Next generation of the self-consistent and environment-dependent Hamiltonian: Applications to various boron allotropes from zero- to three-dimensional structures.

An upgrade of the previous self-consistent and environment-dependent linear combination of atomic orbitals Hamiltonian (referred as SCED-LCAO) has been developed. This improved version of the semi-empirical SCED-LCAO Hamiltonian, in addition to the inclusion of self-consistent determination of charge redistribution, multi-center interactions, and modeling of electron-electron correlation, has taken into account the effect excited on the orbitals due to the atomic aggregation. This important upgrade has been subjected to a stringent test, the construction of the SCED-LCAO Hamiltonian for boron. It was shown that the Hamiltonian for boron has successfully characterized the electron deficiency of boron and captured the complex chemical bonding in various boron allotropes, including the planar and quasi-planar, the convex, the ring, the icosahedral, and the fullerene-like clusters, the two-dimensional monolayer sheets, and the bulk alpha boron, demonstrating its transferability, robustness, reliability, and predictive power. The molecular dynamics simulation scheme based on the Hamiltonian has been applied to explore the existence and the energetics of ∼230 compact boron clusters BN with N in the range from ∼100 to 768, including the random, the rhombohedral, and the spherical icosahedral structures. It was found that, energetically, clusters containing whole icosahedral B12 units are more stable for boron clusters of larger size (N > 200). The ease with which the simulations both at 0 K and finite temperatures were completed is a demonstration of the efficiency of the SCED-LCAO Hamiltonian.

Homelessness in pregnancy.

OBJECTIVES: To evaluate the association, if any, of homelessness or refuge accommodation on delivery and short term perinatal outcomes in an Irish tertiary maternity hospital. METHODS: A retrospective cohort study of 133 singleton pregnancies in women reporting to be homeless or living in refuge at their booking antenatal appointment between 2013 and 2022. Analysis compared sociodemographic characteristics and perinatal outcomes in this cohort to a reference population of 76,858 women with stable living arrangements. RESULTS: Women in the homeless/refuge population were statistically more likely to be single (75.2 % vs 39.5 %, p < 0.001), have an unplanned pregnancy (73.7 % vs 27.2 %, p < 0.001), report a history of psychiatric illness (42.9 % vs 22.4 %, p < 0.001), domestic violence (18.8 % vs 0.9 %, p < 0.001) alcohol consumption in pregnancy (3.0 % vs 0.8 %, p < 0.001) or smoking in pregnancy (41.3 % vs 9.7 %, p < 0.001). They were significantly more likely to have a preterm birth (adjusted OR 1.71 (1.01-2.87) p = 0.04). They also had a significantly lower median birth weight compared to the reference population (birthweight 3270 g vs 3420 g, p < 0.001). CONCLUSION: Women in the homeless and refuge population are more likely to experience poorer perinatal outcomes compared to women with stable living arrangements.

A non-stationary model for simulating the dynamics of ocular aberrations.

The time-evolution of ocular aberrations has been the subject of many studies, but so far there has been little discussion involving the modelling of the underlying temporal statistics. This paper presents a non-stationary modelling approach based on a coloured-noise generator, which can be applied to ocular aberration dynamics. The model parameters are computed from measured ocular aberration data. A custom-built aberrometer based on a Shack-Hartmann sensor was used for measurement. We present simulations based on our modelling approach, and validate them through comparison to real data. This work could be useful in areas such as the testing of ophthalmic devices and the development of improved algorithms for laser refractive surgery.

Temporal dynamics and statistical characteristics of the microfluctuations of accommodation: dependence on the mean accommodative effort.

