Stimulus-responsive block copolymer nano-objects and hydrogels via dynamic covalent chemistry

Herein we demonstrate that dynamic covalent chemistry can be used to induce reversible morphological transitions in block copolymer nano-objects and hydrogels. Poly(glycerol monomethacrylate)–poly(2- hydroxypropyl methacrylate) (PGMA–PHPMA) diblock copolymer nano-objects (vesicles or worms) were prepared via polymerization-induced self-assembly. Addition of 4-carboxyphenylboronic acid (CPBA) leads to the formation of phenylboronate ester bonds with the 1,2-diol pendent groups on the hydrophilic PGMA stabilizer chains; such binding causes a subtle reduction in the packing parameter, which in turn induces either vesicle-to-worm or worm-to-sphere transitions. Moreover, CPBA binding is pH-dependent, so reversible transitions can be achieved by switching the solution pH, with relatively high copolymer concentrations leading to associated (de)gelation. This distinguishes these new physical hydrogels from the covalently cross-linked gels prepared using dynamic covalent chemistry reported in the literature

Accounting for groundwater in future city visions

City planners, urban innovators and researchers are increasingly working on ‘future city’ initiatives to investigate the physical, social and political aspects of harmonized urban living. Despite this, sustainability principles and the importance of urban groundwater are lacking in future city visions. Using London as a case study, the importance of groundwater for cities is highlighted and a range of future city interventions may impact on groundwater are reviewed. Using data from water resource plans and city planning strategies, changes in the groundwater balance which may occur as a result of city interventions are calculated for two future city scenarios: a ‘strategic’ future informed by organisational policy and an ‘aspirational’ future guided by sustainability principles. For London, under a strategic future, preferential investment in industry-scale technologies such as wastewater treatment and groundwater storage would occur. Acknowledgement that behaviour change offers the potential for a faster rate of transformation than innovation technologies is ignored. The capacity of community-led action and smart-home technologies to deliver sustainable water use under an aspirational future is evident, with a measurable impact on urban groundwater. These methods may be used to inform city interventions that consider the social context in addition to environmental constraints and business drivers

Partner Notification in Cases of HIV Infection

To the Editor: Landis et al. (Jan. 9 issue)1 have provided additional support for the concept and practice of partner notification — specifically, the provider-referral approach used in cases of human immunodeficiency virus (HIV) infection. Our experiences2 were quite similar to those of Landis et al., and involved a quite different and more heterogeneous population that has been described elsewhere.3 The standardized approach combining referrals by patients and by providers that our staff routinely used with patients closely resembled the provider-referral approach described by Landis et al

Topological entropy and secondary folding

A convenient measure of a map or flow's chaotic action is the topological entropy. In many cases, the entropy has a homological origin: it is forced by the topology of the space. For example, in simple toral maps, the topological entropy is exactly equal to the growth induced by the map on the fundamental group of the torus. However, in many situations the numerically-computed topological entropy is greater than the bound implied by this action. We associate this gap between the bound and the true entropy with 'secondary folding': material lines undergo folding which is not homologically forced. We examine this phenomenon both for physical rod-stirring devices and toral linked twist maps, and show rigorously that for the latter secondary folds occur.Comment: 13 pages, 8 figures. pdfLaTeX with RevTeX4 macro

Holocene environmental history of a small coastal lake from north-eastern Kamchatka Peninsula.

