skip to main content


Title: Graphitic supramolecular architectures based on corannulene, fullerene, and beyond
In this Feature Article, we survey the advances made in the field of fulleretic materials over the last five years. Merging the intriguing characteristics of fulleretic molecules with hierarchical materials can lead to enhanced properties of the latter for applications in optoelectronic, biomaterial, and heterogeneous catalysis sectors. As there has been significant growth in the development of fullerene- and corannulene-containing materials, this article will focus on studies performed during the last five years exclusively, and highlight the recent trends in designing fulleretic compounds and understanding their properties, that has enriched the repertoire of carbon-rich functional materials.  more » « less
Award ID(s):
2103722
NSF-PAR ID:
10326136
Author(s) / Creator(s):
;
Date Published:
Journal Name:
Chemical Communications
Volume:
57
Issue:
79
ISSN:
1359-7345
Page Range / eLocation ID:
10125 to 10138
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. DNA interfaces with nano, micro, and macro materials have gained widespread attention for various applications. Such interfaces exhibit distinct functions and properties not only due to the unique properties of interfacing materials but also sequence- and conformation-dependent characteristics of the DNA. Therefore, DNA interfaces with diverse dimensional materials have advanced our understanding of the interaction mechanisms and the properties of such interfaces. The unique interfacial properties of such novel materials have applications in nanotechnology, biophysics, cell biology, biosensing, and bioelectronics. The field is growing rapidly with the frequent emergence of new interfaces carrying remarkable interfacial character. In this review article, we have classified the DNA interfaces into 0D, 1D, 2D, and 3D categories based on the types of dimensional materials. We review the key efforts made in the last five years and focus on types of interfaces, interfacing mechanisms, and their state-of-the-art applications. This review will draw a general interest because of the diversity in the DNA materials science but also the unique applications that will play a cutting-edge role in biomedical and biosensing research. 
    more » « less
  2. INTRODUCTION The analysis of the human brain is a central goal of neuroscience, but for methodological reasons, research has focused on model organisms, the mouse in particular. Because substantial homology was found at the level of ion channels, transcriptional programs, and basic neuronal types, a strong similarity of neuronal circuits across species has also been assumed. However, a rigorous test of the configuration of local neuronal circuitry in mouse versus human—in particular, in the gray matter of the cerebral cortex—is missing. The about 1000-fold increase in number of neurons is the most obvious evolutionary change of neuronal network properties from mouse to human. Whether the structure of the local cortical circuitry has changed as well is, however, unclear. Recent data from transcriptomic analyses has indicated an increase in the proportion of inhibitory interneurons from mouse to human. But what the effect of such a change is on the circuit configurations found in the human cerebral cortex is not known. This is, however, of particular interest also to the study of neuropsychiatric disorders because in these, the alteration of inhibitory-to-excitatory synaptic balance has been identified as one possible mechanistic underpinning. RATIONALE We used recent methodological improvements in connectomics to acquire data from one macaque and two human individuals, using biopsies of the temporal, parietal, and frontal cortex. Human tissue was obtained from neurosurgical interventions related to tumor removal, in which access path tissue was harvested that was not primarily affected by the underlying disease. A key concern in the analysis of human patient tissue has been the relation to epilepsy surgery, when the underlying disease has required often year-long treatment with pharmaceuticals, plausibly altering synaptic connectivity. Therefore, the analysis of nonepileptic surgery tissue seemed of particular importance. We also included data from one macaque individual, who was not known to have any brain-related pathology. RESULTS We acquired three-dimensional electron microscopy data from temporal and frontal cortex of human and temporal and parietal cortex of macaque. From these, we obtained connectomic reconstructions and compared these with five connectomes from mouse cortex. On the basis of these data, we were able to determine the effect of the about 2.5-fold expansion of the interneuron pool in macaque and human cortex compared with that of mouse. Contrary to expectation, the inhibitory-to-excitatory synaptic balance on pyramidal neurons in macaque and human cortex was not substantially altered. Rather, the interneuron pool was selectively expanded for bipolar-type interneurons, which prefer the innervation of other interneurons, and which further increased their preference for interneuron innervation from mouse to human. These changes were each multifold, yielding in effect an about 10-fold expanded interneuron-to-interneuron network in the human cortex that is only sparsely present in mouse. The total amount of synaptic input to pyramidal neurons, however, did not change according to the threefold thickening of the cortex; rather, a modest increase from about 12,000 synaptic inputs in mouse to about 15,000 in human was found. CONCLUSION The principal cells of the cerebral cortex, pyramidal neurons, maintain almost constant inhibitory-to-excitatory input balance and total synaptic input across 100 million years of evolutionary divergence, which is particularly noteworthy with the concomitant 1000-fold expansion of the neuronal network size and the 2.5-fold increase of inhibitory interneurons from mouse to human. Rather, the key network change from mouse to human is an expansion of almost an order of magnitude of an interneuron-to-interneuron network that is virtually absent in mouse but constitutes a substantial part of the human cortical network. Whether this new network is primarily created through the expansion of existing neuronal types, or is related to the creation of new interneuron subtypes, requires further study. The discovery of this network component in human cortex encourages detailed analysis of its function in health and disease. Connectomic screening across mammalian species: Comparison of five mouse, two macaque, and two human connectomic datasets from the cerebral cortex. ( A ) Automated reconstructions of all neurons with their cell bodies in the volume shown, using random colors. The analyzed connectomes comprised a total of ~1.6 million synapses. Arrows indicate evolutionary divergence: the last common ancestor between human and mouse, approximately 100 million years ago, and the last common ancestor between human and macaque, about 20 million years ago. ( B ) Illustration of the about 10-fold expansion of the interneuron-to-interneuron network from mouse to human. 
    more » « less
  3. Abstract

