Photochemical degradation of polystyrene

In this work the oxidative degradation of pure polystyrene, polybutadiene and butadiene-modified polystyrene (normally called high impact polystyrene or HIPS) have been studied using a variety of physical and chemical techniques. The changes in dynamic-mechanical properties occurring during the ultra-violet light accelerated weathering of these polymers were followed by a visco-elastometric technique (Rheovibron) in the solid phase over a wide temperature range. Selective cross-linking of the polybutadiene in high-impact polystyrene caused the depression of the low temperature damping peak (tan d) with a corresponding sharp peak in tan d at ambient temperature accompanied by an integral rise in complex modulus. During the same period of photoxidation, the hydroperoxide concentration and gel content increased rapidly, reaching a maximum before decomposing photolytically with the destruction of unsaturation and with the formation of stable oxidation products. Infra-red spectroscopy showed the formation of carbonyl and hydroxyl groups. a,ß-unsaturated carbonyl was also identified and was formed by decomposition of both allylic hydroperoxide and initial peroxidic gel by ß-scission of the graft between polybutadiene and polystyrene. With further photoxidation a more stable ether gel was formed involving the destruction of the conjugating double bond of a,ß-unsaturated carbonyl. Addition of saturated and unsaturated ketones which are potential sensitisers of photoxidation to high-impact polystyrene and polybutadiene failed to photo-initiate the oxygen absorption of the polymers. A prior thermal oxidative treatment on the other hand eliminated the auto- accelerating stage leading to linear kinetics as the concentration of thermally-produced hydroperoxide approached a maximum. Antioxidants which act by destroying hydroperoxide lengthened the induction period to rapid oxygen absorption, whilst a phenolic antioxidant behaved as a weak photo-activator initially and a retarder later. Prior photolysis of high-impact polystyrene photo-activated the unsaturated component and caused similar changes in dynamic-mechanical properties to those found during photoxidation although at a much lower rate. Polybutadiene behaves as a photo-pro-oxidant for the destruction of polystyrene in high-impact polystyrene.

The durability of glass fibre reinforced cements made with new cementitious matrices

Widespread use of glass fibre reinforced cement (GRC) has been impeded by concerns over its durability. Three degradation mechanisms are proposed - fibre corrosion, Ca(OHh precipitation and matrix densification - although their relative importance is debated. Matrices with reduced alkalinities and Ca(OH)2 contents are being developed; the aim of this study was to investigate their hydration and interaction with alkali-resistant fibres to determine the factors controlling their long-term durability, and assess the relevancy of accelerated ageing. The matrices studied were: OPC/calcium-sulphoaluminate cement plus metakaolin (C); OPC plus metakaolin (M); blast-furnace slag cement plus a micro-silica based additive (D); and OPC (O). Accelerated ageing included hot water and cyclic regimes prior to tensile testing. Investigations included pore solution expression, XRD, DTA/TG, SEM and optical petrography. Bond strength was determined from crack spacings using microstructural parameters obtained from a unique image analysis technique. It was found that, for the new matrices - pore solution alkalinities were lower; Ca(OH)2 was absent or quickly consumed; different hydrates were formed at higher immersion temperatures; degradation under 65°C immersion was an order of magnitude slower, and no interfilamental Ca(OH)2 was observed .It was concluded that: fibre weakening caused by flaw growth was the primary degradation mechanism and was successfully modelled on stress corrosion/static fatigue principles. OPC inferiority was attributed partly to its higher alkalinity but chiefly to the growth of Ca(OH)2 aggravating the degradation; and hot water ageing although useful in model formulation and contrasting the matrices, changed the intrinsic nature of the composites rather than simply accelerating the degradation mechanisms.

The influence of Arabian Gulf environment on mechanisms of reinforcement corrosion