AbstractA radiocarbon and tephra-dated sediment core from Lifebuoy Lake, located on the north-east coast of Kamchatka Peninsula, was analysed for pollen, spores, diatoms, chironomids and tephra in order to uncover regional environmental history.The 6500-year environmental history of Lifebuoy Lake correlates with the broad regional patterns of vegetation development and climate dynamics with both diatoms and chironomids showing near-synchronous changes.Between ca. 6300 and 3900calyrBP, the lake ecosystem was naturally enriched, with several Stephanodiscus species dominating the diatom plankton. This natural eutrophication state is likely to be due to a combination of the base-rich catchment geology, the fertilisation effect of several fires in the catchment, silica input from tephra layers and, possibly, nitrogen input from seabirds. The substantial tephra deposit at about 3850calyrBP might have stopped sedimentary phosphorus from entering the lake water thus decreasing the trophic state of the lake and facilitating the shift in diatom composition to a benthic Fragiliariaceae complex.Both diatoms and chironomids showed simultaneous compositional changes, which are also reflected by statistically significant changes in their rates of change 300–400years after the arrival of Pinus pumila in the lake catchment. The rapid increase in both total diatom concentration and the percentage abundance of the large heavy species, Aulacoseira subarctica might be a response to the change in timing and intensity of lake spring turn-over due to the changes in the patterns of North Pacific atmospheric circulation, most notably westward shift of the Aleutian Low.The two highest peaks in A. subarctica abundance at Lifebouy Lake occurred during opposite summer temperature inferences: the earlier peak (3500–2900calyrBP) coincided with warm summers and the latter peak (300calyrBP–present) occurred during the cold summer period. These imply that A. subarctica shows no direct response to the changes of summer air temperature. Instead, it appears to thrive during the periods of increased winter precipitation, thicker ice and late spring turn-over periods, i.e., shows indirect response to climate.The clearest effect of tephra deposition on the lake ecosystem is above 908cm (ca. 3800calyrBP) where the tephra deposit might have caused the shift from Stephanodiscus-dominated planktonic assemblages to the Fragilariaceae complex of benthic species. Tephra deposits might have also contributed towards the development of eutrophic plankton from about 6300calyrBP. It is not certain if several tephra deposits influenced diatom and chironomid changes during the last 300years

Insulin-Like Growth Factor Levels During Pregnancy in the Cow are Affected by Protein Supplementation in the Maternal Diet

To determine if dietary protein supplementation in early pregnancy alters total circulating insulinlike growth factor (IGF) levels, genetically similar heifers were fed diets containing different levels of protein in the first and second trimesters of gestation. The groups were: low/low (L/L), fed a diet containing 7% crude protein (CP) per kg/DM (low protein) in the first and second trimesters; high/high (H/H), fed a diet containing 14% CP per kg/DM (high protein) in the first and second trimesters; low/high (L/H), fed low protein in the first trimester and high in the second trimester and vice versa for the high/low (H/L) group. At day 62 of gestation, there was a significant difference (

General distress, hopelessness-suicidal ideation and worrying in adolescence:concurrent and predictive validity of a symptom-level bifactor model for clinical diagnoses

BACKGROUND: Clinical disorders often share common symptoms and aetiological factors. Bifactor models acknowledge the role of an underlying general distress component and more specific sub-domains of psychopathology which specify the unique components of disorders over and above a general factor. METHODS: A bifactor model jointly calibrated data on subjective distress from The Mood and Feelings Questionnaire and the Revised Children's Manifest Anxiety Scale. The bifactor model encompassed a general distress factor, and specific factors for (a) hopelessness-suicidal ideation, (b) generalised worrying and (c) restlessness-fatigue at age 14 which were related to lifetime clinical diagnoses established by interviews at ages 14 (concurrent validity) and current diagnoses at 17 years (predictive validity) in a British population sample of 1159 adolescents. RESULTS: Diagnostic interviews confirmed the validity of a symptom-level bifactor model. The underlying general distress factor was a powerful but non-specific predictor of affective, anxiety and behaviour disorders. The specific factors for hopelessness-suicidal ideation and generalised worrying contributed to predictive specificity. Hopelessness-suicidal ideation predicted concurrent and future affective disorder; generalised worrying predicted concurrent and future anxiety, specifically concurrent generalised anxiety disorders. Generalised worrying was negatively associated with behaviour disorders. LIMITATIONS: The analyses of gender differences and the prediction of specific disorders was limited due to a low frequency of disorders other than depression. CONCLUSIONS: The bifactor model was able to differentiate concurrent and predict future clinical diagnoses. This can inform the development of targeted as well as non-specific interventions for prevention and treatment of different disorders

Anthropogenic alteration of nutrient supply increases the global freshwater carbon sink

Lakes have a disproportionate effect on the global carbon (C) cycle relative to their area, mediating C transfer from land to atmosphere, and burying organic-C in their sediments. The magnitude and temporal variability of C burial is, however, poorly constrained, and the degree to which humans have influenced lake C cycling through landscape alteration has not been systematically assessed. Here, we report global and biome specific trajectories of lake C sequestration based on 516 lakes and show that some lake C burial rates (i.e., those in tropical forest and grassland biomes) have quadrupled over the last 100 years. Global lake C-sequestration (~0.12 Pg year-1) has increased by ~72 Tg year-1 since 1900, offsetting 20% of annual CO2 freshwater emissions rising to ~30% if reservoirs are included and contributing to the residual continental C sink. Nutrient availability explains ~70% of the observed increase, while rising temperatures have a minimal effect

