“Uncovering” Industrial Symbiosis

Since 1989, efforts to understand the nature of interfirm resource sharing in the form of industrial symbiosis and to replicate in a deliberate way what was largely self‐organizing in Kalundborg, Denmark have followed many paths, some with much success and some with very little. This article provides a historical view of the motivations and means for pursuing industrial symbiosis—defined to include physical exchanges of materials, energy, water, and by‐products among diversified clusters of firms. It finds that “uncovering” existing symbioses has led to more sustainable industrial development than attempts to design and build eco‐industrial parks incorporating physical exchanges. By examining 15 proposed projects brought to national and international attention by the U.S. President's Council on Sustainable Development beginning in the early 1990s, and contrasting these with another 12 projects observed to share more elements of self‐organization, recommendations are offered to stimulate the identification and uncovering of already existing “kernels” of symbiosis. In addition, policies and practices are suggested to identify early‐stage precursors of potentially larger symbioses that can be nurtured and developed further. The article concludes that environmentally and economically desirable symbiotic exchanges are all around us and now we must shift our gaze to find and foster them.     

Protamine‐induced condensation of peptide nanofilaments into twisted bundles with controlled helical geometry

Chiral self‐assembly of peptides is of fundamental interest in the field of biology and material science. Protamine, an alkaline biomacromolecule which is ubiquitous in fish and mammalian, plays crucial roles in directing the helical twisting of DNA. Inspired by this, we reported a bioinspired pathway to direct the hierarchical chiral self‐assembly of a short synthetic dipeptide. The peptide could self‐assemble into negatively charged chiral micelles in water that spontaneously formed a nematic liquid crystalline phase. By incorporation with protamine, the micelles condensed with the protamine into large helical bundles with precisely controlled diameter. Furthermore, to simulate the intracellular environments, we investigated macromolecular crowding on the coassembly of peptide and protamine, which leads to the formation of much thinner helical structures. The results highlight the roles of highly charged biomacromolecules and macromolecular crowding on peptide self‐assembly, which are beneficial for the practical applications of self‐assembling peptides in biomedicine and sensing.     

Helical Polybissilsesquioxane Bundles Prepared Using a Self‐Templating Approach

Polybissilsesquioxanes with single‐handed helical morphologies attracted much attention during the last decade, which could be applied as asymmetric catalysts and chiral stationary phases. Herein, a pair of chiral biphenylene‐bridged bissilsesquioxanes were synthesized. They self‐assembled into helical bundles in ethanol, behavior that was confirmed in field emission scanning electron microscopy images. Circular dichroism analysis indicated that the biphenylene groups twisted in a single‐handed fashion. Single‐handed helical polybissilsesquioxane bundles were prepared via polycondensation of the bissilsesquioxanes, using a self‐templating approach. Because of the shrinkage that occurred during polycondensation, the helical pitches of the bundles were shorter than those of their corresponding organic self‐assemblies. The wide‐angle X‐ray diffraction pattern indicated that there were no π–π interactions among the diphenylene groups. The circular dichroism spectra indicated that the chirality was successfully transferred from the bissilsesquioxane self‐assemblies to the polybissilsesquioxane. The polybissilsesquioxanes displayed a capacity for the adsorption of nitrobenzene and had potential application for enantioseparation. Chirality 28:44–48, 2016. © 2015 Wiley Periodicals, Inc.     

Autoimmunity and the microbiome: T‐cell receptor mimicry of “self” and microbial antigens mediates self tolerance in holobionts

I propose a T‐cell receptor (TcR)‐based mechanism by which immunity mediates both “genetic self” and “microbial self” thereby, connecting microbiome disease with autoimmunity. The hypothesis is based on simple principles. First, TcR are selected to avoid strong cross‐reactivity with “self,” resulting in selection for a TcR repertoire mimicking “genetic self.” Second, evolution has selected for a “microbial self” that mimics “genetic self” so as to share tolerance. In consequence, our TcR repertoire also mimics microbiome antigenicity, providing a novel mechanism for modulating tolerance to it. Also, the microbiome mimics the TcR repertoire, acting as a secondary immune system. I call this TcR‐microbiome mimicry “holoimmunity” to denote immune tolerance to the “holobiont self.” Logically, microbiome‐host mimicry means that autoimmunity directed at host antigens will also attack components of the microbiome, and conversely, an immunological attack on the microbiome may cross‐react with host antigens producing “holoautoimmunity.”