Microfluctuations of accommodation have been the subject of many studies. New technological developments now permit us to study the dynamics of the microfluctuations with unprecedented resolution and accuracy. We aim to characterise their temporal statistics for different levels of accommodative effort, using a custom-built aberrometer. We conducted 46 s long measurements on the dominant eye of 9 young, healthy subjects. The ocular wavefront was sampled every 250 microm across the 3.9 mm measured pupil, at a frame rate of 173 Hz. This enabled us to obtain high resolution estimates of the Power Spectral Density (PSD). Results show that the shape of the estimated PSD for a 4 D effort is distinct from the shape for the two extrema of the accommodation range. The autocorrelation function of the increments of the accommodation signal is also affected by the level of effort, regardless of the refractive error of the subject.

Energetics, relative stabilities, and size-dependent properties of nanosized carbon clusters of different families: fullerenes, bucky-diamond, icosahedral, and bulk-truncated structures.

Structures and relative stabilities of carbon clusters belonging to different families have been investigated for diameters d < or = 5 nm based on an efficient semiempirical molecular dynamics (MD) scheme as well as a density functional theory based simulation. Carbon clusters studied include fullerenes and fullerene-derived structures (e.g., cages and onions), icosahedral structures, bucky-diamond structures, and clusters cut from the bulk diamond with spherical and facetted truncations. The reason for using a semiempirical MD is partly due to the large number of different cases (or carbon allotropes) investigated and partly due to the size of the clusters investigated in this work. The particular flavor of the semiempirical MD scheme is based on a self-consistent and environment-dependent Hamiltonian developed in the framework of linear combination of atomic orbitals. We find that (i) among the families of carbon clusters investigated, fullerene structures have the lowest energy with the relative energy ordering being E(fullerene) < E(onion) < E(icosahedral) < E(bucky-diamond) < E(bulk-truncated), (ii) a crossover between bucky-diamond and icosahedral structures is likely at d approximately 8 nm, (iii) the highest occupied molecular orbital-lowest unoccupied molecular orbital gap as a function of the diameter for the case of fullerenes shows an oscillatory behavior with the gap ranging from 2 eV to 6 meV, and the gap approaching that of gapless graphite for d > 3.5 nm, and (iv) there can be three types of phase transformations depending on the manner of heating and cooling in our simulated annealing studies: (a) a bucky-diamond structure --> an onionlike structure, (b) an onionlike --> a cage structure, and (c) a bucky-diamond --> a cage structure.

Distribution of membrane phospholipids in the rabbit neural retina, optic nerve head and optic nerve.

Since diseases of the neural retina and optic nerve can result in alteration of biological membranes, this study determines similarities and differences in the membrane phospholipid content of the neural retina, optic nerve head, and optic nerve to serve as baseline data. Neural retina, optic nerve head, and optic nerve were dissected, isolated as 5 sets from 20 rabbits and frozen in liquid N2. Separate pooled-tissue extracts were prepared for each set of tissues and phosphorus-31 nuclear magnetic resonance (31P NMR) analyses performed. Ten phospholipids were quantified (respective neural retina, optic nerve head, and optic nerve mole % are given for the 5 major phospholipids detected): phosphatidylcholine (PC), 44.61, 27.67, 26.40; PC plasmalogen or alkylacyl PC (CPLIP); phosphatidylinositol (PI); sphingomyelin (SM); phosphatidylserine (PS), 12.63, 14.77, 15.09; phosphatidylethanolamine (PE), 21.21, 9.59, 8.69; PE plasmalogen (EPLAS), 11.07, 30.96, 33.93; an unidentified (unknown) phospholipid (U) at the chemical-shift value of 0.13 ppm; diphosphatidylglycerol (DPG); and phosphatidic acid (PA), 0.46, 2.92, 1.57. Significant differences between the various tissues were determined by the one-way analysis of variance, using a Scheffé range value of P < 0.05. The neural retina in all phospholipids detected except for the uncharacterized (unknown) phospholipid was significantly different from the optic nerve head tissue. The optic nerve head was significantly different from the optic nerve in PC, CPLIP, PE, EPLAS, U, DPG, and PA. The data provide a baseline for studies on pathologically changed neural retina, optic nerve head, and optic nerve.

Contingent and non-contingent auditory cueing in Parkinson's disease.

