University of Puerto Rico at Humacao

The great taxonomic diversity of the Orchidaceae is often attributed to adaptive radiation for specific pollinators driven by selection for outcrossing. However, when one looks beyond the product to the process, the evidence for selection is less than overwhelming. We explore this problem by discussing relevant aspects of orchid biology and asking which aspects of reproduction explain the intricate pollination mechanisms and diversification of this family. We reaffirm that orchids are primarily pollination limited, the severity of which is affected by resource constraints. Fruit set is higher in temperate than in tropical species, and in species which offer pollinator rewards than those that do not. Reproductive success is skewed towards few individuals in a population and effective population sizes are often small. Population structure, reproductive success and gene flow among populations suggest that in many situations genetic drift may be as important as selection in fostering genetic and morphological variation in this family. Although there is some evidence for a gradualist model of evolutionary change, we believe that the great diversity in this family is largely a consequence of sequential and rapid interplay between drift and natural selection.

We report on the observation of field-effect transistor (FET) behavior in electrospun camphorsulfonic-acid-doped polyaniline/polyethylene oxide (PEO) nanofibers. Saturation channel currents are observed at surprisingly low source–drain voltages. The hole mobility in the depletion regime is 1.4×10−4 cm2/V s, while the one-dimensional (1-D) charge density (at zero gate bias) is calculated to be approximately 1 hole per 50 two-ring repeat units of polyaniline, consistent with the rather high channel conductivity (∼10−3 S/cm). Reducing or eliminating the PEO content in the fiber is expected to enhance device parameters. Electrospinning is thus proposed as a simple method of fabricating one-dimensional polymer FETs.

Bacterial exopolymeric substances (EPS) are molecules released in response to the physiological stress encountered in the natural environment. EPS are structural components of the extracellular matrix in which cells are embedded during biofilm development. The chemical nature and functions of these EPS are dependent on the genetic expression of the cells within each biofilm. Although some bacterial matrices have been characterized, understanding of the function of the EPS is relatively limited, particularly within the Bacillus genus. Similar gaps of knowledge exist with respect to the chemical composition and specific roles of the macromolecules secreted by Bacillus subtilis in its natural environment. In this review, the different EPS from B. subtilis were classified into four main functional categories: structural (neutral polymers), sorptive (charged polymers), surface-active and active polymers. In addition, current information regarding the genetic expression, production and function of the main polymers secreted by B. subtilis strains, particularly those related to biofilm formation and its architecture, has been compiled. Further characterization of these EPS from B. subtilis remains a challenge.

This study explores social interactive features of synchronous computer-mediated communication (CMC)—commonly known as “chat”—as such features unfolded in real time and developed over a nine-week period in two fourth-semester college Spanish classes. The study invoked the Vygotskian sociocultural theoretical framework and employed discourse analysis as a research tool to describe and explain outstanding features of chat room communication. Specific interactional features examined are intersubjectivity, off-task discussion, greetings and leave-takings, identity exploration and role play, humor and sarcasm, and use of the L1 (English). Through these communicative behaviors, learners appropriated the chat room environment, transforming it into a learner-centered discourse community governed by communicative autonomy and the use of language and discourse functions that go beyond those encountered in the typical L2 classroom.

Magnetic hyperthermia treatment requires biocompatible magnetic nanoparticles with improved heating capacities to become a viable clinical method for cancer treatment. Although small superparamagnetic iron oxide nanoparticles under low fields have been favored (linear response theory regime), these nanoparticles present a series of limitations, including relatively low heating efficiency (specific absorption rate or SAR), that need to be overcome to make magnetic hyperthermia an efficient clinical application. We here show that by modifying the shape into deformed cubes (octopods) and tuning their size, their SAR can be greatly increased up to 70% (from 140 to 240 W/g). By using nonhydrolytic thermal decomposition, we have obtained highly crystalline monodisperse nano-octopods for different sizes (17–47 nm), and their heating response has been extensively studied in a wide range of AC fields (20–800 Oe) using combined calorimetric and AC magnetometry experiments. Our results consistently reveal that at AC fields (≤300–400 Oe), the nano-octopods with the smallest size (17 nm) possessed the largest SAR, but for higher AC fields (>400 Oe) the SAR tended to increase with increasing particle size, reaching maximum values up to 415 W/g for the 47 nm octopods. The different response has been attributed to the ratio between the applied field and the anisotropy field, which activates different heating mechanisms: mainly related to viscous losses in the case of the smallest nano-octopods, while mostly attributed to hysteresis losses in the case of the biggest ones. Our study provides important insights into the size-dependent SAR in anisotropic nanoparticles, other than what has been predicted by the linear response theory for the case of spherical nanoparticles, and paves a new pathway for the design and synthesis of novel anisotropic iron oxide nanostructures with optimal heating efficiency for enhanced hyperthermia.

