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Chemical security can be described as the practice of protecting chemicals from people. This editorial introduces the Special Issue on Chemical Security. Herein, we present a concise history of the...

In November 2019, for the first time in the history of the Chemical Weapons Convention, changes were made to Schedule 1 of the Annex on Chemicals. While there is little in the scientific literature regarding any of these newly scheduled chemicals, the carbamates, specifically, prove to be substantially different, both in terms of their chemical composition and their toxicological effects, from all the other scheduled nerve agents and have yet to be fully reported on in the literature. Herein, we present a literature review of the available information on carbamates included in Schedule 1, as well as analogous other carbamates, and provide a summary of their utility and function as cholinesterase inhibitors in general and their toxicities. Though there is a paucity of studies in the literature related to the detection of these newly scheduled quaternary and bisquaternary carbamates and/or their biomarkers, information available on carbamate pesticides may be a solid starting point to further postulate amenable detection methodologies. Lastly, we note some implications of these newly scheduled carbamates for the nonproliferation and disarmament community.

Blister agents damage the skin, eyes, mucous membranes and subcutaneous tissues. Other toxic effects may occur after absorption. The response of the Scientific Advisory Board (SAB) of the Organisation for the Prohibition of Chemical Weapons (OPCW) to a request from the OPCW Director-General in 2013 on the status of medical countermeasures and treatments to blister agents is updated through the incorporation of the latest information. The physical and toxicological properties of sulfur mustard and clinical effects and treatments are summarised. The information should assist medics and emergency responders who may be unfamiliar with the toxidrome of sulfur mustard and its treatment.

The Journal of Chemical Education announces a call for papers for an upcoming special issue on Chemical Security.

Cohesive Hamaker constants of solid materials are measured via optical and dielectric properties (i.e., Lifshitz theory), inverse gas chromatography (IGC), and contact angle measurements. To date, however, a comparison across these measurement techniques for common energetic materials has not been reported. This has been due to the inability of the community to produce samples of energetic materials that are readily compatible with contact angle measurements. Here we overcome this limitation by using physical vapor deposition to produce thin films of five common energetic materials, and the contact angle measurement approach is applied to estimate the cohesive Hamaker constants and surface energy components of the materials. The cohesive Hamaker constants range from 85 zJ to 135 zJ across the different films. When these Hamaker constants are compared to prior work using Lifshitz theory and nonpolar probe IGC, the relative magnitudes can be ordered as follows: contact angle > Lifshitz > IGC. Furthermore, the dispersive surface energy components estimated here are in good agreement with those estimated by IGC. Due to these results, researchers and technologists will now have access to a comprehensive database of adhesion constants which describe the behavior of these energetic materials over a range of settings.

A welfare assessment was conducted during 475 observations of 75 long-line tethered horses and 587 observations of 112 freerange horses kept on public grazing land in South Wales over a six-month period from March to August 2010. The observations included quantitative and qualitative behavioural assessments, assessments of physical welfare and assessments of the environment of the horse. Multi-level modelling was used to identify the significant factors affecting each measure. Tethered horses had similar behavioural repertoires to free-range horses but there were differences related to tethering, such as fewer observations of walking, trotting and cantering, increased vocalisations occurring during the observation and poorer qualitative ‘mood’ scores. There were few observations of severe physical welfare problems in either tethered or free-range horses, however tethered horses were observed more often to have eye abnormalities, hoof cracks, lameness and signs of limb pain but less often with mane and tail tangles, as thin or as dirty. Shelter from wind, rain or sun was available to almost all free-range horses (99.8% of observations) but was only found during 16.5% or fewer observations of tethered horses, giving them a greater risk of poor welfare during inclement weather. Similarly, tethered horses were infrequently observed to have access to clean water, and their willingness to drink when offered water, suggests the provision of water was inadequate and tethered horses may have been thirsty. There were significant confounding effects of the observer or climatic factors for some behavioural and physical measures that should be considered when conducting future studies.

Styrene (S) is lung tumorigenic in mice but not in rats. S and its alkene-oxidized metabolite styrene oxide (SO) were not lung toxic in CYP2F2(-/-) [knockout] mice, indicating S-induced mouse lung tumors are mediated through mouse-specific CYP2F2-generated ring-oxidized metabolite(s) in lung bronchioles. The human relevance of the CYP2F MOA was assessed by insertion of a human CYP2F1, 2A13, 2B6 transgene into CYP2F2(-/-) mice; CYP2F1 expression and activity were confirmed in the transgenic (TG) mice. No evidence of cytotoxicity or increased cell proliferation (BrdU labeling) was seen in TG mice treated with either S or SO (200mg/kg/day ip for 5days). In contrast to S and SO, 4HS (105mg/kg/day ip for 5days) increased BrdU labeling 5-10-fold in WT mice

The vapor pressures (VPs) of many explosive compounds are extremely low, so determining accurate values proves difficult. Many researchers, using a variety of methods, have measured and reported the VPs of explosive compounds at single temperatures, or as a function of temperature using VP equations. There are large variations in reported VPs for many of these compounds, and some errors exist within individual papers. This article provides a review of explosive VPs and describes the methods used to determine them. We have compiled primary VP relationships traceable to the original citations and include the temperature ranges for which they have been determined. Corrected values are reported as needed and described in the text. In addition, after critically examining the available data, we calculate and tabulate VPs at 25°C.

