before and after 8 hr of nonfenestrated scleral lens wear (Keracare, Acculens, Denver, CO). RESULTS: Before lens wear, penetrating keratoplasty eyes displayed significantly greater median values for central corneal thickness (97 µm thicker, P=0.02), IOP (3.89 mm Hg higher, P=0.01), and biomechanical parameter A2 length (0.48 mm longer, P=0.003) compared with keratoconic eyes. No significant changes in corneal biomechanical parameters or IOP were observed after scleral lens wear in either group (all P>0.05). CONCLUSION: Although nonfenestrated scleral contact lenses can induce a subatmospheric pressure after lens settling and compress tissue surrounding the limbus, no significant changes were detected in the corneal biomechanical parameters studied using CORVIS ST after scleral lens wear in eyes with penetrating keratoplasty and keratoconus.

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This article thoroughly addresses the structural, mechanical, vibrational, electronic band structure and the optical properties of the unexplored thallous perchlorate and perbromate fromab initiocalculations. The zone centered vibrational phonon frequencies shows, there is a blue shift in the mid and high frequency range from Cl → Br due to change in mass and force constant with respect to oxygen atom. From the band structure it is clear that the top of the valence band is due to thalliumsstates, whereas the bottom of the conduction band is due to halogensand oxygenpstates, showing similar magnitude of dispersion and exhibits a charge transfer character. These characteristics and the band gap obtained are consistent with that of a favourable scintillators. Our findings deliver directions for the design of efficient TlXO4based scintillators with high performance which are desirable for distinct applications such as medical imaging, high energy physics experiments, nuclear security.

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A systematic analysis of the electronic, thermoelectric and optical properties of triclinic van der Waal's solids NbX2Y2(X = S, Se and Y = Cl, Br, I) is carried out within the framework of density functional theory for bulk and monolayer. The investigated compounds are semiconductors in bulk and monolayer, with band gap values ranging from 1.1 to 1.8 eV. We observed huge anisotropy in the electrical conductivity with the in-plane conductivity being 40 times higher than out-of-plane conductivity in NbS2I2. The observed high power factor and low thermal conductivity in NbX2Y2render these compounds as potential thermoelectric materials. In addition, the calculated optical properties such as refractive index and absorption coefficient reveal the optical anisotropy. We have calculated birefringence for all the studied compounds and a large value of 0.313 is observed for NbSe2I2. The monolayer electronic properties indicate the presence of anomalous quantum confinement. The giant birefringence along with promosing monolayer properties are the highlights of present work which might fetch future device applications in both bulk as well as monolayer.

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The impact of Ta doping on two orthoniobates SmNbO4 and HoNbO4 has been studied using a combination of high-resolution powder diffraction and Density-Functional Theory calculations. In both ANb1-xTaxO4 (A = Sm, Ho) series the unit cell volume decreases as the Ta content increased demonstrating that the effective ionic radii of Ta is smaller than that of Nb in this structure. The average Sm-O distance and volume of the SmO8 polyhedra were invariant of the Ta content across the SmNb1-xTaxO4 solid solution whereas the average M-O (M = Nb or Ta) distance and MO6 polyhedral volume decrease with Ta doping. The analogous Ho oxides HoNb1-xTaxO4 do not form a complete solid solution when the samples were prepared at 1400 °C, rather there is a miscibility gap around x = 0.95, with HoTaO4 exhibiting the M'-type P2/c structure rather than the M-type I2/a structure of HoNbO4. Increasing the synthesis temperature to 1450 °C eliminates the miscibility gap. The energy difference between the P2/c and I2/a structures of HoTaO4 is found to be nearly 30 meV per f.u. with the total energy of the P2/c phase of HoTaO4 being more negative. First-principles calculations, carried out using Density-Functional Theory, reveal significant covalent character in the Nb-O bonds, which is reduced in the corresponding tantalates. Anisotropy in the Born Effective Charge tensors demonstrates the impact of the long M-O bond identified in the structural studies showing that the Nb and Ta cations are effectively six-coordinate. The similarity in the frequency of the intense Raman peak near 800 cm-1 due to the symmetric stretching of the Ta-O bonds is consistent with the description of that both polymorphs of HoTaO4 contain TaO6 octahedra.