Psychrobacter arcticus strain 273-4, which grows at temperatures as low as -10 degrees C, is the first cold-adapted bacterium from a terrestrial environment whose genome was sequenced. Analysis of the 2.65-Mb genome suggested that some of the strategies employed by P. arcticus 273-4 for survival under cold and stress conditions are changes in membrane composition, synthesis of cold shock proteins, and the use of acetate as an energy source. Comparative genome analysis indicated that in a significant portion of the P. arcticus proteome there is reduced use of the acidic amino acids and proline and arginine, which is consistent with increased protein flexibility at low temperatures. Differential amino acid usage occurred in all gene categories, but it was more common in gene categories essential for cell growth and reproduction, suggesting that P. arcticus evolved to grow at low temperatures. Amino acid adaptations and the gene content likely evolved in response to the long-term freezing temperatures (-10 degrees C to -12 degrees C) of the Kolyma (Siberia) permafrost soil from which this strain was isolated. Intracellular water likely does not freeze at these in situ temperatures, which allows P. arcticus to live at subzero temperatures.

Three Gram-negative, non-motile, non-pigmented, oxidase-positive coccobacilli capable of growth at temperatures from −10 to 30 °C and salinities of 0 to 1.7 M NaCl were isolated from Siberian permafrost and characterized. Both 16S rRNA and gyrB gene sequencing studies placed the isolates in the Gammaproteobacteria within the genus Psychrobacter . However, with higher bootstrap values and reproducible tree topologies, gyrB represented a more reliable phylogenetic marker for the taxonomy of Psychrobacter species. DNA–DNA hybridization data supported gyrB tree topologies and established two relatedness groups within the three isolates; neither of these groups was related at the species level to any previously described Psychrobacter species. The two groups of isolates could be differentiated phenotypically from 13 previously described Psychrobacter species using API strips. These results support the existence of two novel species of Psychrobacter , for which we propose the names Psychrobacter cryohalolentis sp. nov. (type strain K5 T =DSM 17306 T =VKM B-2378 T ) and Psychrobacter arcticus sp. nov. (type strain 273-4 T =DSM 17307 T =VKM B-2377 T ).

Cancer is the second largest cause of death worldwide with the number of new cancer cases predicted to grow significantly in the next decades. Biotechnology and medicine can and should work hand-in-hand to improve cancer diagnosis and treatment efficacy. However, success has been frequently limited, in particular when treating late-stage solid tumors. There still is the need to develop smart and synergistic therapeutic approaches to achieve the synthesis of strong and effective drugs and delivery systems. Much interest has been paid to the development of smart drug delivery systems (drug-loaded particles) that utilize passive targeting, active targeting, and/or stimulus responsiveness strategies. This review will summarize some main ideas about the effect of each strategy and how the combination of some or all of them has shown to be effective. After a brief introduction of current cancer therapies and their limitations, we describe the biological barriers that nanoparticles need to overcome, followed by presenting different types of drug delivery systems to improve drug accumulation in tumors. Then, we describe cancer cell membrane targets that increase cellular drug uptake through active targeting mechanisms. Stimulus-responsive targeting is also discussed by looking at the intra- and extracellular conditions for specific drug release. We include a significant amount of information summarized in tables and figures on nanoparticle-based therapeutics, PEGylated drugs, different ligands for the design of active-targeted systems, and targeting of different organs. We also discuss some still prevailing fundamental limitations of these approaches, eg, by occlusion of targeting ligands.

