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PubMedDate not supplied

Accelerated ultraviolet aging of intraocular lens optic materials: a 50 year simulation.

PURPOSE: To introduce an updated accelerated photoaging model for application to intraocular lens (IOL) materials and to apply this model to determine the photostability of AMO PhacoFlex model SI-18NGB and PhacoFlex II model SI-20NGB silicone IOL materials over a simulated 50 years of exposure. SETTING: Research laboratory, AMO Surgical Products, Irvine, California, USA. METHODS: Previous photoaging models and aging parameters, including intraocular exposure intensity, daily exposure duration, and acceleration exponent were critically reviewed and analyzed, and an updated model was introduced. The test specimens were continuously irradiated with ultraviolet (UV) light in a Suntest UV chamber at an intensity of 8 mw/cm2 for 86 days to simulate 50 years of in vivo exposure. The silicone lenses were evaluated for focal length, resolution, and surface integrity, while regular slabs were tested for tensile strength, elongation, hardness, contact angle, and percentage light transmission. The UV-absorption capacity was monitored using ultrathin slabs (0.127 mm). Six replicate samples were used for each determination, and a two-sided t-test with significance set at P < .05 was used to evaluate the difference before and after aging. RESULTS: No significant difference in optical, physical, and surface properties of the lenses and lens materials was found. No change in UV-absorption capacity was observed after a simulated 50 years of accelerated photoaging. CONCLUSION: The AMO PhacoFlex SI-18NGB and PhacoFlex II SI-30NGB silicone lens materials resisted UV light degradation over 50 years of simulated exposure.

Lenses, Intraocular↗
PubMed1999

Accelerating neural network training using weight extrapolations.

The backpropagation (BP) algorithm for training feedforward neural networks has proven robust even for difficult problems. However, its high performance results are attained at the expense of a long training time to adjust the network parameters, which can be discouraging in many real-world applications. Even on relatively simple problems, standard BP often requires a lengthy training process in which the complete set of training examples is processed hundreds or thousands of times. In this paper, a universal acceleration technique for the BP algorithm based on extrapolation of each individual interconnection weight is presented. This extrapolation procedure is easy to implement and is activated only a few times in between iterations of the conventional BP algorithm. This procedure, unlike earlier acceleration procedures, minimally alters the computational structure of the BP algorithm. The viability of this new approach is demonstrated on three examples. The results suggest that it leads to significant savings in computation time of the standard BP algorithm. Moreover, the solution computed by the proposed approach is always located in close proximity to the one obtained by the conventional BP procedure. Hence, the proposed method provides a real acceleration of the BP algorithm without degrading the usefulness of its solutions. The performance of the new method is also compared with that of the conjugate gradient algorithm, which is an improved and faster version of the BP algorithm.

Journal Article↗
PubMed1998

RGS9, a GTPase accelerator for phototransduction.

The rod outer segment phototransduction GAP (GTPase-accelerating protein) has been identified as RGS9, a member of the RGS family of G alpha GAPs. RGS9 mRNA expression is specific for photoreceptor cells, and RGS9 protein colocalizes with other phototransduction components to photoreceptor outer segment membranes. The RGS domain of RGS9 accelerates GTP hydrolysis by the visual G protein transducin (G alpha(t)), and this acceleration is enhanced by the gamma subunit of the phototransduction effector cGMP phosphodiesterase (PDEgamma). These unique properties of RGS9 match those of the rod outer segment GAP and implicate it as a key element in the recovery phase of visual transduction.

Amino Acid Sequence↗
PubMed2003

Accelerated idioventricular rhythm during spinal anesthesia for cesarean section.

During cesarean section under regional anesthesia various anomalies of the electrocardiogram are reported such as bradycardia, supraventricular and ventricular premature beats, supraventricular paroxysmal tachicardia, S-T depression non-significant for myocardial ischemia and second degree atrioventricular block. We describe two cases of accelerated idioventricular rhythm in patients undergoing elective cesarean section with spinal anesthesia of which we have not found mention in the literature. This arrhythmia is not dangerous and does not usually evolve into ventricular fibrillation. During spinal anesthesia, however, it can exacerbate hypotension and, if misdiagnosed, a further administration of ephedrine can increase the duration of accelerated idioventricular rhythm. When necessary, for example in symptomatic hypotension or severe bradycardia, atropine is advised in order to inhibit vagal tone and increase the activity of the sino-atrial node, obtaining a pharmacological overdrive. This therapy is appropriate even if the frequency of the accelerated idioventricular rhythm is high.