Competing orders in a magnetic field: spin and charge order in the cuprate superconductors

We describe two-dimensional quantum spin fluctuations in a superconducting Abrikosov flux lattice induced by a magnetic field applied to a doped Mott insulator. Complete numerical solutions of a self-consistent large N theory provide detailed information on the phase diagram and on the spatial structure of the dynamic spin spectrum. Our results apply to phases with and without long-range spin density wave order and to the magnetic quantum critical point separating these phases. We discuss the relationship of our results to a number of recent neutron scattering measurements on the cuprate superconductors in the presence of an applied field. We compute the pinning of static charge order by the vortex cores in the `spin gap' phase where the spin order remains dynamically fluctuating, and argue that these results apply to recent scanning tunnelling microscopy (STM) measurements. We show that with a single typical set of values for the coupling constants, our model describes the field dependence of the elastic neutron scattering intensities, the absence of satellite Bragg peaks associated with the vortex lattice in existing neutron scattering observations, and the spatial extent of charge order in STM observations. We mention implications of our theory for NMR experiments. We also present a theoretical discussion of more exotic states that can be built out of the spin and charge order parameters, including spin nematics and phases with `exciton fractionalization'.Comment: 36 pages, 33 figures; for a popular introduction, see http://onsager.physics.yale.edu/superflow.html; (v2) Added reference to new work of Chen and Ting; (v3) reorganized presentation for improved clarity, and added new appendix on microscopic origin; (v4) final published version with minor change

The transfer of diatoms from freshwater to footwear materials: An experimental study assessing transfer, persistence, and extraction methods for forensic reconstruction

In recent years there has been growing interest in environmental forms of trace evidence, and ecological trace evidence collected from footwear has proved valuable within casework. Simultaneously, there has been growing awareness of the need for empirical experimentation to underpin forensic inferences. Diatoms are unicellular algae, and each cell (or ‘frustule’) consists of two valves which are made of silica, a robust material that favours their preservation both in sediments and within forensic scenarios. A series of experiments were carried out to investigate the transfer and persistence of diatoms upon common footwear materials, a recipient surface that has historically been overlooked by studies of persistence. The effectiveness of two novel extraction techniques (jet rinsing, and heating and agitation with distilled water) was compared to the established extraction technique of hydrogen peroxide digestion, for a suite of five common footwear materials: canvas, leather, and ‘suede’ (representing upper materials), and rubber and polyurethane (representing sole materials). It was observed that the novel extraction technique of heating and agitation with distilled water did not extract fewer diatom valves, or cause increased fragmentation of valves, when compared to peroxide digestion, suggesting that the method may be viable where potentially hazardous chemical reactions may be encountered with the peroxide digestion method. Valves could be extracted from all five footwear materials after 3 min of immersion, and more valves were extracted from the rougher, woven upper materials than the smoother sole materials. Canvas yielded the most valves (a mean of 2511/cm2) and polyurethane the fewest (a mean of 15/cm2). The persistence of diatoms on the three upper materials was addressed with a preliminary pilot investigation, with ten intervals sampled between 0 and 168 h. Valves were seen to persist in detectable quantities after 168 h on all three upper materials. However, some samples produced slides with no valves, and the earliest time after which no diatom valves were found was 4 h after the transfer. Analysis of the particle size distributions over time, by image analysis, suggests that the retention of diatoms may be size-selective; after 168 h, no particles larger than 200 μm2 could be found on the samples of canvas, and > 95% of the particles on the samples of suede were less than or equal to 200 μm2. A pilot investigation into the effects of immersion interval was carried out upon samples of canvas. Greater numbers of valves were extracted from the samples with longer immersion intervals, but even after 30 s, > 500 valves could be recovered per cm2, suggesting that footwear may be sampled for diatoms even if the contact with a water body may have been brief. These findings indicate that, if the variability within and between experimental runs can be addressed, there is significant potential for diatoms to be incorporated into the trace analysis of footwear and assist forensic reconstructions