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PURPOSE: To quantify the effect of a single scleral lens design on visual acuity and ocular higher-order aberrations in eyes with post-LASIK ectasia, keratoconus and pellucid marginal degeneration (PMD) that could not achieve satisfactory vision with spectacles or soft contact lenses. METHODS: Forty-six eyes of 28 participants fitted with diagnostic scleral lenses (KeraCare) were analysed, including 19, 15 and 12 eyes with post-LASIK ectasia, keratoconus and PMD, respectively. Corrected distance visual acuity (CDVA) and ocular aberrations were measured prior to lens wear and during lens wear after 60 min of settling. An i-Trace aberrometer was used to determine aberrations over a 4.5 mm diameter pupil. RESULTS: Before lens wear, the median (95% confidence interval) values across all groups were: CDVA 0.30 (0.30, 0.40) logMAR, spherical equivalent refraction -2.75 (-5.25, -2.12) D, cylindrical refraction 3.75 (2.50, 5.00) D, higher-order-root-mean-square error (HO-RMS) 0.90 (0.64, 1.03) µm and vertical coma co-efficient C(3,-1) -0.32 (-0.42, -0.12) µm. RMS coma of 0.52 (0.40, 0.74) µm was higher for the keratoconus group than for the other groups (p < 0.05). During lens wear, values improved considerably across all groups: CDVA 0.0 (0.0, 0.00) logMAR, spherical equivalent refraction -0.50 (-0.75, +0.50) D, cylindrical refraction 0.50 (0.00, 0.50) D, HO-RMS 0.32 (0.26, 0.42) µm and C(3,-1) +0.12 (+0.02, +0.19) µm (all p < 0.001 compared to pre-lens wear). While reduced significantly, RMS coma remained higher in the keratoconus group at 0.35 (0.31, 0.52) µm than in the post-LASIK ectasia and PMD groups at 0.17 (0.12, 0.21) µm and 0.07 (0.02, 0.46) µm, respectively (p < 0.05). CONCLUSIONS: The KeraCare scleral contact lens reduced ocular aberrations and improved visual acuity in patients with post-LASIK ectasia, keratoconus and PMD. The sign of vertical coma changed in keratoconus and PMD.

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Half-Heusler thermoelectric materials are potential candidates for high thermoelectric efficiency. We report high-pressure thermoelectric and structural property measurements, density functional theory calculations on the half-Heusler material TiNiSn, and an increase of 15% in the relative dimensionless figure of merit, ZT, around 3 GPa. Thermal and electrical properties were measured utilizing a specialized sample cell assembly designed for the Paris-Edinburgh large-volume press to a maximum pressure of 3.5 GPa. High-pressure structural measurements performed up to 50 GPa in a diamond-anvil cell indicated the emergence of a new high-pressure phase around 20 GPa. A first-principles structure search performed using an ab initio random structure search approach identified the high-pressure phase as an orthorhombic type, in good agreement with the experimental results.

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ABSTRACT: This case report describes a unique presentation of bilateral sequential acute corneal hydrops that manifested several years after laser in situ keratomileusis. Initial management included anterior chamber perfluoropropane gas injection and corneal suturing. Longer-term visual rehabilitation involved the use of scleral lenses which significantly reduced lower- and higher-order ocular aberrations.