Journal Article↗
PubMed2000

Development of a sealed-accelerator-tube neutron generator

Sealed-accelerator-tube neutron generators are being developed in Lawrence Berkeley National Laboratory (LBNL) for applications ranging from neutron radiography to boron neutron capture therapy and neutron activation analysis. The new generation of high-output neutron generators is based on the D-T fusion reaction, producing 14.1-MeV neutrons. The main components of the neutron tube--the ion source, the accelerator and the target--are all housed in a sealed metal container without external pumping. Thick-target neutron yield computations are performed in this paper to estimate the neutron yield of titanium and scandium targets. With an average deuteron beam current of 1 A and an energy of 120 keV, a time-averaged neutron production of approximately 10(14) n/s can be estimated for a tritiated target, for both pulsed and cw operations. In mixed deuteron/triton beam operation, a beam current of 2 A at 150 keV is required for the same neutron output. Recent experimental results on ion sources and accelerator columns are presented and discussed.

Journal Article↗
PubMed2003

Perceptual acceleration of objects in stream: evidence from flash-lag displays.

An object in continuous motion is perceived ahead of the briefly flashed object, although the two images are physically aligned (Nijhawan, 1994), the phenomenon called flash-lag effect. Flash-lag effects have been found also with other continuously changing features such as color, pattern entropy, and brightness (Sheth, Nijhawan, & Shimojo, 2000) as well as with streamed pre- and post-target input without any change of the feature values of streaming items in feature space (Bachmann & Põder, 2001a. 2001b). We interpret all instances of the flash-lag as a consequence of a more fundamental property of conscious perception in general: acceleration of the speed with which samples of perceptual information become represented in explicit format immediately after the stimulation onset. Decreased visual latency of the samples of stimulus information from the streamed input leads to the relative perceptual lag for the separately flashed stimulus because it is not preceded by adjacent sensory input that would have accelerated its perception. Experimental support for the notion of perceptual acceleration is reviewed.

Humans↗
PubMed2006

Accelerated immunotherapy schedules: review of efficacy and safety.

OBJECTIVE: To provide a comprehensive evaluation of accelerated immunotherapy build-up schedules in terms of adverse reactions and clinical efficacy. DATA SOURCES: Peer-reviewed studies and review articles were selected from the PubMed database for articles published in the years 1976 to 2006 using the following keywords: rush, cluster immunotherapy in combination with allergic rhinitis, asthma, Hymenoptera, and imported fire ant. STUDY SELECTION: Studies were selected if they provided safety and efficacy information on accelerated allergen immunotherapy schedules. Most of the studies reviewed were double-blind, placebo controlled, but some open-observational studies were included if they provided immunotherapy safety or other information the author thought was relevant. RESULTS: A wide range of systemic reactions were reported in the literature with inhalant allergens: ranging from 27% to 100% of the patients in rush immunotherapy studies and 0% to 79% of patients in the cluster studies. Predictors of systemic reactions with rush immunotherapy were forced expiratory volume in 1 second less than 80% of predicted and a high degree of skin test reactivity. Premedication clearly reduces the risk of systemic reactions with rush immunotherapy, but the effect on cluster schedules was not as clear. CONCLUSION: Accelerated immunotherapy build-up schedules in selected patients may provide a rapid alternative to conventional build-up schedules without a significant increase in risk.

Allergens↗
PubMed2001

Androgen-accelerated bone maturation in mice is not attenuated by Faslodex, an estrogen receptor blocker.

Androgens accelerate bone maturation, but it is unclear to what extent this process may be mediated by estrogens derived from aromatization of androgens. In this study, we investigated whether an estrogen-blocking agent, Faslodex (ICI 182,780), can attenuate testosterone-accelerated skeletal maturation in immature mice. On days of life 2-8, mouse pups received either testosterone propionate (50 microg/100 g body weight), Faslodex (100 microg/100 g body weight), a combination of Faslodex + testosterone, or vehicle alone. Skeletal maturation was assessed in the forepaw and the lumbar spine. Testosterone caused acceleration of bone maturation (p < 0.05, compared with vehicle), predominantly of axial bones. Faslodex, however, failed to block the effect of testosterone, such that the mice receiving Faslodex + testosterone had skeletal maturation scores similar to those treated with testosterone alone. These results suggest that androgens have the capacity to stimulate bone maturation directly, probably via their own receptors.