The reduction in the useful-service life of reinforced concrete construction in the Arabian Gulf is attributed to reinforcement corrosion. While this phenomenon is primarily related to chloride ions, the concomitant pressure of sulfate salts may accelerate the deterioration process. Another factor which might influence reinforcement corrosion is the elevated ambient temperature. While few studies have been conducted to evaluate the individual effect of sulfate contamination and temperature on chloride binding and reinforcement corrosion, the synergistic effect of these factors on concrete durability, viz.-a-viz., reinforcement corrosion, needs to be evaluated. Further, the environmental conditions of the Arabian Gulf are also conducive for accelerated carbonation. However, no data are available on the concomitant effect of chloride-sulfate contamination and elevated temperature on the carbonation behaviour of plain and blended cements.This study was conducted to evaluate the conjoint effect of chloride-sulfate contamination and temperature on the pore solution chemistry and reinforcement corrosion. The effect of chloride-sulfate contamination and elevated temperature on carbonation in plain and blended cements was also investigated. Pore solution extraction and analysis, X-ray diffraction, differential thermal analysis, scanning electron microscopy, DC linear polarization resistance and AC impedance spectroscopy techniques were utilized to study the effect of experimental parameters on chloride binding, reinforcement corrosion and carbonation.The results indicated that the concomitant presence of chloride and sulfate salts and temperature significantly influences the durability performance of concrete by: (i) decreasing the chloride binding, (ii) increasing reinforcement corrosion, and (iii) accelerating the carbonation process. To avoid such deterioration, it is advisable to minimize both chloride and sulfate contamination contributed by the mixture ingredients. Due to the known harmful role of sulfate ions in decreasing the chloride binding and increasing reinforcement corrosion, limits on allowable sulfate contamination in concrete should also be established.

Polypropylene as a reductive agent for dehalogenation of brominated organic compounds

A new method for debromination of organics by a reductive medium like polypropylene is investigated. The reaction is carried out in inert atmosphere to avoid rapid oxidation of the polymer. Through this detoxification procedure, hydrogen bromide and small brominated alkanes are formed. Experiments in closed ampoules are carried out with tetrabromobisphenol A, dibromophenol, pentabromodiphenyl ether, dichlorophenol and an oil formed by pyrolysis of printed circuit boards in the Haloclean® process. The reaction is examined under isothermal conditions in a temperature range between 300 and 400°C and a residence time between 10 and 30 min. Optimal conditions were found at 350°C and at a residence time of 20 min. As chlorinated phenols are not destroyed under these conditions, the process may be a valuable procedure to gain hydrogen bromide out of mixtures of halogenated feed materials. Also, under atmospheric pressure, a reaction between polypropylene and brominated compounds takes place as could be proved by thermogravimetric analysis. Bromobenzene has an accelerating effect on the rate of weight loss of the polymer, but at higher concentrations, it can also be slowed down. © 2003 Elsevier Ltd. All rights reserved.

Advances in characterisation, calibration and data processing speed of optical coherence tomography systems

This thesis describes advances in the characterisation, calibration and data processing of optical coherence tomography (OCT) systems. Femtosecond (fs) laser inscription was used for producing OCT-phantoms. Transparent materials are generally inert to infra-red radiations, but with fs lasers material modification occurs via non-linear processes when the highly focused light source interacts with the materials. This modification is confined to the focal volume and is highly reproducible. In order to select the best inscription parameters, combination of different inscription parameters were tested, using three fs laser systems, with different operating properties, on a variety of materials. This facilitated the understanding of the key characteristics of the produced structures with the aim of producing viable OCT-phantoms. Finally, OCT-phantoms were successfully designed and fabricated in fused silica. The use of these phantoms to characterise many properties (resolution, distortion, sensitivity decay, scan linearity) of an OCT system was demonstrated. Quantitative methods were developed to support the characterisation of an OCT system collecting images from phantoms and also to improve the quality of the OCT images. Characterisation methods include the measurement of the spatially variant resolution (point spread function (PSF) and modulation transfer function (MTF)), sensitivity and distortion. Processing of OCT data is a computer intensive process. Standard central processing unit (CPU) based processing might take several minutes to a few hours to process acquired data, thus data processing is a significant bottleneck. An alternative choice is to use expensive hardware-based processing such as field programmable gate arrays (FPGAs). However, recently graphics processing unit (GPU) based data processing methods have been developed to minimize this data processing and rendering time. These processing techniques include standard-processing methods which includes a set of algorithms to process the raw data (interference) obtained by the detector and generate A-scans. The work presented here describes accelerated data processing and post processing techniques for OCT systems. The GPU based processing developed, during the PhD, was later implemented into a custom built Fourier domain optical coherence tomography (FD-OCT) system. This system currently processes and renders data in real time. Processing throughput of this system is currently limited by the camera capture rate. OCTphantoms have been heavily used for the qualitative characterization and adjustment/ fine tuning of the operating conditions of OCT system. Currently, investigations are under way to characterize OCT systems using our phantoms. The work presented in this thesis demonstrate several novel techniques of fabricating OCT-phantoms and accelerating OCT data processing using GPUs. In the process of developing phantoms and quantitative methods, a thorough understanding and practical knowledge of OCT and fs laser processing systems was developed. This understanding leads to several novel pieces of research that are not only relevant to OCT but have broader importance. For example, extensive understanding of the properties of fs inscribed structures will be useful in other photonic application such as making of phase mask, wave guides and microfluidic channels. Acceleration of data processing with GPUs is also useful in other fields.