The title compound, C 20H 25NO 4, the product formed in the Amadori rearrangement of L-rhamnose with dibenzylamine, is shown by X-ray crystallographic analysis to be a rare example of an Amadori product crystallizing in a furanose form. © 2005 International Union of Crystallography Printed in Great Britain - all rights reserved.

The ring size of both the lactone and the ketal protecting group in the title compound, C9H14O5, have been established by X-ray crystallographic analysis. The crystal structure consists of hydrogen-bonded spirals parallel to the b axis.

The unknown relative configurations in the title compound, C13H13N3O4, of the acetal carbon and of the quaternary carbon bearing the azide were determined by X-ray crystallographic analysis; the absolute configuration was defined by the use of 2-C-methyl-D-lyxonolactone as a starting material. There are two mol-ecules in the asymmetric unit (Z′ = 2). © 2007 International Union of Crystallography. All rights reserved.

Saccharinic acids, branched 2-C-methyl-aldonic acids, may be accessed via a green procedure from aldoses by sequential conversion to an Amadori ketose and treatment with calcium hydroxide; d-galactose and d-glucose are converted to 2-C-methyl-d-lyxono-1,4-lactone (with a small amount of 2-C-methyl-d-xylono-1,4-lactone) and 2-C-methyl-d-ribono-1,4-lactone. Inversion of configuration at C-4 of the branched lactones allows access to 2-C-methyl-l-ribono-1,4-lactone and 2-C-methyl-l-lyxono-1,4-lactone, respectively. d-Xylose affords 2-C-methyl-d-threono-1,4-lactone and 2-C-methyl-d-erythrono-1,4-lactone, whereas l-arabinose, under similar conditions, gave the enantiomers 2-C-methyl-l-threono-1,4-lactone and 2-C-methyl-l-erythrono-1,4-lactone. © 2006.

The electrical stability of low-voltage organic transistors based on phosphonic acid self-assembled monolayer (SAM) dielectrics is investigated using four different semiconductors. The threshold voltage shift in these devices shows a stretched-exponential time dependence under continuous gate bias with a relaxation time in the range of 10(3)-10(5) s, at room temperature. Differences in the bias instability of transistors based on different self-assembled monolayers and organic semiconductors suggest that charge trapping into localized states in the semiconductor is not the only mechanism responsible for the observed instability. By applying 1-5 s long programming voltage pulses of 2-3 V in amplitude, a large reversible threshold voltage shift can be produced. The retention time of the programmed state was measured to be on the order of 30 h. The combination of low voltage operation and relatively long retention times makes these devices interesting for ultra-low power memory applications.

Kienböck’s disease, defined as avascular necrosis of the lunate, is a relatively rare condition with a poorly understood etiology. Conservative and invasive treatments for Kienböck’s disease exist, including wrist immobilization, surgical joint-leveling procedures, vascularized bone grafting, proximal row carpectomy, and total wrist arthrodesis. Staging Kienböck’s disease using radiography assumes near complete avascularity of the lunate. The staging distinguishes only the “state of collapse” in an ordinal classification scheme and does not allow localization or indicate partial involvement of the lunate, which the image contrast from MRI may provide. In this short communication, we report the treatment of a patient’s Kienböck’s disease by combining MRI with mathematical modeling to optimize the congruency between the curvature of donor and recipient sites of an autologous osteoarticular plug transfer. Follow-up MRI and radiographs at 1 year postoperatively demonstrated gradual graft incorporation and bone healing. The purpose of this study was to describe the feasibility of a novel surgical technique. The results indicate that donor site selection for autologous osteoarticular transfer using a quantitative evaluation of articular surface curvature may be beneficial for optimizing the likelihood for restoring the radius of curvature and thus joint articulation following cartilage repair.

The uses of self-assembled monolayers (SAMs) of dipolar molecules or of adsorbed molecular acceptors on electrode materials are common strategies to increase their work function, thereby facilitating hole injection into an organic semiconductor deposited on top. Here it is shown that a combination of both approaches can surpass the performance of the individual ones. By combined experimental and theoretical methods it is revealed that in a three-component system, consisting of an indium-tin-oxide (ITO) electrode, a carbazole-based phosphonic acid SAM, and a molecular acceptor layer on top of the SAM, charge transfer occurs from the ITO through the SAM to the acceptor layer, resulting in an electrostatic field drop over the charge-neutral SAM. This result is in contrast to common expectations of either p-doping the carbazole of the SAM or charge transfer complex formation between the carbazole and the acceptor molecules. A high work function of 5.7 eV is achieved with this combined system; even higher values may be accessible by exploiting the fundamental charge redistribution mechanisms identified here with other material combinations.