Protein stability remains one of the main factors limiting the realization of the full potential of protein therapeutics. Poly(ethylene glycol) (PEG) conjugation to proteins has evolved into an important tool to overcome instability issues associated with proteins. The observed increase in thermodynamic stability of several proteins upon PEGylation has been hypothesized to arise from reduced protein structural dynamics, although experimental evidence for this hypothesis is currently missing. To test this hypothesis, the model protein alpha-chymotrypsin (alpha-CT) was covalently modified with PEGs with molecular weights (M(W)) of 700, 2,000 and 5,000 and the degree of modification was systematically varied. The procedure did not cause significant tertiary structure changes. Thermodynamic unfolding experiments revealed that PEGylation increased the thermal transition temperature (T(m)) of alpha-CT by up to 6 degrees C and the free energy of unfolding [DeltaG(U) (25 degrees C)] by up to 5 kcal/mol. The increase in stability was found to be independent of the PEG M(W) and it leveled off after an average of four PEG molecules were bound to alpha-CT. Fourier-transformed infrared (FTIR) H/D exchange experiments were conducted to characterize the conformational dynamics of the PEG-conjugates. It was found that the magnitude of thermodynamic stabilization correlates with a reduction in protein structural dynamics and was independent of the PEG M(W). Thus, the initial hypothesis proved positive. Similar to the thermodynamic stabilization of proteins by covalent modification with glycans, PEG thermodynamically stabilizes alpha-CT by reducing protein structural dynamics. These results provide guidance for the future development of stable protein formulations.

The use of enzymes in organic solvents to introduce chirality to a number of relevant organic compounds has been well documented. However, there are still major drawbacks in such applications, in particular the frequently much lower enzyme activity under nonaqueous conditions. In addition, the reaction outcome (substrate enantioselectivity and reaction rates) cannot be accurately predicted. To overcome these limitations, herein we introduce methyl-β-cyclodextrin (MβCD) as a new macrocyclic additive to simultaneously enhance the activity and enantioselectivity of dehydrated subtilisin Carlsberg suspended in neat organic solvents. MβCD was efficient in dramatically increasing the activity and significantly improving the enantioselectivity of subtilisin in co-lyophilizates when compared to the powder lyophilized from buffer alone. The initial rate determined for the transesterification between sec-phenethyl alcohol and vinyl butyrate increased by up to 164-fold and the enantioselectivity could be doubled. In addition, marked solvent effects were noted. To investigate the possible relationship between enzyme structure and these kinetic data, the secondary structure of subtilisin was investigated by Fourier transform infrared (FTIR) spectroscopy under all relevant conditions. Using the α-helix content determined from the amide I vibrational band as the main quantitative parameter, we found that MβCD is partially efficient in ameliorating dehydration-induced structural perturbations. Suspension of the subtilisin−MβCD co-lyophilizate in the various solvents revealed solvent-induced structural perturbations in some of them (e.g., acetonitrile), while no such changes were observed in others (e.g., THF and 1,4-dioxane). For the first time the results demonstrated that enantioselectivity and structural intactness in the various solvents were clearly related. Increase in the enzyme activity in contrast is mainly caused by increased structural mobility of subtilisin in the solvents by MβCD. We conclude that it is important to carefully select the additive and the solvent system to achieve high enantioselectivity and activity in such applications. Simultaneous improvement of both enzyme properties requires careful optimization of the enzyme formulation and proper selection of a suitable solvent. FTIR spectroscopy has proven to be a very valuable methodology to structurally guide such an optimization procedure.

We present a quantitative model for phase shifts observed in scanning conductance microscopy and show excellent agreement with data on samples of (conducting) single wall carbon nanotubes and insulating poly(ethylene oxide) (PEO) nanofibers. The model takes into account phase shifts due to the electrostatic (capacitive) forces exerted on the tip by sample and substrate, using simple approximate geometries. Data for large diameter, conducting doped polyaniline/PEO nanofibers are qualitatively explained. This quantitative approach is used to determine the dielectric constant of PEO nanofiber, a general method that can be extended to other dielectric nanowires.

The electronic properties of graphene are tunable via doping, making it attractive in low dimensional organic electronics. Common methods of doping graphene, however, adversely affect charge mobility and degrade device performance. We demonstrate a facile shadow mask technique of defining electrodes on graphene grown by chemical vapor deposition (CVD) thereby eliminating the use of detrimental chemicals needed in the corresponding lithographic process. Further, we report on the controlled, effective, and reversible doping of graphene via ultraviolet (UV) irradiation with minimal impact on charge mobility. The change in charge concentration saturates at ∼2 × 1012 cm–2 and the quantum yield is ∼10−5 e/photon upon initial UV exposure. This simple and controlled strategy opens the possibility of doping wafer-size CVD graphene for diverse applications.