On the Coherence Between Probability and Possibility Measures

* This paper is supported by CICYT (Spain) under Project TIN 2005-08943-C02-01.

Editorial overview:new protein production tools for structural biology

Full text: The idea of producing proteins from recombinant DNA hatched almost half a century ago. In his PhD thesis, Peter Lobban foresaw the prospect of inserting foreign DNA (from any source, including mammalian cells) into the genome of a λ phage in order to detect and recover protein products from Escherichia coli [ 1 and 2]. Only a few years later, in 1977, Herbert Boyer and his colleagues succeeded in the first ever expression of a peptide-coding gene in E. coli — they produced recombinant somatostatin [ 3] followed shortly after by human insulin. The field has advanced enormously since those early days and today recombinant proteins have become indispensable in advancing research and development in all fields of the life sciences. Structural biology, in particular, has benefitted tremendously from recombinant protein biotechnology, and an overwhelming proportion of the entries in the Protein Data Bank (PDB) are based on heterologously expressed proteins. Nonetheless, synthesizing, purifying and stabilizing recombinant proteins can still be thoroughly challenging. For example, the soluble proteome is organized to a large part into multicomponent complexes (in humans often comprising ten or more subunits), posing critical challenges for recombinant production. A third of all proteins in cells are located in the membrane, and pose special challenges that require a more bespoke approach. Recent advances may now mean that even these most recalcitrant of proteins could become tenable structural biology targets on a more routine basis. In this special issue, we examine progress in key areas that suggests this is indeed the case. Our first contribution examines the importance of understanding quality control in the host cell during recombinant protein production, and pays particular attention to the synthesis of recombinant membrane proteins. A major challenge faced by any host cell factory is the balance it must strike between its own requirements for growth and the fact that its cellular machinery has essentially been hijacked by an expression construct. In this context, Bill and von der Haar examine emerging insights into the role of the dependent pathways of translation and protein folding in defining high-yielding recombinant membrane protein production experiments for the common prokaryotic and eukaryotic expression hosts. Rather than acting as isolated entities, many membrane proteins form complexes to carry out their functions. To understand their biological mechanisms, it is essential to study the molecular structure of the intact membrane protein assemblies. Recombinant production of membrane protein complexes is still a formidable, at times insurmountable, challenge. In these cases, extraction from natural sources is the only option to prepare samples for structural and functional studies. Zorman and co-workers, in our second contribution, provide an overview of recent advances in the production of multi-subunit membrane protein complexes and highlight recent achievements in membrane protein structural research brought about by state-of-the-art near-atomic resolution cryo-electron microscopy techniques. E. coli has been the dominant host cell for recombinant protein production. Nonetheless, eukaryotic expression systems, including yeasts, insect cells and mammalian cells, are increasingly gaining prominence in the field. The yeast species Pichia pastoris, is a well-established recombinant expression system for a number of applications, including the production of a range of different membrane proteins. Byrne reviews high-resolution structures that have been determined using this methylotroph as an expression host. Although it is not yet clear why P. pastoris is suited to producing such a wide range of membrane proteins, its ease of use and the availability of diverse tools that can be readily implemented in standard bioscience laboratories mean that it is likely to become an increasingly popular option in structural biology pipelines. The contribution by Columbus concludes the membrane protein section of this volume. In her overview of post-expression strategies, Columbus surveys the four most common biochemical approaches for the structural investigation of membrane proteins. Limited proteolysis has successfully aided structure determination of membrane proteins in many cases. Deglycosylation of membrane proteins following production and purification analysis has also facilitated membrane protein structure analysis. Moreover, chemical modifications, such as lysine methylation and cysteine alkylation, have proven their worth to facilitate crystallization of membrane proteins, as well as NMR investigations of membrane protein conformational sampling. Together these approaches have greatly