Parkinson's disease (PD) patients and their normal controls performed two experiments involving a sequential movement task, depressing a series of buttons at choice points along a response board. Visual or auditory cues were presented prior to each move according to various contingencies. PD, a disorder characterised by degeneration of the basal ganglia (BG), typically manifests with poor execution of motor sequences. We found that external cueing facilitated motor sequencing in PD patients. In particular, auditory cues which occurred late in the movement cycle maximally facilitated switching between subcomponents of a sequence. Based on physiological findings reported in the primate literature [Brotchie et al., Brain 114, 1685-1702, 1978; Schultz and Romo, Exp. Brain Res. 1, 363-384, 1992], it is suggested that external cues enhance performance by replacing defective, internally generated cues (discharges) of the BG. This has implications for the use of physical training strategies in the treatment of PD.

Distribution of membrane phospholipids in the crystalline lens.

PURPOSE: To determine the phospholipid content of specific anatomic regions within the crystalline lens. METHODS: Phospholipid extracts of tissues dissected from 5 sets of 10 rabbit lenses were analyzed by 31P nuclear magnetic resonance spectroscopy. Twenty-nine pathway-specific metabolic indexes were calculated from groups of phospholipids and ratios of phospholipids. RESULTS: Phospholipid levels (mole percent) were determined from the capsule with attached epithelium, the cortex, and the nucleus. Eleven phospholipids were detected with significant regional differences in the lens phospholipid profiles. The levels of phosphatidylcholine (PC), PC plasmalogen-alkylacyl PC, phosphatidylinositol (PI), phosphatidylethanolamine (PE), and diphosphatidylglycerol (DPG), and of the lyso derivatives (lyso PC and lyso PE) were greater in the capsule plus epithelium than in the cortex or the nucleus. Levels of sphingomyelin, phosphatidylserine, and PE plasmalogen (EPLAS) were less in the capsule plus epithelium than in the cortex or the nucleus. PC, PC plasmalogen-alkylacyl PC, EPLAS, and lyso PE had nearly equal amounts in the cortex and the nucleus. PI, lyso PC, and DPG could not be detected in the nucleus. DPG was only detected in the capsule plus epithelium. An unidentified phospholipid at 0.13 ppm was approximately equal in the cortex and the nucleus, but it could not be detected in the capsule plus epithelium. CONCLUSIONS: These differences demonstrate a significant heterogeneity among these anatomic regions of the lens, and differences in the nucleus relative to other regions studied are consistent with those in membranes that less readily undergo transitions from the relatively impermeable lamellar phase to the more permeable hexagonal HII phase.

The DBA/2J strain and prepulse inhibition of startle: a model system to test antipsychotics?

RATIONALE: Prepulse inhibition (PPI) of the startle response in mice is increasingly used as a paradigm of sensory gating with potential predictive and construct validity towards schizophrenia. OBJECTIVES: Establishment of a mouse PPI paradigm in which typical and atypical antipsychotic drugs directly improve a low performance PPI. METHODS: Three strains of mice--C57Bl/6J, 129S6/SvEvTac and DBA/2J--were tested in a startle paradigm with three prepulse intensities, 2, 4 and 8 dB above background. RESULTS: Under these conditions, risperidone (0, 0.25, 0.5 and 1 mg/kg i.p.) and clozapine (0, 1, 3 and 9 mg/kg i.p.) improved PPI in all three strains, with order of effect in DBA/2J > 129S6SvEvTac > C57Bl/6J. The DBA/2J strain showed larger PPI-enhancing effects, without disturbing the basal startle response. Two alpha7 nicotinic receptor agonists, GTS-21 (1-10 mg/kg i.p.) and AR-R17779 (1-10 mg/kg i.p.) were inactive in the PPI procedure in DBA/2J mice. CONCLUSIONS: DBA/2J mice were very sensitive to the antipsychotic-like effects of atypical (clozapine) and typical (risperidone) antipsychotics, and this strain is proposed as a model to directly measure sensory gating properties of drugs. Alpha7 Nicotinergic receptor agonists were ineffective in this PPI paradigm.