     

From “Overweight” to “About Right”: Evidence of a Generational Shift in Body Weight Norms

In this article, we describe differences in the self‐perception of weight status in the United States between the two most recent National Health and Nutrition Examination Survey (NHANES) periods (1988–1994 and 1999–2004), and test the hypothesis that secular increases in adult mean BMI, adult obesity, and childhood obesity contributed to changes over time in weight perceptions. We find that the probability of self‐classifying as overweight is significantly lower on average in the more recent survey, for both women and men, controlling for objective weight status and other factors. Among women, the decline in the tendency to self‐classify as overweight is concentrated in the 17–35 age range, and is more pronounced among women with normal BMI than those with overweight BMI. Among men, the shift away from feeling overweight is roughly equal across age groups. Overweight men exhibit a sharper decline in feeling overweight than normal weight men. Despite the declines in feeling overweight between surveys, weight misperception did not increase significantly for men and decreased by a sizable margin among women. We interpret the findings as evidence of a generational shift in social norms related to body weight. As a result, people may be less likely to desire weight loss than previously, limiting the effectiveness of public health campaigns aimed at weight reduction. On the other hand, there may be health benefits associated with improved body image.     

Chiral Molecular Science: How were the absolute configurations of chiral molecules determined? “Experimental results and theories”

Molecular chirality is a key concept in chemistry, bioscience, and molecular technology, like the invention of a light‐powered chiral molecular motor explained in this review. Thus, the primary research subject is how to determine the absolute configuration (AC) of chiral compounds. This review article focuses on the principle, theory, and practice of the nonempirical methods for determining ACs of chiral compounds, i.e., the Bijvoet method in X‐ray crystallography and the circular dichroism (CD) exciton chirality method, together with the historical aspects of AC determination. The theoretical equations of X‐ray crystallography and exciton CD spectroscopy are explained in detail, and these equations are useful for readers to understand the principle and mechanism of these methods. This review also focuses on the relative methods, where the internal reference with known AC is used and the relative configuration is determined by X‐ray crystallography and/or ¹H nuclear magnetic resonance (NMR) diamagnetic anisotropy method. In these cases, CSDP acid and MαNP acid are useful for the chiral resolution of racemic alcohols, where their diastereomeric esters are easily separable by high‐performance liquid chromatography (HPLC) on silica gel. Thus, these methods are useful for the preparation of enantiopure compounds and simultaneous determination of their ACs. In this review article, the above methods are explained mainly based on the author's own research results.     

Synthesis and Chiral Recognition of Nickel(II) Macrocyclic Complex with (R)‐Naphthylethyleneamine Pendant Groups and its Self‐Assembled Framework

A novel nickel(II) hexaaza macrocyclic complex, [Ni(L^R,R)](ClO₄)₂ ( 1 ), containing chiral pendant groups was synthesized by an efficient one‐pot template condensation and characterized (L^R,R═1,8‐di((R)‐α‐methylnaphthyl)‐1,3,6,8,10,13‐hexaazacyclotetradecane). The crystal structure of compound 1 was determined by single‐crystal X‐ray analysis. The complex was found to have a square‐planar coordination environment for the nickel(II) ion. Open framework [Ni(L^R,R)]₃[C₆H₃(COO)₃]₂ ( 2 ) was constructed from the self‐assembly of compound 1 with deprotonated 1,3,5‐benzenetricarboxylic acid, BTC^3?. Chiral discrimination of rac‐1,1′‐bi‐2‐naphthol and rac‐2,2,2‐trifluoro‐1‐(9‐anthryl)ethanol was performed to determine the chiral recognition ability of the chiral complex ( 1 ) and its self‐assembled framework ( 2 ). Binaphthol showed a good chiral discrimination on the framework ( 2 ). The optimum experimental conditions for the chiral discrimination were examined by changing the weight ratio between the macrocyclic complex 1 or self‐assembled framework 2 and racemates. The detailed synthetic procedures, spectroscopic data including single‐crystal X‐ray analysis, and the results of the chiral recognition for the compounds are described. Chirality, 25:54‐58, 2013 © 2012 Wiley Periodicals, Inc.     

Der „Sekundenkleber“ der Stummelfüßer

Novel insights into the “superglue” of velvet worms The biological “superglue” of velvet worms provides inspiration towards circular processing of advanced polymers. In nature, velvet worms employ a fluid, protein‐rich secretion for hunting and defense, which forms rapidly into stiff fibers. The fluid‐to‐fiber transition occurs outside the body without regulations, indicating that the “instructions” for assembly are programmed into the protein building blocks. Electrostatic interactions between oppositely charged protein domains and free ions drive protein folding, self‐organization (coacervation) and stabilization of the building blocks into nanoscale droplets. Yet, nanodroplets can be instantly transformed via simple mechanical stimulus as proteins partially unfold, merge together and form a strong network, which solidifies into a fiber. The mechanism is based on basic physico‐chemical principles. Thus, by extracting these principles, new methods of synthesizing sustainable polymer‐based materials can be developed.     