facilitated the structure determination of more than 40 membrane proteins to date. It may be an advantage to produce a target protein in mammalian cells, especially if authentic post-translational modifications such as glycosylation are required for proper activity. Chinese Hamster Ovary (CHO) cells and Human Embryonic Kidney (HEK) 293 cell lines have emerged as excellent hosts for heterologous production. The generation of stable cell-lines is often an aspiration for synthesizing proteins expressed in mammalian cells, in particular if high volumetric yields are to be achieved. In his report, Buessow surveys recent structures of proteins produced using stable mammalian cells and summarizes both well-established and novel approaches to facilitate stable cell-line generation for structural biology applications. The ambition of many biologists is to observe a protein's structure in the native environment of the cell itself. Until recently, this seemed to be more of a dream than a reality. Advances in nuclear magnetic resonance (NMR) spectroscopy techniques, however, have now made possible the observation of mechanistic events at the molecular level of protein structure. Smith and colleagues, in an exciting contribution, review emerging ‘in-cell NMR’ techniques that demonstrate the potential to monitor biological activities by NMR in real time in native physiological environments. A current drawback of NMR as a structure determination tool derives from size limitations of the molecule under investigation and the structures of large proteins and their complexes are therefore typically intractable by NMR. A solution to this challenge is the use of selective isotope labeling of the target protein, which results in a marked reduction of the complexity of NMR spectra and allows dynamic processes even in very large proteins and even ribosomes to be investigated. Kerfah and co-workers introduce methyl-specific isotopic labeling as a molecular tool-box, and review its applications to the solution NMR analysis of large proteins. Tyagi and Lemke next examine single-molecule FRET and crosslinking following the co-translational incorporation of non-canonical amino acids (ncAAs); the goal here is to move beyond static snap-shots of proteins and their complexes and to observe them as dynamic entities. The encoding of ncAAs through codon-suppression technology allows biomolecules to be investigated with diverse structural biology methods. In their article, Tyagi and Lemke discuss these approaches and speculate on the design of improved host organisms for ‘integrative structural biology research’. Our volume concludes with two contributions that resolve particular bottlenecks in the protein structure determination pipeline. The contribution by Crepin and co-workers introduces the concept of polyproteins in contemporary structural biology. Polyproteins are widespread in nature. They represent long polypeptide chains in which individual smaller proteins with different biological function are covalently linked together. Highly specific proteases then tailor the polyprotein into its constituent proteins. Many viruses use polyproteins as a means of organizing their proteome. The concept of polyproteins has now been exploited successfully to produce hitherto inaccessible recombinant protein complexes. For instance, by means of a self-processing synthetic polyprotein, the influenza polymerase, a high-value drug target that had remained elusive for decades, has been produced, and its high-resolution structure determined. In the contribution by Desmyter and co-workers, a further, often imposing, bottleneck in high-resolution protein structure determination is addressed: The requirement to form stable three-dimensional crystal lattices that diffract incident X-ray radiation to high resolution. Nanobodies have proven to be uniquely useful as crystallization chaperones, to coax challenging targets into suitable crystal lattices. Desmyter and co-workers review the generation of nanobodies by immunization, and highlight the application of this powerful technology to the crystallography of important protein specimens including G protein-coupled receptors (GPCRs). Recombinant protein production has come a long way since Peter Lobban's hypothesis in the late 1960s, with recombinant proteins now a dominant force in structural biology. The contributions in this volume showcase an impressive array of inventive approaches that are being developed and implemented, ever increasing the scope of recombinant technology to facilitate the determination of elusive protein structures. Powerful new methods from synthetic biology are further accelerating progress. Structure determination is now reaching into the living cell with the ultimate goal of observing functional molecular architectures in action in their native physiological environment. We anticipate that even the most challenging protein assemblies will be tackled by recombinant technology in the near future.