Emedastine ophthalmic solution 0.05% versus levocabastine ophthalmic suspension 0.05% in the treatment of allergic conjunctivitis using the conjunctival allergen challenge model.

PURPOSE: To compare a new ocular antihistamine, emedastine difumarate (Emadine Ophthalmic Solution 0.05%; Alcon Laboratories, Fort Worth, Texas), with the marketed ocular antihistamine, levocabastine hydrochloride (Livostin Ophthalmic Suspension 0.05%; CIBA Vision, Atlanta, Georgia), in the treatment of allergic conjunctivitis after conjunctival allergen challenge. METHODS: We performed a prospective, double-masked, randomized, contralateral eye study comparing emedastine 0.05% in one eye with levocabastine 0. 05% or emedastine vehicle (placebo) in the contralateral eye. Efficacy was determined 10 minutes and 2 hours after administration of study medications. Ocular itching and redness scores were recorded 3, 5, and 10 minutes after conjunctival allergen challenge. RESULTS: A total of 97 subjects with a history of allergic conjunctivitis and a positive response to a diagnostic test were evaluable for safety analysis, and 91 subjects were evaluable for the efficacy analysis. Emadastine 0.05% was statistically significantly more effective than levocabastine 0.05% in reducing ocular itching after conjunctival allergen challenge in both the 10-minute and the 2-hour challenge (P <.05). Emedastine 0.05% and levocabastine 0.05% were statistically equivalent in reducing conjunctival redness after conjunctival allergen challenge, although emedastine tended to be more efficacious than levocabastine at every observation time point. CONCLUSIONS: After conjunctival allergen challenge, emadastine 0.05% is significantly more effective than levocabastine 0.05% in reducing ocular itching associated with allergic conjunctivitis. The two compounds are equivalent in controlling the conjunctival redness associated with allergic conjunctivitis.

Histopathology of the ocular surface after eye rubbing.

PURPOSE: This study demonstrates the effects of eye rubbing on ocular surface tissue. METHODS: Rabbits (3-4 kg; n = 24) were killed at 0, 4-h, 8-h, and 12-h intervals after a 5-min period of eye rubbing. Ocular surface tissues were studied by light and scanning electron microscopy. Contralateral eyes served as controls. Eye rubbing was accomplished by using digital pressure over the closed eyelid with a force sufficient to appreciate by palpation the orbital rim. Biomicroscopic examination revealed marked vascular injection of the conjunctiva. Ocular surface tissues studied included the lid margins, the upper and lower tarsal conjunctivae, the bulbar conjunctiva, and the cornea. RESULTS: Changes in the ocular surface included dramatic alteration in the upper tarsal conjunctiva when compared with controls. The cornea and bulbar and lower tarsal conjunctiva were not altered when compared with control tissues, except for some increase in exfoliating cells in the cornea. The surface epithelial cells of the upper tarsal conjunctiva had a spheroidal structure and were markedly elevated, the microprojections were altered, and there was evidence of increased cellular exfoliation. These changes were most pronounced at the 0 and 4-h time points, less noticeable at 8 h, and no appreciable changes were observed when compared with control tissues at 12 h. CONCLUSION: This study demonstrates that eye rubbing causes surface alterations in the stratified cuboidal to columnar epithelial surface of the upper tarsal conjunctiva while sparing the stratified squamous epithelial surface of the distal lid margins and cornea.

Tear film lipid layer thickness as a function of blinking.

Alterations in the tear film lipid layer as a function of blinking were investigated using a custom-designed specular reflection monitoring system. The tear film lipid layer of 104 subjects under conditions of normal ("baseline") blinking and "forceful" blinking was quantitated on the basis of specific interference colors. Deliberate, forceful blinking was found to significantly increase the lipid layer thickness (LLT) of the tear film. The magnitude of increase was found to be correlated with the baseline LLT values; individuals with baseline LLT values of 75-150 nm demonstrated a mean increase in LLT of 33 nm following forceful blinking, whereas subjects with baseline LLT values < or = 60 nm experienced a mean increase of 19 nm. The difference in the magnitude of increase between the groups was highly significant (p = 0.0001). The data suggest that, in addition to playing a role in the spreading of lipid across the tear film, the blinking mechanism may be important in the maintenance of the lipid layer by augmenting the expression of lipids from the meibomian glands.