The dielectric permittivity and electric breakdown strength of nanocomposites comprising poly(vinylidene fluoride-co-hexafluoro propylene) and phosphonic acid surface-modified BaTiO(3) nanoparticles have been investigated as a function of the volume fraction of nanoparticles. The mode of binding of pentafluorobenzylphosphonic acid on the BaTiO(3) particles was investigated using infrared and (31)P solid-state nuclear magnetic resonance spectroscopy, and the phosphonic acid was found to form well ordered, tightly bound monolayers. The effective permittivity of nanocomposites with low volume fractions (50%) was in good agreement with standard theoretical models, with a maximum relative permittivity of 35. However, for nanoparticle volume fractions of greater than 50%, the effective permittivity was observed to decrease with increasing nanoparticle volume fraction, and this was correlated with an increase in porosity of the spin-coated nanocomposite films. The dielectric breakdown strength was also found to decrease with increasing volume fraction of the BaTiO(3) nanoparticles, with an abrupt decrease observed around 10% and a gradual decrease for volume fractions of 20-50%. Comparison of these results with model calculations, using statistical particle packing simulations and effective medium theory for the permittivity and breakdown strength, indicates the important roles of nanoparticle percolation and porosity of the nanocomposites on the dielectric properties. The measured energy density at a field strength of 164 V/mum, well below the breakdown strength, increased to a value of 3.2 J/cm(3) as the nanoparticle volume fraction is increased to 50%, roughly in line with the trend of the permittivity. The calculated maximum energy densities indicate maximal extractable energy (7-8 J/cm(3) at 1 kHz) for two different particle volume fractions, as a result of the interplay of the dependencies of permittivity and breakdown strength on volume fraction.

Indium−tin oxide (ITO) electrodes have been modified with both fluorinated alkyl and aryl phosphonic acids [n-hexylphosphonic acid (HPA) and n-octadecylphosphonic acid (ODPA); 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl phosphonic acid (FHOPA), pentafluorobenzyl phosphonic acid (PFBPA), and tetrafluorobenzyl-1,4-diphosphonic acid (TFBdiPA)]. These are modifiers designed to control both wetting properties toward nonpolar molecular solids and to provide a wide range of tunability in effective surface work function. The molecular nature of surface attachment and changes in electronic and wetting properties were characterized by X-ray photoelectron spectroscopy (XPS), UV-photoelectron spectroscopy (UPS), photoelastic modulation infrared reflection−absorption spectroscopy (PM-IRRAS), and contact angle measurements using both water and hexadecane. Interface dipoles from the PA modifiers contribute to shifts in the low kinetic energy regions of UPS spectra (local vacuum level shifts, which translate into change...

Materials with high dielectric permittivity are important in electronic components such as capacitors, gate dielectrics, memories, and power-storage devices. Conventional highpermittivity materials such as barium titanate (BT) can be processed into thin films by using chemical solution deposition yielding a relative permittivity (er) of about 2500 and relatively low dielectric loss but require high-temperature sintering, which is not compatible with many substrate materials. Polymer-based dielectrics, such as biaxially oriented polypropylene (BOPP), have good processability with high dielectric strengths (∼ 640 V lm) suitable for high-energy-density capacitors, but the storage capacity (ca. 1–1.2 J cm) is limited by the low er (ca. 2.2) of these materials. [6] Various approaches to high-er materials based on nanocomposites containing metal particles or other conductive materials have been pursued. Such nanocomposites have afforded huge er values but the resulting materials are limited by the high-temperature processing required, high dielectric loss, or low dielectric strength. Polymer/ceramic nanocomposites in which high-er metal oxide nanoparticles such as BT and lead magnesium niobate–lead titanate (PMN–PT) are incorporated into a polymer host are of significant current interest. The combination of high-er nanoparticles with high-dielectric-strength polymer hosts offers the potential to obtain processable highperformance dielectric materials. Simple solution processing of BT particles in a polymer host generally results in poor film quality and inhomogeneities, which are mainly caused by agglomeration of the nanoparticles. Addition of surfactants, such as phosphate esters and oligomers thereof, can improve the dispersion of BT nanoparticles in host polymers and consequently the overall nanocomposite film quality. However, in such systems, residual free surfactant can lead to high leakage current and dielectric loss. Thus, approaches to bind surface modifiers to BT nanoparticles via robust chemical bonds are highly desirable. Ramesh et al. have reported on the use of trialkoxysilane surface modifiers for the dispersion of BT nanoparticles in epoxy polymer hosts resulting in nanocomposites with reasonably high er, up to 45. [12] With the objective of identifying ligands that can form stable bonds to a BT surface through coordination or condensation, we have investigated a series of different ligand functionalities. In this Communication, we report that phosphonic acid ligands effect robust surface modification of BT and related nanoparticles and that the use of particles modified with suitable phosphonic acid ligands leads to well-dispersed BT nanocomposite films with high er and high dielectric strength. We have investigated the binding of a variety of ligands to the surface of BT nanoparticles, as the stability of the binding on the surface is vital to effective surface modification. We examined the following set of ligands, each bearing an aliphatic octyl chain with a different terminal binding group: C8H17-X, where X = PO(OH)2 (OPA), SO2ONa (OSA), Si(OCH3)3 (OTMOS), and CO2H (OCA). Trialkoxysilanes are widely used surface modifiers for silicate, indium tin oxide, and other metal oxide surfaces. Phosphonic acids have been reported to modify TiO2, ZrO2, and indium tin oxide surfaces and are thought to couple to the surface of metal oxides either by heterocondensation with surface hydroxyl groups or coordination to metal ions on the surface. Carboxylic acid and sulfonic acid groups may also bind to the surface in a similar manner. A sample of each ligand was mixed with BT nanoparticles (30–50 nm, 0.5 mmol ligand/ g BT) in an ethanol/water solution and stirred at 80 °C, followed by extensive washing with ethanol or water and centrifugation to remove excess and/or physisorbed ligand. The treated BT nanoparticles were dried and characterized by using Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). Figure 1a shows a comparison of FTIR spectra in the C–H stretching region for the BT nanoparticles treated with the ligands described above, followed by washing. These results C O M M U N IC A IO N