Designing immunogenic peptides

Peptides fulfill many roles in immunology, yet none are more important than their role as immunogenic epitopes driving the adaptive immune response, our ultimate bulwark against infectious disease. Peptide epitopes are mediated primarily by their interaction with major histocompatibility complexes (T-cell epitopes) and antibodies (B-cell epitopes). As pathogen genomes continue to be revealed, both experimental and computational epitope mapping are becoming crucial tools in vaccine discovery1,2. Immunoinformatics offers many tools, techniques and approaches for in silico epitope characterization, which is capable of greatly accelerating epitope design. © 2013 Nature America, Inc. All rights reserved.

Hierarchical mesoporous Pd/ZSM-5 for the selective catalytic hydrodeoxygenation of m-cresol to methylcyclohexane

Mesopore incorporation into ZSM-5 enhances the dispersion of Pd nanoparticles throughout the hierarchical framework, significantly accelerating m-cresol conversion relative to a conventional microporous ZSM-5, and dramatically increasing selectivity towards the desired methylcyclohexane deoxygenated product. Increasing the acid site density further promotes m-cresol conversion and methylcyclohexane selectivity through efficient dehydration of the intermediate methylcyclohexanol.

Ecological correlates of successful colonization in the life history of the Cuban treefrog, {\it Osteopilus septentrionalis\/} (Anura: Hylidae)

Ten correlates of successful colonization were tested and met in the life history of the Cuban treefrog in Florida and the Caribbean. Like many successful colonizing species of animals, the Cuban treefrog was highly fecund; reproduction was possible at a small body size in males (27.0 mm) and females (45.0 mm), and large females could lay large clutches and eggs throughout the year. Generation times were short in this species thereby accelerating the colonization process. Tadpoles and post-metamorphic individuals could exploit a wide range of physical conditions with respect to weather conditions and structure of the habitat. The Cuban treefrog occupied the terrestrial-arboreal niche which was only marginally exploited by other species in Florida. Habitat preference of the Cuban treefrog was for mesophytic forests and disturbed areas, and both habitats were found in native and introduced ranges. The ability to coexist with man further enabled the Cuban treefrog to expand its geographic range. A broad diet enabled the Cuban treefrog to exploit a wide range of prey species and sizes thereby alleviating an important constraint to colonization success. The Cuban treefrog was gregarious and vagile, thereby accelerating the process of dispersal which is crucial to the colonization process. Thus, many features in its life history enabled the Cuban treefrog to rapidly disperse and colonize, often in high population densities, many kinds of sites in its native and introduced range. Conformity to these correlates by the Cuban treefrog ultimately provides predictive power regarding the future colonization of this tropical frog. ^

Ecosystem structure in disturbed and restored subtropical seagrass meadows

Shallow seagrass ecosystems frequently experience physical disturbance from vessel groundings. Specific restoration methods that modify physical, chemical, and biological aspects of disturbances are used to accelerate recovery. This study evaluated loss and recovery of ecosystem structure in disturbed seagrass meadows through plant and soil properties used as proxies for primary and secondary production, habitat quality, benthic metabolism, remineralization, and nutrient storage and exchange. The efficacy of common seagrass restoration techniques in accelerating recovery was also assessed. Beyond removal of macrophyte biomass, disturbance to seagrass sediments resulted in loss of organic matter and stored nutrients, and altered microbial and infaunal communities. Evidence of the effectiveness of restoration actions was variable. Fill placement prevented additional erosion, but the resulting sediment matrix had different physical properties, low organic matter content and nutrient pools, reduced benthic metabolism, and less primary and secondary production relative to the undisturbed ecosystem. Fertilization was effective in increasing nitrogen and phosphorus availability in the sediments, but concurrent enhancement of seagrass production was not detected. Seagrass herbivores removed substantial seagrass biomass via direct grazing, suggesting that leaf loss to seagrass herbivores is a spatially variable but critically important determinant of seagrass transplanting success. Convergence of plant and sediment response variables with levels in undisturbed seagrass meadows was not detected via natural recovery of disturbed sites, or through filling and fertilizing restoration sites. However, several indicators of ecosystem development related to primary production and nutrient accumulation suggest that early stages of ecosystem development have begun at these sites. This research suggests that vessel grounding disturbances in seagrass ecosystems create more complex and persistent resource losses than previously understood by resource managers. While the mechanics of implementing common seagrass restoration actions have been successfully developed by the restoration community, expectations of consistent or rapid recovery trajectories following restoration remain elusive.

Hospitality IT: What Does the Future Hold?

The impact of information technology (IT) is far-reaching and driving dramatic shifts in business paradigms. Trends suggest greater adoption of IT will continue and develop at accelerating rates. Hence, hotel operators and executives must learn how to embrace IT and capitalize on the many capabilities it has to offer while minimizing the threats. The authors attempt to provide a sense of focus and a roadmap to help hoteliers understand the issues, see the future, and find an appropriate on ramp to the information superhighway.