Animals↗
PubMed1988

Acceleration of cleavage of the carbon-cobalt bond of sterically hindered alkylcobalamins by binding to apoprotein of diol dehydrase.

Cleavage of the C-Co bond of sterically hindered alkylcobalamins bearing neither an adenine moiety nor functional groups, such as isobutylcobalamin, neopentylcobalamin, and cyclohexylcobalamin, was markedly accelerated by their interaction with apoprotein of diol dehydrase, although these cobalamins do not function as coenzyme. Acceleration of the conversion of alkylcobalamins to enzyme-bound hydroxocobalamin was stoichiometric and obeyed first-order reaction kinetics. These results, together with strong competitive inhibition by these alkylcobalamins with respect to adenosylcobalamin, indicate that acceleration of the C-Co bond cleavage by the apoenzyme is due to labilization of their C-Co bond by binding to the active site of the enzyme. This labilization is considered to be caused by a steric distortion of the corrin ring which is induced by specific tight interaction of the cobalamin moiety with apoprotein. The importance of such a labilizing effect for activation of the C-Co bond of adenosylcobalamin in enzymatic reactions is discussed.

Allosteric Site↗
PubMed2005

Oxidative metabolites accelerate Alzheimer's amyloidogenesis by a two-step mechanism, eliminating the requirement for nucleation.

The process of amyloid formation by the amyloid beta peptide (Abeta), i.e., the misassembly of Abetapeptides into soluble quaternary structures and, ultimately, amyloid fibrils, appears to be at the center of Alzheimer's disease (AD) pathology. We have shown that abnormal oxidative metabolites, including cholesterol-derived aldehydes, modify Abeta and accelerate the early stages of amyloidogenesis (the formation of spherical aggregates). This process, which we have termed metabolite-initiated protein misfolding, could explain why hypercholesterolemia and inflammation are risk factors for sporadic AD. Herein, the mechanism by which cholesterol metabolites hasten Abeta 1-40 amyloidogenesis is explored, revealing a process that has at least two steps. In the first step, metabolites modify Abeta peptides by Schiff base formation. The Abeta-metabolite adducts form spherical aggregates by a downhill polymerization that does not require a nucleation step, dramatically accelerating Abeta aggregation. In agitated samples, a second step occurs in which fibrillar aggregates form, a step also accelerated by cholesterol metabolites. However, the metabolites do not affect the rate of fibril growth in seeded aggregation assays; their role appears to be in initiating amyloidogenesis by lowering the critical concentration for aggregation into the nanomolar range. Small molecules that block Schiff base formation inhibit the metabolite effect, demonstrating the importance of the covalent adduct. Metabolite-initiated amyloidogenesis offers an explanation for how Abeta aggregation could occur at physiological nanomolar concentrations.

Alzheimer Disease↗
PubMedDate not supplied

Accelerated biodegradation of poly(vinyl alcohol) by glycosidations of the hydroxyl groups or addition of sugars.

Biodegradabilities of N-acetyl-d-glucosamine (GlcNAc)- (1) and chitobiose-substituted (2) poly(vinyl alcohol)s (PVA)s in a soil suspension (pH 6.5) were investigated at 25 degrees C for 40 days. Biochemical oxygen demand of 1 with a degree of substitution of 0.2-0.3 (DP = 430-480) was higher than that of PVA under the degradation condition. Size exclusion chromatography, (1)H NMR, and Fourier-transform infrared measurements of the recovered sample indicated that biodegradation of the PVA main chain was accelerated by partial glycosidation of hydroxyl groups in PVA. Similar acceleration was observed in a PVA/GlcNAc (50:50, w/w) mixture. Microbes which relate with degradation of the glycosidated polymers were grown in a culture medium including the soil suspension and the polymer as the carbon source. Polyacrylamide gel electrophoresis (SDS-PAGE) and IR measurements indicated that a cell-free extract derived from GlcNAc-substituted PVA was different from that in the PVA/GlcNAc mixture. The results suggested that the PVA main chain in GlcNAc-substituted PVA was cleaved by a different microorganism or via a mechanism different from that in the mixture. Chitobiose-substituted PVA 2 showed more enhanced acceleration, indicating that the sugar length influenced the degradability.