    Poly(ether imide) (PEI) from polycondensation of 2,2‐bis[4‐(3,4‐dicarboxyphenoxy) phenyl] propane dianhydride (BPADA) andm‐phenylenediamine (mPD) is a type of high‐temperature engineering thermoplastics that have high glass transition temperature and outstanding mechanical properties. Owing to its wide use in many fields including automotive, aircraft, and electronics, the research of PEI has surged in the last few decades. As science and technology continue to progress rapidly, there is a growing demand for PEIs with better properties. Although a few approaches have successfully improved the properties of PEI, it is recognized that these approaches require complex procedures and are uneconomical. Contrastingly, end‐group modification of PEI is highly effective, simple, and economical. Over the last few years, our group has extensively studied the methods for improving the properties of PEI through end‐group modification. The end‐group moieties and polymer blocks introduce multiple hydrogen bonding, electrostatics, and microphase separation to PEI. In this article, we first classify the end groups based on their characteristics. Then, we compare their effects on the properties of PEIs, including thermal, rheological, mechanical, optical, flame‐retardant, and morphological, and discuss the roots of these effects. The in‐depth comparisons and discussion generate principles to guide the synthesis of PEIs with tailored properties by modifying the end groups. This timely article will provide insights into the synthesis of other novel high‐temperature polymers and entice endeavors to develop novel end groups.