We use electroabsorption spectroscopy to measure the change in built-in potential (VBI) across the polymer photoactive layer in diodes where indium tin oxide electrodes are systematically modified using dipolar phosphonic acid self-assembled monolayers (SAMs) with various dipole moments. We find that VBI scales linearly with the work function (Φ) of the SAM-modified electrode over a wide range when using a solution-coated poly(p-phenylenevinylene) derivative as the active layer. However, we measure an interfacial parameter of S = eΔVBI/ΔΦ < 1, suggesting that these ITO/SAM/polymer interfaces deviate from the Schottky–Mott limit, in contrast to what has previously been reported for a number of ambient-processed organic-on-electrode systems. Our results suggest that the energetics at these ITO/SAM/polymer interfaces behave more like metal/organic interfaces previously studied in UHV despite being processed from solution.

Saccharinic acids (2- C -methyl aldonic acids) may be formed by treatment of Amadori ketoses with calcium hydroxide or by the Kiliani reaction of 1-deoxy ketoses with cyanide. Thus (i) N , N -dibenzyl or N , N -dimethyl-1-amino-1-deoxy- d -fructose with aqueous calcium hydroxide afforded 2- C -methyl- d -ribono-1,4-lactone under green conditions and (ii) reaction of methyl magnesium bromide with 2,3- O -isopropylidene- d -erythronolactone gave 1-deoxy-3,4- O -isopropylidene- d -ribulose, which on subsequent treatment with aqueous sodium cyanide and hydrolysis, formed 2- C -methyl- d -arabinono-1,4-lactone. Such branched sugar lactones are likely to be of value as chirons containing branched carbon chains.

Bis-thymine units were used to noncovalently cross-link a complementary diamidopyridine-functionalized copolymer. Upon combination in noncompetitive solvents, discrete micron-scale spherical aggregates were formed arising from specific three-point polymer-cross-linker hydrogen bonding interactions. The diameter of these microspheres could be controlled through spacer structure. The cross-linking process was fully thermally reversible, with complete dissolution observed at 50 degrees C and reformation of the aggregates upon return to ambient temperature. This process could be repeated multiply, with lower particle dispersity observed arising from the annealing process.

We have explored the interactions of mono- and multivalent guests with Recognition-Induced Polymersomes (RIPs) formed from complementary random copolymers featuring diamidopyridine and thymine functionality. Addition of monovalent guests featuring imide functionality to these RIPs induced a temporary swelling of the vesicles, followed by dissociation of the vesicles due to competitive binding of the guest. Conversely, multivalent thymine-functionalized nanoparticle guests were rapidly incorporated into the RIPs, inducing a contraction of RIP diameter over time. These mono- and multivalent interactions were extremely specific: highly analogous control systems showed no interaction with the RIP structures. Taken together, these studies demonstrate highly selective molecular “lock and key” control over higher-order assembly and recognition processes.