“Making coin” and the networker: Masculine self‐making in the Australian professional managerial class

In this article I unpack the labour of “networking” to understand the changes in sociality and worker identity that have occurred in the Australian professional managerial class workforce under post‐Fordism. Drawing on fieldwork undertaken at the interface of the pubic service and private consultancy firms in Canberra, I break from dominant readings of intimacy in post‐Fordism which preference either a downwards imposition of “ways of being” from capital to worker, or a reactive self‐regulation in line with objective external structures. Networking, I argue, is as much about being recognised as patron as it is about any tangible economic benefits. The intimate relations and self‐fashioning of networking constitute attempts to embody particular classed, sexualised, gendered fantasies of the figure of “the networker” in post‐Fordist Australian business culture. This interpretation does not necessitate overlooking the tangible results of networking, and I discuss too, how masculine fantasy structures the topography of workplaces.     

A Usage Scenario Independent “Air Chargeable” Flexible Zinc Ion Energy Storage Device

A rationally designed “air chargeable” energy storage device is demonstrated, which can be effectively charged by harvesting pervasive energy from the ambient environment. For an “air chargeable” zinc‐ion capacitor system, the system simply consists of a flexible bifunctional “U” shaped electrode (with the functions of energy harvesting and storage), a zinc metal electrode in middle, and two different polyelectrolytes (polyacrylamide and sodium polyacrylate) sandwiched between the zinc metal and “U” shaped electrode. When the zinc‐ion capacitor is exhausted, it can be quickly charged to 88% within 10 min by simply opening the sealing tape and allowing the air diffuse in. The capacitor exhausting‐air charging processes are repeated 60 times and the whole system works well. When the external power supplier is available, both the zinc‐ion capacitor and “air charging” component can be fully recovered. A large capacity (≈1000 mAh) “air chargeable” zinc‐vanadium battery is also demonstrated. The zinc‐vanadium battery can be fully charged by air in 1 h. This work offers a usage scenario independent reliable self‐chargeable power supply system as a promising approach to solve the intermittent and unpredictable nature of currently developed self‐chargeable devices.     

Hourglass Triboelectric Nanogenerator as a “Direct Current” Power Source

Hourglass, or sandglass, is known for centuries to record the passage of time. Here, an hourglass triboelectric nanogenerator (HG‐TENG) is reported as a power source by harnessing the kinetic energy of falling particles. By employing the geometry of an hourglass and replacing the sand with a mixture of polytetrafluoroethylene (PTFE) pellets and Al balls, the HG‐TENG delivers a train of electrical pulses of the same sign without a rectifier bridge. When the volume ratio of the PTFE pellets to the Al balls is 1:1, the HG‐TENG is able to light up 160 commercial light emitting diodes intermittently for 18 s. Furthermore, it is demonstrated that the HG‐TENG can also serve as a self‐powered UV counterfeit detector.     

Unusual Formation of CoO@C “Dandelions” Derived from 2D Kagóme MOLs for Efficient Lithium Storage

Despite great breakthroughs, the search for anode materials with high performance for lithium‐ion batteries (LIBs) remains challenging. Hence, engineering advantageous structures via effective routes can bring new possibilities to the development of the LIB field. Herein, the precise synthesis of three‐dimensional (3D) hybrids of ultrathin carbon‐wrapped CoO (CoO@C) dandelions is reported by the pyrolysis of two‐dimensional (2D) Kagóme metal–organic layers (MOLs) at 400 °C under an Ar atmosphere. Due to the special coordination structure of the paternal MOLs, the resulting CoO nanowires show a small diameter of 5–10 nm and are uniformly confined within the ultrathin carbon layer. Based on the time‐dependent pyrolysis experiments, a crystal transformation mechanism of in situ self‐templated‐recrystallization‐self‐assembly accompanied by phase and morphology changes is first presented to reveal the formation of the 3D dandelion‐like spheres with assembly of nanowire arrays from a 2D Kagóme MOL. By virtue of structural and compositional features, including a 3D array structure, the small size of the primary ultrathin nanowires, and a uniform ultrathin graphitic carbon layer, these unique CoO@C dandelions display high specific capacity, good rate capability, and excellent cycling stability. Importantly, this approach can be extended to accurately synthesize other desired composite structures.     