Biodegradation, Environmental↗
PubMedDate not supplied

Acceleration of enzymatic reaction of trypsin through the formation of water-soluble complexes with poly(ethylene glycol)-block-poly(alpha,beta-aspartic acid).

The amidase activity of bovine pancreas trypsin in water-soluble complexes with poly(ethylene glycol)-block-poly(alpha,beta-aspartic acid) (PEG-PAA) was evaluated by a colorimetric assay using L-lysine p-nitroanilide as a substrate. The enzymatic reaction of trypsin was accelerated through the complexation with PEG-PAA. By determining the kinetic parameters of the enzymatic reaction of trypsin, it was confirmed that the catalytic rate constant of the complexed trypsin was 15 times higher than that of the native trypsin. From the evaluation of pH dependence of initial reaction rate, it was indicated that this acceleration was induced by a stabilization of the imidazolium ion of the His residue in the catalytic site, the Asp-His-Ser triad, of trypsin due to the Asp units of PEG-PAA. The hydrogen bonded Asp-His pairs are critical constituents in several key enzymatic reactions including serine protease and apurinic endonucleases, and it was expected that the acceleration of the catalytic reaction might occur for other enzymes by the formation of water-soluble complexes with PEG-PAA.

Amino Acids↗
PubMed2003

Ketone enolization by lithium hexamethyldisilazide: structural and rate studies of the accelerating effects of trialkylamines.

Mechanistic studies of the enolization of 2-methylcyclohexanone mediated by lithium hexamethyldisilazide (LiHMDS; TMS2NLi) in toluene and toluene/amine mixtures are described. NMR spectroscopic studies of LiHMDS/ketone mixtures in toluene reveal the ketone-complexed cyclic dimer (TMS2NLi)2(ketone). Rate studies using in situ IR spectroscopy show the enolization proceeds via a dimer-based transition structure, [(TMS2NLi)2(ketone)]++. NMR spectroscopic studies of LiHMDS/ketone mixtures in the presence of relatively unhindered trialkylamines such as Me2NEt reveal the quantitative formation of cyclic dimers of general structure (TMS2NLi)2(R3N)(ketone). Rate studies trace a >200-fold rate acceleration to a dimer-based transition structure, [(TMS2NLi)2(R3N)(ketone)]++. Amines of intermediate steric demand, such as Et3N, are characterized by recalcitrant solvation, saturation kinetics, and exceptional (>3000-fold) accelerations traced to the aforementioned dimer-based pathway. Amines of high steric demand, such as i-Pr2NEt, do not observably solvate (TMS2NLi)2(ketone) but mediate enolization via [(TMS2NLi)2(R3N)(ketone)]++ with muted accelerations. The most highly hindered amines, such as i-Bu3N, do not influence the LiHMDS structure or the enolization rate. Overall, surprisingly complex dependencies of the enolization rates on the structures and concentrations of the amines derive from unexpectedly simple steric effects. The consequences of aggregation, mixed aggregation, and substrate-base precomplexation are discussed.

Amines↗
PubMed2005

Phosphorylation effects on cis/trans isomerization and the backbone conformation of serine-proline motifs: accelerated molecular dynamics analysis.

The presence of serine/threonine-proline motifs in proteins provides a conformational switching mechanism of the backbone through the cis/trans isomerization of the peptidyl-prolyl (omega) bond. The reversible phosphorylation of the serine/threonine modulates this switching in regulatory proteins to alter signaling and transcription. However, the mechanism is not well understood. This is partly because cis/trans isomerization is a very slow process and, hence, difficult to study. We have used our accelerated molecular dynamics method to study the cis/trans proline isomerization, preferred backbone conformation of a serine-proline motif, and the effects of phosphorylation of the serine residue. We demonstrate that, unlike normal molecular dynamics, the accelerated molecular dynamics allows for the system to escape very easily from the trans isomer to cis isomer, and vice versa. Moreover, for both the unphosphorylated and phosphorylated peptides, the statistical thermodynamic properties are recaptured, and the results are consistent with experimental values. Isomerization of the proline omega bond is shown to be asymmetric and strongly dependent on the psi backbone angle before and after phosphorylation. The rates of escape decrease after phosphorylation. Also, the alpha-helical backbone conformation is more favored after phosphorylation. This accelerated molecular dynamics approach provides a general approach for enhancing the conformational transitions of molecular systems without having prior knowledge of the location of the minima and barriers on the potential-energy landscape.