The recently discovered superconductor MgB2 with Tc at 39 K has great potential in superconducting microelectronics. Thermodynamics studies with the calculation of phase diagrams (CALPHAD) modelling technique show that due to the high volatility of Mg, MgB2 is only thermodynamically stable under fairly high Mg overpressures for likely in situ growth temperatures. This provides a helpful insight into the appropriate processing conditions for MgB2 thin films, including the identification of the pressure–temperature region for adsorption-controlled growth. The initial MgB2 thin films were made by pulsed laser deposition followed by in situ annealing. The cross-sectional transmission electron microscopy reveals a nanocrystalline mixture of textured MgO and MgB2 with very small grain sizes. A zero-resistance transition temperature of 34 K and a zero-field critical current density of 1.3 × 106 A cm−2 were obtained. The qualities of these films are limited by the thermodynamic stability conditions, which favour deposition techniques that can maintain a high flux of Mg.

Evidence base : primary care nurses have previously been shown to be effective at improving urinary incontinence in women under 60 years, by teaching pelvic floor exercises. We tried to apply this finding to practice. R&D project : this development project involved devising and delivering an evidence-based training package, ideally to one nurse member of every practice-based primary care team (about 70). Patient outcomes were to be assessed at 6 months, and the process of changing practice recorded. Despite extending the project, only 16 nurses received training, and only a handful of patients were recruited. Impediments to progress : the large number of factors which presented difficulties are discussed using the Clinical Standards Advisory Group’s framework for describing evidence-based service changes in primary care. These included lack of GP support, insufficient ‘grass roots’ enthusiasm, time constraints and the heavy workloads of primary care nurses, work not fitting into existing roles, no product champion, no supporting changes in secondary care. Conclusion : neither evidence nor education alone are sufficient to change practice. Current changes in primary care organisation may influence future attempts to change nurse practice in the promotion of continence.

We present a theoretical characterization, based on density functional theory, of the indium tin oxide surface and of the nature of the binding sites that determine the adsorption of phosphonic acid monolayers. The validity of our theoretical description is assessed by comparing our first-principles results to X-ray photoelectron spectroscopy data.

In women and rhesus monkeys, both the negative and positive feedback actions of estradiol (E2) on gonadotropin secretion (inhibition followed by a surge) can be exerted directly at the level of the pituitary gland. We have tested the hypothesis that the positive feedback action of E2 represents but an“ escape” from its negative feedback inhibition of gonadotropin secretion consequent to a desensitization of the gonadotropes occasioned by sustained exposure to elevated concentrations of the steroid. We have attempted to replicate such a desensitization by blocking the negative feedback action of E2 by the administration of a potent estrogen receptor antagonist devoid of any agonistic properties (ZM 182,780) to rhesus monkeys in the midfollicular phase of the menstrual cycle (n = 14). The estrogen antagonist, administered at a dose that in separate experiments completely blocked both the negative and the positive feedback effect of exogenous E2 on pituitary LH secretion, failed to produce a surge-like incre...

The relative roles of infant suckling and of maternal prolactin (PRL) secretion in lactational anovulation were studied in ovary-intact and ovariectomized rhesus monkeys nursing young that had been removed from their natural mothers. Hypothalamic gonadotropin-releasing hormone (GnRH) pulse generator activity was monitored electrophysiologically in freely behaving animals by radiotelemetry. Serum luteinizing hormone, PRL, estradiol, and progesterone were also measured. Suckling inhibited GnRH pulse generator activity and ovarian cyclicity in all ovary-intact females but had no such effect on the pulse generator in long-term ovariectomized animals. When PRL secretion was suppressed by daily bromocriptine administration, GnRH pulse generator activity remained significantly inhibited and ovulation was prevented in four monkeys (6 trials), whereas in two females (6 trials) a rapid increase in pulse generator frequency and the resumption of ovarian cyclicity were observed although suckling activity was maintained. One monkey displayed both response types. Although these results indicate that suckling per se is able to restrain GnRH pulse generator activity in the absence of PRL, they also suggest that the relative importance of these determinants is variable depending on factors that remain to be determined. The present study also confirms the permissive role of the ovary in the lactational suppression of GnRH pulse generator activity.

Traditional cross-correlation considers situations where two functions or data sets are linked by a constant shift either in time or space. Correlation provides estimates of such shifts even in the presence of considerable noise corruption. This makes the technique valuable in applications like sonar, displacement or velocity determination and pattern recognition. When regions are decomposed into patches in applications such as Particle Image Velocimerty it also allows estimates to be made of whole displacement/flow fields. The fundamental problem with traditional correlation is that patch size and hence statistical reliability must be compromised with resolution. This article develops a natural generalization of cross-correlation which removes the need for such compromises by replacing the constant shift with a function of time or space. This permits correlation to be applied globally to a whole domain retaining any long-range coherences present and dramatically improves statistical reliability by using all the data present in the domain for each estimate.

The new uranyl phosphate [(UO2)3(PO4)O(OH)(H2O)2](H2O) (1) with an unprecedented framework structure has been synthesized at 150 and 185 degrees C. The structure (tetragonal, P4(2)/mbc, a = 14.015(1) A, c = 13.083(2) A, V = 2575.6(4) A(3), Z = 8) contains uranyl phosphate chains composed of uranyl pentagonal and hexagonal bipyramids and phosphate tetrahedra linked by sharing of polyhedral edges. The uranyl phosphate chains are aligned both along [100] and [010] and are linked into a novel framework structure involving channels along [001]. Topologically identical chains occur linked into sheets in more than a dozen uranyl phosphate minerals, but these chains have never been observed in opposing orientations and linked into a framework as in 1.