Design and synthesis of a stereodynamic catalyst with reversal of selectivity by enantioselective self‐inhibition

Chirality plays a pivotal role in an uncountable number of biological processes, and nature has developed intriguing mechanisms to maintain this state of enantiopurity. The strive for a deeper understanding of the different elements that constitute such self‐sustaining systems on a molecular level has sparked great interest in the studies of autoinductive and amplifying enantioselective reactions. The design of these reactions remains highly challenging; however, the development of generally applicable principles promises to have a considerable impact on research of catalyst design and other adjacent fields in the future. Here, we report the realization of an autoinductive, enantioselective self‐inhibiting hydrogenation reaction. Development of a stereodynamic catalyst with chiral sensing abilities allowed for a chiral reaction product to interact with the catalyst and change its selectivity in order to suppress its formation, which caused a reversal of selectivity over time.     

Prescribed “Breaks” as a Means to Disrupt Weight Control Efforts

Objective: Research on long‐term maintenance of weight loss is hampered by the fact that relapse typically does not occur until after 6 months. We sought to determine whether relapses could be induced earlier by intentionally interrupting the momentum of weight loss during a treatment program and thus provide a model for weight maintenance research. Research Methods and Procedures: Subjects (N = 142) were recruited at two centers and randomly assigned to a control group, a long break group (LB), or a short break group (SB). The control group received a standard behavioral weight loss program with 14 weekly sessions; the LB and SB groups received the same. However, the LB group took a 6‐week break after lesson 7, and the SB group took a 2‐week break after lessons 3, 6, and 9. Participants were instructed to stop all weight loss efforts during breaks. Results: Participants seemed to take breaks as prescribed, with interruptions in self‐monitoring, dietary adherence, and self‐weighing (but not in exercise). However, participants quickly resumed these behaviors after the break. Breaks produced a slowing of weight loss or slight regain, but weight losses during the breaks were not significantly different from the control group. Importantly, overall weight losses (0 to 5 months or 0 to 11 months) did not differ between conditions. Discussion: This study was not successful in developing a method to experimentally produce weight loss relapses. However, the finding that prescribed breaks do not have adverse effects may have clinical application.     

Enantiomeric assay of escitalopram S(+)‐enantiomer and its “in‐process impurities” using two different techniques

The enantiomeric purity of escitalopram oxalate ESC and its “in‐process impurities,” namely, ESC‐N‐oxide, ESC‐citadiol, and R(?)‐enantiomer were studied in drug substance and products using high‐performance liquid chromatography (HPLC)‐UV (Method I), synchronous fluorescence spectroscopy (SFS) (Method IIA), and first derivative SFS (Method IIB). Method I describes as an isocratic HPLC‐UV for the direct resolution and determination of enantiomeric purity of ESC and its “in‐process impurities.” The proposed method involved the use of α_l‐acid glycoprotein (AGP) chiral stationary phase. The regression plots revealed good linear relationships of concentration range of 0.25 to 100 and 0.25 to 10 μg mL^?1 for ESC and its impurities. The limits of detection and quantifications for ESC were 0.075 and 0.235 μg mL^?1, respectively. Method II involves the significant enhancement of the fluorescence intensities of ESC and its impurities through inclusion complexes formation with hydroxyl propyl‐β‐cyclodextrin as a chiral selector in Micliavain buffer. Method IIA describes SFS technique for assay of ESC at 225 nm in presence of its impurities: R(?)‐enantiomer, citadiol, and N‐oxide at ?λ of 100 nm. This method was extended to (Method IIB) to apply first derivative SFS for the simultaneous determination of ESC at 236 nm and its impurities: the R(?)‐enantiomer, citadiol, and N‐oxide at 308, 275, and 280 nm, respectively. Linearity ranges were found to be 0.01 to 1.0 μg mL^?1 for ESC and its impurities with lower detection and quantification limits of 0.033/0.011 and 0.038/0.013 μg mL^?1 for SFS and first derivative synchronous fluorescence spectra (FDSFS), respectively. The methods were used to investigate the enantiomeric purity of escitalopram.     