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The present work describes a density-functional theory (DFT) study of TlReO4 in combination with powder x-ray diffraction experiments as a function of temperature and Raman measurements at ambient temperature. X-ray diffraction measurements reveal three different structures as a function of temperature. A monoclinic structure (space group P21/c) is observed at room temperature while two isostructural tetragonal structures (space group I41/a) are found at low- and high-temperature. In order to complement the experimental results first-principles DFT calculations were performed to compute the structural energy differences. From the total energies it is evident that the monoclinic structure has the lowest total energy when compared to the orthorhombic structure, which was originally proposed to be the structure at room temperature, which agrees with our experiments. The structural and vibrational properties of the low- and room-temperature phase of TlReO4 have been calculated using DFT. Inclusion of van der Waals correction to the standard DFT exchange correlation functional is found to improve the agreement with the observed structural and vibrational properties. The Born effective charge of these phases has also been studied which shows a combination of ionic and covalent nature, resembling metavalent bonding. Calculations of zone-center phonon frequencies lead to the symmetry assignment of previously reported low-temperature Raman modes. We have determined the frequencies of the eight infrared-active, 13 Raman-active and three silent modes of low-temperature TlReO4 along with 105 infrared-active and 108 Raman-active modes for room-temperature TlReO4. Phonons of these two phases of TlReO4 are mainly divided into three regions which are below 150 cm-1 due to vibration of whole crystal, 250 to 400 cm-1 due to wagging, scissoring, rocking and twisting and above 900 cm-1 due to stretching in ReO4 tetrahedron. The strongest infrared peak is associated to the internal asymmetric stretching of ReO4 whereas the strongest Raman peak is associated to the internal symmetric stretching of ReO4. We have also measured the room-temperature Raman spectra of monoclinic TlReO4 identifying up to 28 modes. This Raman spectrum has been interpreted by comparison with the previously reported Raman frequencies of the low-temperature phase and our calculated Raman frequencies of low- and room-temperature phases of TlReO4.

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PURPOSE: Assessment of repeatability of Orbscan III in measuring steep keratometry (sKm), flat keratometry (fKm), thinnest corneal thickness (TCT), anterior chamber depth (ACD), white-to-white diameter (WTW) and 3 mm and 5 mm zonal irregularity in healthy eyes. METHODS: In this prospective observatioanl study 100 eyes of 50 participants underwent three consecutive scans on Orbscan III by a single examiner with a gap of 5 minutes between scans. Statistical analysis was performed to assess the repeatability of sKm, fKm, TCT, WTW, ACD and parameters of 3- and 5 mm irregularity. Within subject standard deviation (Sw), coefficient of variation (CoV) and test retest variability (TRT) was calculated for the commonly used parameters. WERE THE MAIN OUTCOME MEASURES.: The repeatability of sKm, fKm, TCT, WTW, ACD, 3 mm and 5 mm zonal irregularity on Orbscan III. RESULTS: Total of 50 patients (25 male and 25 female) who fulfilled inclusion and exclusion criteria were assessed. sKm, fKm, TCT and WTW were found to have a TRT of 0.31, 0.29. 21.5 and 0.27, respectively, and the ICC values were found to be over 0.9, denoting high repeatability. Repeat measurements of parameters of irregularity and ACD were found to be statistically similar, again denoting similarity between repeat measurements. CONCLUSION: Orbscan III provides repeatable measurements of Sim-k, anterior chamber depth, thinnest corneal thickness, 3 mm and 5 mm zonal irregularity and white-to-white diameter in healthy eyes.

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We present a thorough density functional theory based computational study of crystalline properties of cubane caged potential energetic material octanitrocubane (ONC). As expected for a layered molecular solid, van der Waals corrections are inevitable and the same has been incorporated to capture the ground state properties more accurately. Study of Born effective charge and zone centered phonon frequencies using density functional perturbation theory reveals the important role of N2, N4 type nitrogen and associated oxygen atoms in contributing to the high intensity infrared modes. From the calculated electronic band structure we can conclude that ONC is an insulator with a band gap of 5.31 eV. The optical properties of ONC are found to be nearly isotropic in low energy region in spite of strong anisotropic crystal structure.