Transparent metal oxides, in particular, indium tin oxide (ITO), are critical transparent contact materials for applications in next-generation organic electronics, including organic light emitting diodes (OLEDs) and organic photovoltaics (OPVs). Understanding and controlling the surface properties of ITO allows for the molecular engineering of the ITO-organic interface, resulting in fine control of the interfacial chemistries and electronics. In particular, both surface energy matching and work function compatibility at material interfaces can result in marked improvement in OLED and OPV performance. Although there are numerous ways to change the surface properties of ITO, one of the more successful surface modifications is the use of monolayers based on organic molecules with widely variable end functional groups. Phosphonic acids (PAs) are known to bind strongly to metal oxides and form robust monolayers on many different metal oxide materials. They also demonstrate several advantages over other functionalizing moieties such as silanes or carboxylic acids. Most notably, PAs can be stored in ambient conditions without degradation, and the surface modification procedures are typically robust and easy to employ. This Account focuses on our research studying PA binding to ITO, the tunable properties of the resulting surfaces, and subsequent effects on the performance of organic electronic devices. We have used surface characterization techniques such as X-ray photoelectron spectroscopy (XPS) and infrared reflection adsorption spectroscopy (IRRAS) to determine that PAs bind to ITO in a predominantly bidentate fashion (where two of three oxygen atoms from the PA are involved in surface binding). Modification of the functional R-groups on PAs allows us to control and tune the surface energy and work function of the ITO surface. In one study using fluorinated benzyl PAs, we can keep the surface energy of ITO relatively low and constant but tune the surface work function. PA modification of ITO has resulted in materials that are more stable and more compatible with subsequently deposited organic materials, an effective work function that can be tuned by over 1 eV, and energy barriers to hole injection (OLED) or hole-harvesting (OPV) that can be well matched to the frontier orbital energies of the organic active layers, leading to better overall device properties.

Styrene induces lung tumors in mice but not in rats. Although metabolism of styrene to 7,8-styrene oxide (SO) by CYP2E1 has been suggested as a mediator of styrene toxicity, lung toxicity is not attenuated in CYP2E1 knockout mice. However, styrene and/or SO metabolism by mouse lung Clara cell-localized CYP2F2 to ring-oxidized cytotoxic metabolite(s) has been postulated as a key metabolic gateway responsible for both lung toxicity and possible tumorigenicity. To test this hypothesis, the lung toxicity of styrene and SO was evaluated in C57BL/6 (WT) and CYP2F2(−/−) knockout mice treated with styrene (400mg/kg/day, gavage, or 200 or 400mg/kg/day, ip) or S- or R-SO (200mg/kg/day, ip) for 5days. Styrene treated WT mice displayed significant necrosis and exfoliation of Clara cells, and cumulative BrdU-labeling index of S-phase cells was markedly increased in terminal bronchioles of WT mice exposed to styrene or S- or RSO. In contrast, Clara and terminal bronchiole cell toxicity was not observed in CYP2F2(−/−) mice exposed to either styrene or SO. This study clearly demonstrates that the mouse lung toxicity of both styrene and SO is critically dependent on metabolism by CYP2F2. Importantly, the human isoform of CYP2F, CYP2F1, is expressed at much lower levels and likely does not catalyze significant styrene metabolism, supporting the hypothesis that styrene-induced mouse lung tumors may not quantitatively, or possibly qualitatively, predict lung tumor potential in humans.

In the course of previous studies using continuous monitoring of the electrophysiological correlates of GnRH pulse generator activity, characterized by episodic increases in hypothalamic multiunit electrical activity (MUA volley), it was noticed that the nocturnal slowing of pulse generator frequency was an acute phenomenon observable in the first MUA volleys after the lights were turned off, as was the increase in frequency when the lights were turned on in the morning. This suggested that the reduction in pulse generator frequency at night may not be the consequence of an intrinsic diurnal rhythm, but an effect of light per se. Indeed, as reported herein, such an effect was observed when the lights were turned on or off at times other than the normal illumination period (normal light schedule, lights on from 0700-1900 h). That this was not simply a response to arousal was shown by awakening the animals with loud recorded noises in total darkness at the same unaccustomed times without a resulting change in frequency. This suggests that the effect of light is specific, perhaps mediated by the retino-hypothalamic tract. This direct action of light, however, is superimposed upon a diurnal rhythm, as shown by a reduction in pulse generator frequency during the subjective night when the monkeys were kept in constant light or constant darkness.