On and Off the Stage at Atlanta Greek Picnic: Performances of Collective Black Middle-Class Identities and the Politics of Belonging

This dissertation presents a thick ethnography that engages in the micro-analysis of the situationality of black middle-class collective identification processes through an examination of performances by members of the nine historically black sororities and fraternities at Atlanta Greek Picnic, an annual festival that occurs at the beginning of June in Atlanta, Georgia. It mainly attracts undergraduate and graduate members of these university-based organizations, as they exist all over the United States. This exploration of black Greek-letter organization (BGLO) performances uncovers processes through which young black middle-class individuals attempt to combine two universes that are at first glance in complete opposition to each other: the domain of the traditional black middle-class values with representations and fashions stemming from black popular culture. These constructions also attempt to incorporate—in a contradiction of sorts— black popular cultural elements in the objective to deconstruct the social conservatism that characterizes middle-class values, particularly in relation to sexuality and its representation in social behaviors and performances. This negotiation between prescribed v middle-class values of respectability and black popular culture provides a space wherein black individuals challenge and/or perpetuate those dominant tropes through identity performances that feed into the formation of black sexual politics, which I examine through a variety of BGLO staged and non-staged performances.

Avaliação de compatibilidade entre pasta de cimento e fluido de perfuração não-aquoso utilizados em poços petrolíferos

Compatibility testing between a drilling fluid and a cement slurry is one of the steps before an operation of cementing oil wells. This test allows us to evaluate the main effects that contamination of these two fluids may cause the technological properties of a cement paste. The interactions between cement paste and drilling fluid, because its different chemical compositions, may affect the cement hydration reactions, damaging the cementing operation. Thus, we carried out the study of the compatibility of non-aqueous drilling fluid and a cement slurry additives. The preparation procedures of the non-aqueous drilling fluid, the cement paste and completion of compatibility testing were performed as set out by the oil industry standards. In the compatibility test is evaluated rheological properties, thickening time, stability and compressive strength of cement pastes. We also conducted analyzes of scanning electron microscopy and X-ray diffraction of the mixture obtained by the compatibility test to determine the microstructural changes in cement pastes. The compatibility test showed no visual changes in the properties of the cement paste, as phase separation. However, after the addition of nonaqueous drilling fluid to cement slurry there was an increased amount of plastic viscosity, the yield point and gel strength. Among the major causative factors can include: chemical reaction of the components present in the non-aqueous drilling fluid as the primary emulsifier, wetting agent and paraffin oil, with the chemical constituents of the cement. There was a reduction in the compressive strength of the cement paste after mixing with this drilling fluid. Thickening test showed that the oil wetting agent and high salinity of the non-aqueous fluid have accelerating action of the handle of the cement paste time. The stability of the cement paste is impaired to the extent that there is increased contamination of the cement slurry with the nonaqueous fluid. The X-ray diffraction identified the formation of portlandite and calcium silicate in contaminated samples. The scanning electron microscopy confirmed the development of the identified structures in the X-ray diffraction and also found the presence of wells in the cured cement paste. The latter, formed by the emulsion stability of the drilling fluid in the cement paste, corroborate the reduction of mechanical strength. The oil wetting agent component of the non-aqueous drilling fluid, the modified cement hydration processes, mainly affecting the setting time.

Diadenosine polyphosphates after laser in situ keratomileusis and photorefractive keratectomy refractive techniques

Purpose:  To study the concentrations of diadenosine polyphosphates in the ocular surface after PRK and LASIK. Methods:  Sixty-one patients (30 males and 31 females) with ages ranging from 20 to 63 (34.04 ± 9.13 years) were recruited in Balear Institute of Ophthalmology, Palma de Mallorca, Spain. LASIK was performed in 92 eyes of 46 patients and PRK in 25 eyes of 15 patients. Variations in the levels of diadenosine polyphosphate (Ap4A and Ap5A), Schirmer I (Jones test), TBUT, corneal staining together with the Dry Eye Questionnaire to evaluate discomfort and dryness were studied. All tests were performed at the preoperative visit and at 1-day, 2-week, 1-month and 3-month postoperative visits. Results:  Ap4A showed a 5 and 3.5 fold increase at the 1-day visit for LASIK and PRK, respectively. LASIK patients continued having higher statistically significant concentrations (p = 0.01) all over the follow-up. Ap5A showed no significant differences at any visit. Tear volume decreased during the 3 months in LASIK. The PRK cases had a normal volume at 1 month. TBUT in LASIK increased at the 1-day visit (p = 0,002) and decreased from the 2 weeks onwards and for the PRK, decreased by a 35% at the 1-day visit and kept reduced for a month. Discomfort only increased at the 1-day visit (p = 0.007). Dryness frequency was similar in all visits. Conclusions:  Ap4A levels only are increased in refractive surgery patients during the first day after the surgery. This increasing suggests that Ap4A may help accelerating the healing process.