Il existe une importante littérature sur la question de l’humour, tant dans la tradition rhétorique que littéraire et stylistique, sans compter les écrits dans les domaines philosophique et psychologique. À passer en revue ces écrits, on est frappé par leur justesse, mais en même temps, en les confrontant, par les contradictions entre certaines définitions (particulièrement sur l’ironie), ou par leur flou au point de ne plus pouvoir déterminer ce qu’est l’humour. L’article reprend cette question en proposant une catégorisation des faits humoristiques selon un certain nombre de paramètres issus de l’analyse du discours, catégorisation qui a servi de base à un travail d’analyse comparée entre les faits humoristiques dans les contextes culturels français et espagnols.

Atomic force microscopy (AFM) has been widely employed as a nanoscopic lithography technique. In this review, we summarize the current state of research in this field. We introduce the various forms of the technique, such as nanoshaving, nanografting and dip-pen nanolithography, which we classify according to the different interactions between the AFM probe and the substrate during the nanolithography fabrication process. Mechanical force, applied by the tip to the substrate, is the variable that can be controlled with good precision in AFM and it has been utilized in patterning self-assembled monolayers. In such applications, the AFM tip can break some relatively weak chemical bonds inside the monolayer. In general, the state of the art for AFM nanolithography demonstrates the power, resolution and versatility of the technique.

The genera Exiguobacterium and Psychrobacter have been frequently detected in and isolated from polar permafrost and ice. These two genera have members that can grow at temperatures as low as -5 and -10 degrees C, respectively. We used quantitative PCR (Q-PCR) to quantify members of these genera in 54 soil or sediment samples from polar, temperate and tropical environments to determine to what extent they are selected by cold environments. These results were further analyzed by multiple linear regression to identify the most relevant environmental factors corresponding to their distribution. Exiguobacterium was detected in all three climatic zones at similar densities, but was patchier in the temperate and tropical samples. Psychrobacter was present in almost all polar samples, was at highest densities in Antarctica sediment samples, but was in very low densities and infrequently detected in temperate and tropical soils. Clone libraries, specific for the 16S rRNA gene for each genus, were constructed from a sample from each climatic region. The clone libraries were analyzed for alpha and beta diversities, as well as for variation in population structure by using analysis of molecular variance. Results confirm that both genera were found in all three climatic zones; however, Psychrobacter populations seemed to be much more diverse than Exiguobacterium in all three climatic zones. Furthermore, Psychrobacter populations from Antarctica are different from those in Michigan and Puerto Rico, which are similar to each other.

The spin state of [Fe(H2B(pz)2)2(bipy)] thin films is mediated by changes in the electric field at the interface of organic ferroelectric polyvinylidene fluoride with trifluoroethylene (PVDF-TrFE). Signatures of the molecular crossover transition are evident in changes in the unoccupied states and the related shift from diamagnetic to paramagnetic characteristics. This may point the way to the molecular magneto-electric effect on devices.

Abstract The Near-Earth Object (NEO) Surveyor mission is a NASA Observatory designed to discover and characterize asteroids and comets. The mission’s primary objective is to find the majority of objects large enough to cause severe regional impact damage (>140 m in effective spherical diameter) within its 5 yr baseline survey. Operating at the Sun–Earth L1 Lagrange point, the mission will survey to within 45° of the Sun in an effort to find objects in the most Earth-like orbits. The survey cadence is optimized to provide observational arcs long enough to distinguish near-Earth objects from more distant small bodies that cannot pose an impact hazard reliably. Over the course of its survey, NEO Surveyor will discover ∼200,000–300,000 new NEOs down to sizes as small as ∼10 m and thousands of comets, significantly improving our understanding of the probability of an Earth impact over the next century.