Meibomian gland phospholipids.

The content of the meibomian gland lipid exprimate is known, but little is known about the phospholipids that comprise the glandular cells. The purpose of the present study is to identify and quantitate the phospholipid complement of the meibomian gland cells that produce the lipid secretion of meibomian oil and which is vital to tear film stability. Eyelids (n = 50) were excised from rabbits, and after surgical removal of surrounding tissues, the tarsal plates with and without expressing meibomian oil were extracted and phospholipids of the plates quantified by 31P nuclear magnetic resonance (NMR). Seventeen phospholipids were quantified from tarsal plates expressed of oil and tarsal plates containing meibomian oil: alkylacylphosphatidylcholine (AAPC), dihydrosphingomyelin (DHSM), dimethylphosphatidylethanolamine, diphosphatidylglycerol (cardiolipin), ethanolamine plasmalogen (EPLAS), lysoethanolamine plasmalogen, lysophosphatidylcholine, lysophosphatidylethanolamine, lysophosphatidylserine, phosphatidic acid, phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylglycerol, phosphatidylinositol, phosphatidylserine, sphingomyelin (SM), sphingosylphosphorylcholine. The six zwitterionic and neutral phospholipids, DHSM, EPLAS, PE, SM, AAPC, and PC together comprise 79.5% of the total meibomian gland phospholipid profile (in meibomian oil this value is 84.2%). The zwitterionic and neutral phospholipids dominate meibomian gland phospholipid profiles. Since the meibomian gland cells undergo holocrine secretion and form the meibomian glad secretion, such a composition is consistent with the hypothesis that a chemically stable lamellar surfactant layer phospholipids bind non-polar meibomian oil to the aqueous layer of the tear film.

Initial in vivo tear protein deposition on individual hydrogel contact lenses.

We investigated and compared the initial composition, morphology, and time course of deposits on individual soft contact lenses of different water contents and surface charges in order to evaluate the potential for antigenic reactions and to predict the optimal frequency of lens replacement. Newly manufactured lenses were worn for graduated periods of time from 1 min to 8 h by subjects who were first adapted to daily wear soft lenses. The morphology and composition of the deposits were analyzed by histological staining, light microscopy, scanning electron microscopy (SEM), sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) with silver nitrate staining, and immunofluorescence microscopy. The protein bands of the acrylamide gels were divided according to their molecular weights into six groups which have been defined in the literature from tear analyses by electrophoretic techniques and include lysozyme, proteins migrating faster than albumin (PMFA), protein G, albumin, lactoferrin, and other proteins heavier than albumin such as Ig-G and secretory Ig-A. Specific proteins (lysozyme, PMFA, and protein G) were detected on individual lenses after as little as 1 min of wear. There was an increasing amount of protein deposited as the wearing time increased. Differences in the rates and amounts of deposition were more dependent on lens water content and ionic characteristics than on intersubject differences. Such early significant protein deposition may occur in wearers of disposable lenses as well as in those subject to complications due to accumulation of protein.

Leukemia inhibitory factor (LIF) inhibits basal bone resorption in fetal rat long bone cultures.