Luminescent probing of the simplest chiral α‐amino acid–alanine in an enantiopure and racemic state

Luminescent spectroscopy combined with the technique of luminescent probing with rare earth ions (europium, gadolinium, terbium) and an actinide ion (uranyl) was used to differentiate enantiopure and racemic alanine, the simplest chiral proteinogenic amino acid. Using the achiral luminescent probes, small differences between pure L and DL alanine in the solid state were strongly amplified. Based on the observed electronic transitions of the probes, the position of the triplet level of the coordinated alanine was estimated. Formation of homo‐ and heterochiral complexes between enantiomers of alanine and the metal ions is discussed as a possible mechanism of chiral self‐discrimination.     

Enantiomeric separation of prothioconazole and prothioconazole‐desthio on chiral stationary phases

Prothioconazole is a type of broad‐spectrum triazole thione fungicide developed by the Bayer Company. Prothioconazole‐desthio is the main metabolite of prothioconazole in the environment. In our study, enantiomeric separation of prothioconazole and prothioconazole‐desthio was performed on various chiral stationary phases (CSPs) by high‐performance liquid chromatography (HPLC). It was found that polysaccharide CSPs showed better ability than brushing CSPs in enantiomeric separation. The successful chiral separation of prothioconazole could be achieved on self‐made Chiralcel OD, commercialized Chiralcel OJ‐H and Lux Cellulose‐1. Chiralpak IA, Chiralpak IB, Chiralpak IC, Chiralcel OD, Chiralpak AY‐H, Chiralpak AZ‐H, and Lux Cellulose‐1 realized the baseline separation of prothioconazole‐desthio enantiomers. Simultaneous enantiomeric separation of prothioconazole and prothioconazole‐desthio was performed on Lux Cellulose‐1 using acetonitrile (ACN) and water as mobile phase. In most cases, low temperature favored the separation of two compounds. The influence of the mobile phase ratio or type was deeply discussed. We obtained larger Rs and longer analysis time with a smaller proportion of isopropanol (IPA) or ethanol and more water content at the same temperature. The ratio of ACN and water had influences on the outflow orders of prothioconazole‐desthio enantiomers. This work provides a new approach for chiral separation of prothioconazole and prothioconazole‐desthio with a discussion of chiral separation mechanism on different CSPs.     

Chiral Resolution and Absolute Configuration of the Enantiomers of the Psychoactive “Designer Drug” 3,4‐Methylenedioxypyrovalerone

Illicit rac‐MDPV (3,4‐methylenedioxypyrovalerone), manufactured in clandestine labs, has become widely abused for its cocaine‐like stimulant properties. It has recently been found as one of the toxic materials in the so‐called “bath salts,” producing, among other effects, psychosis and tachycardia in humans when introduced by any of the several routes of administration (e.g., intravenous, oral, etc.). The considerable toxicity of this “designer drug” probably resides in one of the enantiomers of the racemate. In order to obtain a sufficient amount of the enantiomers of rac‐MDPV to determine their activity, we improved the known synthesis of rac‐MDPV and found chemical resolving agents, (+)‐ and (–)‐2’‐bromotetranilic acid, that gave the MDPV enantiomers in >96% enantiomeric excess as determined by ¹H nuclear magnetic resonance and chiral high‐performance liquid chromatography. The absolute stereochemistry of these enantiomers was determined by single‐crystal X‐ray diffraction studies. Chirality 27:287‐293, 2015. Published 2015. This article is a U.S. Government work and is in the public domain in the USA.     

The “online brain”: how the Internet may be changing our cognition

The impact of the Internet across multiple aspects of modern society is clear. However, the influence that it may have on our brain structure and functioning remains a central topic of investigation. Here we draw on recent psychological, psychiatric and neuroimaging findings to examine several key hypotheses on how the Internet may be changing our cognition. Specifically, we explore how unique features of the online world may be influencing: a) attentional capacities, as the constantly evolving stream of online information encourages our divided attention across multiple media sources, at the expense of sustained concentration; b) memory processes, as this vast and ubiquitous source of online information begins to shift the way we retrieve, store, and even value knowledge; and c) social cognition, as the ability for online social settings to resemble and evoke real‐world social processes creates a new interplay between the Internet and our social lives, including our self‐concepts and self‐esteem. Overall, the available evidence indicates that the Internet can produce both acute and sustained alterations in each of these areas of cognition, which may be reflected in changes in the brain. However, an emerging priority for future research is to determine the effects of extensive online media usage on cognitive development in youth, and examine how this may differ from cognitive outcomes and brain impact of uses of Internet in the elderly. We conclude by proposing how Internet research could be integrated into broader research settings to study how this unprecedented new facet of society can affect our cognition and the brain across the life course.