Amino Acid Motifs↗
PubMed2000

Acceleration of pH variation in cloudy apple juice using electrodialysis with bipolar membranes.

The purpose of this study was to accelerate pH variation in cloudy apple juice using electrodialysis (ED). The testing was conducted using two ED configurations. The bipolar and cationic membrane configuration showed that reducing the spacing from 8 to 0.75 mm had little effect on treatment time, whereas stacking eight bipolar membranes reduced acidification time by 30%, although the treatment still took too long (21 min). Furthermore, it was not possible to acidify apple juice to a pH of 2.0 to completely inhibit enzymatic browning. The bipolar and anionic membrane configuration helped to accelerate the acidification step by a factor of 3, increasing the yield from 3.3 to 10 L of juice/m(2) membrane/min. Moreover, treatment time was inversely proportional to the size of the membrane stack. The speed at which the pH of acidified juice returned to its initial value was, however, 4 times slower than the speed of acidification, giving a yield of 2.5 L of juice/m(2) membrane/min. By accelerating the acidification step, ED treatment with bipolar and anionic membranes results in more effective polyphenol oxidase activity and more rapid control of juice browning at pH 2.0. Also, the treatment has very little effect on the chemical composition and organoleptic quality of apple juice.

Beverages↗
PubMed2005

Mechanism of poly(acrylic acid) acceleration of antithrombin inhibition of thrombin: implications for the design of novel heparin mimics.

The bridging mechanism of antithrombin inhibition of thrombin is a dominant mechanism contributing a massive approximately 2500-fold acceleration in the reaction rate and is also a key reason for the clinical usage of heparin. Our recent study of the antithrombin-activating properties of a carboxylic acid-based polymer, poly(acrylic acid) (PAA), demonstrated a surprisingly high acceleration in thrombin inhibition (Monien, B. H.; Desai, U. R. J. Med. Chem. 2005, 48, 1269). To better understand this interesting phenomenon, we have studied the mechanism of PAA-dependent acceleration in antithrombin inhibition of thrombin. Competitive binding studies with low-affinity heparin and a heparin tetrasaccharide suggest that PAA binds antithrombin in both the pentasaccharide- and the extended heparin-binding sites, and these results are corroborated by molecular modeling. The salt-dependence of the K(D) of the PAA-antithrombin interaction shows the formation of five ionic interactions. In contrast, the contribution of nonionic forces is miniscule, resulting in an interaction that is significantly weaker than that observed for heparins. A bell-shaped profile of the observed rate constant for antithrombin inhibition of thrombin as a function of PAA concentration was observed, suggesting that inhibition proceeds through the "bridging" mechanism. The knowledge gained in this mechanistic study highlights important rules for the rational design of orally available heparin mimics.

Acrylic Resins↗
PubMed2000

Structure-activity relationships in the acceleration of a hetero Diels-Alder reaction by metalloporphyrin hosts.

At 0.33 mM in dichloromethane at 25 degrees C the cyclic metalloporphyrin hosts 5, 7, 8, and 10 accelerate 12-fold, 260-fold, 1130-fold, and 250-fold, respectively, the reaction of 1 and 2 and also bind the product 3 very strongly. These observations combined with previously measured results with hosts 6, 9, and 11 allowed us to explore the influence of host geometry changes on acceleration rates and product binding over a wide range of host molecules of different size, ranging from extremely tightly strapped to very relaxed. To estimate the Zn-Zn distance in the transition-state complex, we carried out quantum mechanical calculations (at the HF/6-31G level) for the transition state to form 3. The structure-activity relationships found for hosts 5-11, along with the structural features calculated for the transition-state structure between 1 and 2 and previously crystallographically observed for product-free hosts and for a host.product complex,(4) suggest that both host preorganization as well as host flexibility are key features leading to high acceleration rates and product binding and that it is the delicate balance between the two structural features that leads to maximum efficiency.

Catalysis↗