Leukemia inhibitory factor (LIF) has a wide variety of biologic actions. In vivo, its net effect on bone is to increase new bone formation. Recently, the sequence of human LIF was found to differ by only a single amino acid from that of human differentiation-inducing factor (D-factor). The effects of LIF on bone appear to be complex since purified murine D-factor and recombinant LIF stimulate bone resorption in cultured newborn mouse calvaria. To examine further the responses of bone to LIF, we studied the effects of recombinant human LIF (glycosylated and nonglycosylated) and recombinant human D-factor (non-glycosylated) on resorption in another in vitro organ culture model, fetal rat long bones. Both LIF preparations and D-factor inhibited basal bone resorption rates by 25% to 44% in these cultures. Resorption rates in maximally inhibited LIF-treated cultures were similar to those in devitalized bones. Inhibitory effects typically occurred at concentrations of greater than or equal to 10 ng/mL (0.5 nM) for the non-glycosylated LIF and D-factor and 1000 U/mL for glycosylated LIF. Neither LIF nor D-factor blocked the resorptive response to interleukin 1 (IL 1) or parathyroid hormone (PTH) nor did they alter total DNA synthesis. Hence, their inhibitory effects appeared to be specific for the mechanisms regulating basal resorptive activity. These results demonstrate that LIF has potent inhibitory actions on basal resorption rates in these cultures. These effects may be important for the anabolic responses that LIF has on bone in vivo. In addition, they may also be involved in the interactions between inflammatory or tumor cells and bone.

The effect of time, patching, and lens flexibility on RGP lens adherence.

The effects of time, eye patching, and lens flexibility on rigid lens adherence was evaluated in five overnight, in-laboratory test sessions. Patching was investigated with a group of 11 subjects in two overnight test sessions. Sleep time and lens flexibility were investigated in three separate overnight test sessions with two groups of subjects wearing two lens types of fluorosilicone materials (Dk 92 and 60). Adherence occurred in a significant portion of eyes within a 2-hour time period, and the incidence increased throughout the night. There was no significant difference between the incidence of adherence for lenses of a flexible material compared to lenses of a more rigid material (p greater than 0.6, X2 test), nor did patching have a significant influence on the incidence of adherence. The mechanism of lens adherence may be related to several factors including arbitrary lens movement to a peripheral corneal position, the creation of a geometric spacing between the lens and the eye, lid forces producing a negative pressure, and an increase in tear viscosity throughout the night.

Distribution of membrane phospholipids in the rabbit uvea.

BACKGROUND AND AIMS: Since the uveal tract becomes involved in inflammatory disorders, which are known to affect lipid metabolism, we studied normal membrane phospholipids (PLs) in order to (1) determine baseline PL profiles of the iris, ciliary body, and choroid, and (2) compare and contrast PL profiles of the uveal tissues. METHODS: Iris, ciliary body and choroid tissues were isolated from rabbit eyes (n = 30) and extracted with chloroform-methanol using a modified Folch procedure. Quantitative tissue PL profiles were obtained using 31P nuclear magnetic resonance. RESULTS: Fourteen PLs were detected and quantitated in all three uveal tissues among which was one unidentified PL at -0.17 ppm. The five major PLs in the iris, ciliary body and choroid, respectively, have the following PL composition (mole percent of total phosphorus): ethanolamine plasmalogen 14.58, 15.07, 16.52; phosphatidylethanolamine 13.10, 12.40, 9.23; phosphatidylserine 11.24, 10.27, 12.13; sphingomyelin (SM) 11.10, 11.97, 18.21; and phosphatidylcholine (PC) 36.61, 36.70, 29.88. Additionally, lysophosphatidic acid, phosphatidic acid, lysophosphatidylcholine, phosphatidylinositol, and PC plasmalogen or alkacyl PC were detected in all tissues. Sphingosylphosphorylcholine also was detected in the ciliary body and choroid. Lysophosphatidylethanolamine was detected in the choroid. In addition, 42 PL metabolic indexes were calculated from these data, which permitted pathway-specific lipid analyses. CONCLUSION: This study establishes baseline PL profiles of the uveal tract tissues and will permit comparisons with tissues from eyes with inflammatory disorders. The PL concentrations in conjunction with the indexes demonstrate that overall the choroid has membranes that are less permeable to ion translocation than either the iris or the ciliary body, although there are compensatory concentration changes between the SM and PC components among these three tissues.