In the ovariectomized rhesus monkey, estradiol (E2) markedly reduces the frequency of the GnRH pulse generator as monitored by LH pulse frequency and the concurrent changes in hypothalamic electrical activity, an action mimicked by morphine. In addition, the duration of the increments in multiunit electrical activity (MUA volleys) that precede each LH pulse is decreased by estrogen administration, an action also shared by morphine. The role of endogenous opioids in these actions of E2 was investigated in 8 ovariectomized animals restrained in primate chairs. They were fitted with indwelling cardiac catheters and with bilateral arrays of recording electrodes chronically implanted in the mediobasal hypothalamus. Physiological serum E2 levels achieved by subcutaneous implantation of E2-containing Silastic capsules increased MUA volley interval from 50.8 +/- (SEM) 1.6 min in the control period to 81.1 +/- 6.2 min following E2. Mean MUA volley duration decreased from 21.9 +/- 1.0 to 13.0 +/- 0.7 min. The placement of empty Silastic capsules had no effect on MUA volley duration or interval. Naloxone administration (2.5 mg bolus followed by a 1 mg/h infusion lasting 4-8 h) completely (n = 4) or partially (n = 2) blocked the effects of E2 on MUA volley interval in 6 of the 8 monkeys, and was without effect in the remainder. In contrast, however, naloxone had little or no effect on the action of E2 on MUA volley duration, (13.0 +/- 0.7 vs. 14.0 +/- 0.9 min). These findings suggest that the inhibitory action of E2 on GnRH pulse generator frequency, like that of all other gonadal steroids studied to date, may be mediated by endogenous opioids.(ABSTRACT TRUNCATED AT 250 WORDS)

The activity of the GnRH pulse generator in the rhesus monkey is associated with abrupt increases in multiunit electrical activity (MUA) volleys recorded from the mediobasal hypothalamus that precede each pulse of LH in the peripheral circulation. In long-term ovariectomized animals the duration of these MUA volleys is 10-25 min and consists of a brief initial 'overshoot' followed by a plateau phase that ends in a rapid decline to baseline activity. In intact monkeys, however, the MUA volley lasts only 1-3 min, a duration equivalent to the overshoot in ovariectomized animals. In addition, the maximal frequency of neuronal activity during each MUA volley is reduced in normal animals when compared to castrates. As shown in earlier studies, estradiol given to ovariectomized monkeys causes a reduction in the duration of MUA volleys to that characteristic of intact animals within 3-5 h. In contrast to this acute effect of estradiol, the increase in MUA volley duration following ovariectomy is a gradual phenomenon, 4-6 weeks being required to achieve the MUA volley duration observed in long-term ovariectomized monkeys. A similar slow time course was observed for the increase in maximal neuronal frequency during each MUA volley. This protracted effect of ovariectomy on MUA volley duration and firing rate may be the consequence of hypothalamic remodelling but this consideration must be tempered by the observation that estradiol reverses these phenomena within hours.

Previous studies in mature fetal sheep have shown that alcohol depresses cerebral blood flow (CBF), cerebral O2 consumption (CMRO2), and cerebral glucose consumption (CMRglu). This effect earlier in gestation might contribute to the pathogenesis of fetal alcohol syndrome. Physiologic studies of immature fetal sheep have demonstrated lower CBF, CMRO2, and CMRglu as well as a blunted vasodilatory response to hypoxia compared with mature fetal sheep. The purpose of this study was to determine whether immature fetal responses to alcohol are blunted compared with near-term fetal responses. We studied seven immature fetal sheep in utero at 92 +/- 1 d gestation (term = 147 d) 2 d after placement of vascular catheters. Pure ethanol (1 g/kg) was infused i.v. to the mother over 1 h. We measured CBF and myocardial blood flow by radioactive microspheres and calculated CMRO2 and CMRglu using arterial and sagittal sinus O2 and glucose concentrations. At a fetal ethanol concentration of 33 + 8 mmol/L (150 +/- 37 mg/dL), there were no significant changes in CBF, CMRO2, or CMRglu. There was mild hypoglycemia (glucose concentration = 1.05 +/- 0.2 versus 1.33 +/- 0.2 mM baseline) and lactic acidemia (lactate concentration = 1.29 +/- 0.3 versus 1.07 +/- 0.2 mM baseline). Cardiovascular variables were unchanged as was myocardial blood flow. The immature fetal sheep brain shows no significant cerebrovascular and metabolic response to acute alcohol intoxication compared with mature fetal sheep. Mild hypoglycemia and lactic acidemia did develop. The reason for the developmental differences in response to alcohol and their relationship to fetal alcohol syndrome remain to be elucidated.