     
    more » « less
  4. Abstract STUDY QUESTION To what extent does the use of mobile computing apps to track the menstrual cycle and the fertile window influence fecundability among women trying to conceive? SUMMARY ANSWER After adjusting for potential confounders, use of any of several different apps was associated with increased fecundability ranging from 12% to 20% per cycle of attempt. WHAT IS KNOWN ALREADY Many women are using mobile computing apps to track their menstrual cycle and the fertile window, including while trying to conceive. STUDY DESIGN, SIZE, DURATION The Pregnancy Study Online (PRESTO) is a North American prospective internet-based cohort of women who are aged 21–45 years, trying to conceive and not using contraception or fertility treatment at baseline. PARTICIPANTS/MATERIALS, SETTING, METHODS We restricted the analysis to 8363 women trying to conceive for no more than 6 months at baseline; the women were recruited from June 2013 through May 2019. Women completed questionnaires at baseline and every 2 months for up to 1 year. The main outcome was fecundability, i.e. the per-cycle probability of conception, which we assessed using self-reported data on time to pregnancy (confirmed by positive home pregnancy test) in menstrual cycles. On the baseline and follow-up questionnaires, women reported whether they used mobile computing apps to track their menstrual cycles (‘cycle apps’) and, if so, which one(s). We estimated fecundability ratios (FRs) for the use of cycle apps, adjusted for female age, race/ethnicity, prior pregnancy, BMI, income, current smoking, education, partner education, caffeine intake, use of hormonal contraceptives as the last method of contraception, hours of sleep per night, cycle regularity, use of prenatal supplements, marital status, intercourse frequency and history of subfertility. We also examined the impact of concurrent use of fertility indicators: basal body temperature, cervical fluid, cervix position and/or urine LH. MAIN RESULTS AND THE ROLE OF CHANCE Among 8363 women, 6077 (72.7%) were using one or more cycle apps at baseline. A total of 122 separate apps were reported by women. We designated five of these apps before analysis as more likely to be effective (Clue, Fertility Friend, Glow, Kindara, Ovia; hereafter referred to as ‘selected apps’). The use of any app at baseline was associated with 20% increased fecundability, with little difference between selected apps versus other apps (selected apps FR (95% CI): 1.20 (1.13, 1.28); all other apps 1.21 (1.13, 1.30)). In time-varying analyses, cycle app use was associated with 12–15% increased fecundability (selected apps FR (95% CI): 1.12 (1.04, 1.21); all other apps 1.15 (1.07, 1.24)). When apps were used at baseline with one or more fertility indicators, there was higher fecundability than without fertility indicators (selected apps with indicators FR (95% CI): 1.23 (1.14, 1.34) versus without indicators 1.17 (1.05, 1.30); other apps with indicators 1.30 (1.19, 1.43) versus without indicators 1.16 (1.06, 1.27)). In time-varying analyses, results were similar when stratified by time trying at study entry (<3 vs. 3–6 cycles) or cycle regularity. For use of the selected apps, we observed higher fecundability among women with a history of subfertility: FR 1.33 (1.05–1.67). LIMITATIONS, REASONS FOR CAUTION Neither regularity nor intensity of app use was ascertained. The prospective time-varying assessment of app use was based on questionnaires completed every 2 months, which would not capture more frequent changes. Intercourse frequency was also reported retrospectively and we do not have data on timing of intercourse relative to the fertile window. Although we controlled for a wide range of covariates, we cannot exclude the possibility of residual confounding (e.g. choosing to use an app in this observational study may be a marker for unmeasured health habits promoting fecundability). Half of the women in the study received a free premium subscription for one of the apps (Fertility Friend), which may have increased the overall prevalence of app use in the time-varying analyses, but would not affect app use at baseline. Most women in the study were college educated, which may limit application of results to other populations. WIDER IMPLICATIONS OF THE FINDINGS Use of a cycle app, especially in combination with observation of one or more fertility indicators (basal body temperature, cervical fluid, cervix position and/or urine LH), may increase fecundability (per-cycle pregnancy probability) by about 12–20% for couples trying to conceive. We did not find consistent evidence of improved fecundability resulting from use of one specific app over another. STUDY FUNDING/COMPETING INTEREST(S) This research was supported by grants, R21HD072326 and R01HD086742, from the Eunice Kennedy Shriver National Institute of Child Health and Human Development, USA. In the last 3 years, Dr L.A.W. has served as a fibroid consultant for AbbVie.com. Dr L.A.W. has also received in-kind donations from Sandstone Diagnostics, Swiss Precision Diagnostics, FertilityFriend.com and Kindara.com for primary data collection and participant incentives in the PRESTO cohort. Dr J.B.S. reports personal fees from Swiss Precision Diagnostics, outside the submitted work. The remaining authors have nothing to declare. TRIAL REGISTRATION NUMBER N/A. 
    more » « less
  5. Abstract

    Neither of us can remember people talking about stimuli‐responsive polymers when we were students. Even though this was still in the last century, it was almost 70 years after Staudinger's seminal paper “Über Polymerisation”![1]By the time we entered graduate school in the early 1990 s, the first papers on polymer light emitting diodes appeared, while research on electrically conducting, nonlinear optical, and other “functional” polymers was already in full swing. Looking back, there were some stimuli‐responsive materials that were around at the time,[2–6]but it took the better part of the last 30 years until the field had developed into what we think is one of the most vibrant areas of polymer science.[8–12]Before the potential usefulness of this class of materials was recognized, researchers were focused on developing polymeric materials that would not respond to external influences, and in fact maintain (in particular) their mechanical properties in a wide range of environments. This has led to the development of many environmentally robust polymers, which have come to impact basically every aspect of our daily life. Ironically, this long‐sought stability now comes back to haunt us in the form of plastic pollution, but this is another story. The concept of materials that adapt their properties in response to changing environmental conditions might appear like a complete reversal with respect to the original goals of creating stable materials. However, eventually a) it was recognized that materials that respond to a specific stimulus in a predictable and useful manner would significantly broaden the potential usefulness of polymers, and b) the field of polymer science had developed to the point where the rational design, preparation, and characterization of such materials became possible. The expression‘stimuli‐responsive polymer’ had been first used in the 1980’s, however its use really only gained popularity a few decades later. In the early days, terms such asenvironmentally‐sensitiveorenvironmentally‐responsive polymers,stimuli‐reversibleorstimuli‐sensitive polymers, orpolymers with phase transitionshave also been used.

     
    more » « less