Vanadate is known to inhibit several phosphatases including Na+, K+-ATPase, alkaline phosphatase, and glyceraldehyde-3-P dehydrogenase. Inhibition presumably results because vanadium adopts a stable structure which resembles the transition state of phosphate during the reactions involving these enzymes. We performed experiments to further examine the effects of vanadate (VO3-4) on erythrocyte (red blood cells (RBC] glycolytic intermediates. RBC obtained from human subjects were centrifuged and washed with lactated Ringer's 5% dextrose. 31P nuclear magnetic resonance analysis of the RBC revealed the characteristic peaks for the 3-phosphate and 2-phosphate of 2,3-diphosphoglycerate (DPG), inorganic phosphate (Pi), and ATP. Incubation of RBC with 10(-6) M VO3-4 led to a disappearance of ATP and 2,3-DPG while the peak for Pi increased. By the end of 4 h over 90% of the VO3-4 had been reduced to VO2+ (vanadyl) in the RBC. The effects of 10(-4) M iodoacetamide and 10(-5) M ethacrynic acid, known inhibitors of glyceraldehyde-3-P dehydrogenase that act by interactions with sulfhydryl groups (-SH) of the enzyme, were similar to those of VO3-4. Incubation with vanadyl did not affect the peaks for Pi, 2-DPG, or 3-DPG. Furthermore, using electron spin resonance we demonstrated that in the presence of glyceraldehyde-3-P dehydrogenase, VO3-4 is reduced to VO2+. The findings demonstrate that VO3-4 inhibits glycolysis at micromolar concentrations and that the ion is reduced to VO2+ in the cell. The similarity of the effect of VO3-4 to those of iodoacetamide and ethacrynic acid suggests that interactions with -SH groups is its mechanism of inhibition. Since under physiological conditions intracellular VO3-4 concentrations are in the micromolar range and may exist in oxidized and/or reduced forms, VO3-4 could regulate the activity of glyceraldehyde-3-P dehydrogenase through changes in the redox state of the enzyme rather than by substituting for the PO3-4 ion.

Abstract The current study examines whether the fear of being laughed at (gelotophobia) can be assessed reliably and validly by means of a self-report instrument in different countries of the world. All items of the GELOPH (Ruch and Titze, GELOPH〈46〉, University of Düsseldorf, 1998; Ruch and Proyer, Swiss Journal of Psychology 67:19–27, 2008b) were translated to the local language of the collaborator (42 languages in total). In total, 22,610 participants in 93 samples from 73 countries completed the GELOPH. Across all samples the reliability of the 15-item questionnaire was high (mean alpha of .85) and in all samples the scales appeared to be unidimensional. The endorsement rates for the items ranged from 1.31% through 80.00% to a single item. Variations in the mean scores of the items were more strongly related to the culture in a country and not to the language in which the data were collected. This was also supported by a multidimensional scaling analysis with standardized mean scores of the items from the GELOPH〈15〉. This analysis identified two dimensions that further helped explaining the data (i.e., insecure vs. intense avoidant-restrictive and low vs. high suspicious tendencies towards the laughter of others). Furthermore, multiple samples derived from one country tended to be (with a few exceptions) highly similar. The study shows that gelotophobia can be assessed reliably by means of a self-report instrument in cross-cultural research. This study enables further studies of the fear of being laughed at with regard to differences in the prevalence and putative causes of gelotophobia in comparisons to different cultures.

Tea polyphenols (PP) are known as potent antioxidants. At the same time, PP have been repeatedly reported to oxidize by molecular oxygen with the formation of active forms of oxygen. In this work, the Clark electrode technique was applied to study the kinetics of the autoxidation of tea extracts and individual tea PP as well as model PP, catechol, gallic acid, and pyrogallol. Aqueous extracts of both green and black teas were found to undergo extensive autoxidation under physiological conditions. The addition of superoxide dismutase (SOD) and milk resulted in a significant decrease in the rate of oxidation. Studied individually, PP were found to autoxidize at a rate, which increased with pH, proportional to PP concentration and nearly proportional to oxygen concentration. The collected data were used for the extrapolation/interpolation of the starting rates of oxidation to the standard conditions (at pH 7.40, 100 microM PP, 200 microM O2). PP oxidizability is basically determined by that of the key PP fragment (pyrogallol > gallate > catechol). Meta-OH groups do not contribute to the oxidation even at pH 13.0. Similar to tea brew, the oxidation of individual PP was inhibited by milk and SOD addition, with catechol being the only exception (the oxidation of catechol was accelerated when SOD was added). Comparison of the autoxidation of PP (o-hydroquinones) with that of p-hydroquinones (Roginsky, V.; Barsukova, T. K. J. Chem. Soc., Perkin Trans. 2 2000, 1575-1582) displays the dramatic difference both in the oxidizability and in the kinetic regularities. The difference in the kinetics has been suggested to be due to the difference in the initiation of the chain process. Whereas for p-hydroquinones the oxidation is initiated by the reaction between hydroquinone and a corresponding quinone, the oxidation of o-hydroquinones is likely started by direct interaction between substrate and molecular oxygen. As the second process is much slower, this may explain the relatively low oxidizability of PP as compared to p-hydroquinones.