Continuous monitoring of the electrophysiological manifestations of GnRH pulse generator activity was achieved by radiotelemetry throughout the menstrual cycles of unrestrained rhesus monkeys. The characteristic increases in hypothalamic multiunit activity (MUA volleys) associated with each LH pulse measured in the peripheral circulation were of lower frequency during the luteal phase than in the follicular phase of the cycle. Multiunit activity volley frequency increased as functional luteolysis progressed and achieved maxima of approximately one volley per hour within the first few days of the follicular phase. Unexpectedly, a dramatic decline in pulse generator frequency was observed coincidentally with the initiation of the preovulatory LH surge. Evidence is presented to support the conclusion that this deceleration of pulse generator activity is the consequence of the preovulatory rise in plasma estrogen concentration. As reported in women, a significant reduction in GnRH pulse generator frequency was observed at night during the follicular phase, but not during the luteal phase, of the menstrual cycle.

Readily crystallized 2-C-methyl-d-ribono-1,4-lactone is formed in a one-pot procedure from d-glucose without any protecting groups by treatment with dimethylamine to give an Amadori ketose and then with aqueous calcium hydroxide in yields of approximately 25%; 2-C-methyl-l-ribono-1,4-lactone is similarly produced from l-glucose. 3,4-O-Isopropylidene-2-C-methyl-d-arabinono-1,5-lactone and 2-C-methyl-d-arabinono-1,4-lactone were prepared in a combined 60% yield by the Kiliani reaction of sodium cyanide with a protected 1-deoxy-d-ribulose derived from d-erythronolactone; the enantiomeric arabinonolactones are similarly available from l-erythronolactone. © 2008 Elsevier Ltd. All rights reserved.

Infiltration of planar 2D silicon photonic crystals with nanocomposites using a simple melt processing technique is presented. The nanocomposites that were developed by evenly dispersing functionalized TiO 2 nanoparticles into a photoconducting polymer exhibit high optical quality and tunable refractive index. The infiltrated photonic crystals show tuning of the photonic band-gap that is controllable by the adjustment of the nanoparticle loading level. These results may be useful in the development of tunable photonic devices, hybrid light emitting diodes and photovoltaics.

Polymer/ceramic nanocomposites provide a means of combining the high permittivities (εr) of metal oxide nanoparticles with the solution-processability and high dielectric strength of polymeric hosts. Simple mixing of nanoparticles and polymers generally results in poor quality nanocomposites due to the agglomeration of nanoparticles and poor miscibility of nanoparticles with host materials. We have shown that surface modification of metal oxide nanoparticles with phosphonic acid-based ligands affords robust surface modification and improves the processiblity and the quality of the resulting nanocomposites. We report on the use of phosphonic-acid modified barium titanate (BaTiO3, BT) nanoparticles in dielectric nanocomposites and their applications to high-energy-density capacitors and solution-processable high permittivity gate insulators in organic field-effect transistors (OFETs). Surface modification of BT nanoparticles enabled the formation of high quality nanocomposite thin films with ferroelectric polymer hosts such as poly(vinylidene fluoride-co-hexafluoropropylene), P(VDF-HFP), with large volume fractions (up to 50 vol. %), which are potentially useful materials for electrical energy storage. Similarly, the use of phosphonic acid-modified BT nanoparticles in cross-linked poly(4-vinylphenol) (PVP) allowed to form gate insulators for OFETs. High quality nanocomposite thin films at high nanoparticle volume fractions (up to 37 vol. %) with a large capacitance density (∼50 nF/cm2) and a low leakage current (10−8 A/cm2) were obtained. Pentacene-based p-type OFETs using these nanocomposites showed a large on/off current ratio (Ion/off 104 ∼ 106). We will also present the results from a recent experimental and theoretical study where the BT nanoparticle volume fraction was systematically varied in P(VDF-HFP) host, εr = 11, to find the optimum permittivity and dielectric strength, which provided a guideline for the optimization of the volume fraction for achieving maximum energy density.

The effect of corticotropin-releasing factor (CRF) on the hypothalamic gonadotropin-releasing hormone (GnRH) pulse generator, the central neuronal system governing pulsatile pituitary luteinizing horm

MD-adapt is an architecture for shamble common interfaces for medical devices in support of the goals of MDPnP. This paper proposes an architecture for enabling an open source, community-based effort to create a pool of reusable device interface implementations. The MD-adapt architecture consists of a standardized API (application programming interface) and a device metadata format, and supports building modular and portable medical device communications software adapters that run on a variety of relevant OS platforms.

The value of readily available 2-C-methyl aldonic acids in short syntheses of carbon branched piperidines containing quaternary centers is demonstrated. The effect of the introduction of a 4-C-methyl group into piperidine imino sugar inhibitors of l-fucosidases and d-galactosidases is reported. © 2007 Elsevier Ltd. All rights reserved.

The title tagatosamine, C20H25NO5.CH 4O, formed in the Amadori rearrangement of D-galactose with dibenzylamine, is shown to crystallize as the α-anomer, in contrast to the β-anomer formed in the Amadori reaction of D-glucose with dibenzylamine. © 2005 International Union of Crystallography Printed in Great Britain - all rights reserved.