Bioinspired Self-Assembly of Metalloporphyrins and Polyelectrolytes into Hierarchical Supramolecular Nanostructures for Enhanced Photocatalytic H2 Production in Water.

Polypeptides, as natural polyelectrolytes, are assembled into tailored proteins to integrate chromophores and catalytic sites for photosynthesis. Mimicking nature to create the water-soluble nanoassemblies from synthetic polyelectrolytes and photocatalytic molecular species for artificial photosynthesis is still rare. Here, we report the enhancement of the full-spectrum solar-light-driven H2 production within a supramolecular system built by the co-assembly of anionic metalloporphyrins with cationic polyelectrolytes in water. This supramolecular photocatalytic system achieves a H2 production rate of 793 and 685 µmol h-1 g-1 over 24 h with a combination of Mg or Zn porphyrin as photosensitizers and Cu porphyrin as a catalyst, which is more than 23 times higher than that of free molecular controls. With a photosensitizer to catalyst ratio of 10000 : 1, the highest H2 production rate of >51,700 µmol h-1 g-1 with a turnover number (TON) of >1,290 per molecular catalyst was achieved over 24 h irradiation. The hierarchical self-assembly not only enhances photostability through forming ordered stackings of the metalloporphyrins but also facilitates both energy and electron transfer from antenna molecules to catalysts, and therefore promotes the photocatalysis. This study provides structural and mechanistic insights into the self-assembly enhanced photostability and catalytic performance of supramolecular photocatalytic systems.

Two-dimensional Supramolecular Polymers Based on Selectively Recognized Aromatic Cation-π and Donor-Acceptor Motifs for Photocatalytic Hydrogen Evolution.

Two-dimensional (2D) organic polymers have recently received considerable interest, especially those whose architectures are held together via supramolecular engineering. However, current approaches toward supramolecular 2D structures usually suffer from mutual interference of noncovalent interactions and lack of intrinsic functions. Herein, we report well-regulated 2D supramolecular polymers (2DSPs) through an aromatics-selective recognition strategy of cation-π and donor-acceptor (D-A) motifs, which are derived from C4 -symmetric cationic monomers and electron-withdrawing molecules. By subtly designing the strength and direction of noncovalent driving forces, the mutual interference between cation-π and D-A interactions is effectively avoided, enabling the construction of 2DSPs in aqueous solution. On this basis, the resultant 2DSPs possess boosted photocatalytic hydrogen evolution activity at a rate of 600 µmol g-1 h-1 , which is mainly ascribed to the specific stacking mode of cation-π/D-A motifs and the ordered 2D structures.

Chirality-Controlled Supramolecular Donor-Acceptor Copolymerization with Distinct Energy Transfer Efficiency.

Chirality delivers substantial value to the field of supramolecular polymers, not only serving as a probe to monitor the dynamic assembly process but providing access to chiroptical materials. The current study demonstrates that, for supramolecular donor-acceptor copolymers, their comonomer organization modes can be greatly influenced by stereocommunication at the molecular level. The enantiopure N-[(1R or 1S)-phenylethyl]benzamides are incorporated into two structurally similar comonomers, locating between the π-aromatic diethynylacene core and the alkyl chain peripheries. Parallel arrangement of the stereogenic methyl units brings steric hindrance between the homochiral comonomers, which is relieved for the heterochiral comonomers due to the adoption of staggered arrangement. It consequently steers randomly mixed organization for the homochiral supramolecular copolymers within the nanofibers. In comparison, the heterochiral counterparts form nanoparticles in an alternate donor-acceptor organization manner. The variation of comonomer arrangement modes gives rise to distinct energy transfer efficiency at the supramolecular level. Overall, the elaborate manipulation of stereogenic centers in the comonomer structures exerts significant impacts on the characteristics of supramolecular copolymers, which could be useful for chiral sensing, recognition, and optoelectronic applications.

Impact analysis of environmental and social factors on early-stage COVID-19 transmission in China by machine learning.

As a highly contagious disease, COVID-19 caused a worldwide pandemic and it is still ongoing. However, the infection in China has been successfully controlled although its initial transmission was also nationwide and has caused a serious public health crisis. The analysis on the early-stage COVID-19 transmission in China is worth investigating for its guiding significance on prevention to other countries and regions. In this study, we conducted the experiments from the perspectives of COVID-19 occurrence and intensity. We eliminated unimportant factors from 113 variables and applied four machine learning-based classification and regression models to predict COVID-19 occurrence and intensity, respectively. The influence of each important factor was analysed when applicable. Our optimal model on COVID-19 occurrence prediction presented an accuracy of 91.91% and the best R2 of intensity prediction reached 0.778. Linear regression-based model was identified as unable to fit and predict the intensity, and thus only the variable influence on COVID-19 occurrence can be explained. We found that (1) CO VID-19 was more likely to occur in prosperous cities closer to the epicentre and located on higher altitudes, (2) and the occurrence was higher under extreme weather and high minimum relative humidity. (3) Most air pollutants increased the risk of COVID-19 occurrence except NO2 and O3, and there existed a lag effect of 6-7 days. (4) NPIs (non-pharmaceutical interventions) did not show apparent effect until two weeks after.

Investigation of the Amide Linkages on Cooperative Supramolecular Polymerization of Organoplatinum(II) Complexes.

Cooperative supramolecular polymerization of π-conjugated compounds into one-dimensional nanostructures has received tremendous attentions in recent years. It is commonly achieved by incorporating amide linkages into the monomeric structures, which provide hydrogen bonds for intermolecular non-covalent complexation. Herein, the effect of amide linkages is elaborately studied, by comparing supramolecular polymerization behaviors of two structurally similar monomers with the same platinum(II) acetylide cores. As compared to the N-phenyl benzamide linkages, N-[(1S)-1-phenylethyl] benzamide linkages give rise to effective chirality transfer behaviors due to the closer distances between the chiral units and the platinum(II) acetylide core. They also provide stronger intermolecular hydrogen bonding strength, which consequently brings higher thermo-stability and enhanced gelation capability for the resulting supramolecular polymers. Supramolecular polymerization is further strengthened by varying the monomers from monotopic to ditopic structures. Hence, with the judicious modulation of structural parameters, the current study opens up new avenues for the rational design of supramolecular polymeric systems.

Single-Photon Near-Infrared-Responsiveness from the Molecular to the Supramolecular Level via Platination of Pentacenes.

Near-infrared (NIR) responsiveness is important for various applications. Currently, single-photon NIR-responsive systems are rare compared to systems that display two-photon absorption and triplet-triplet annihilation processes. Supramolecular stacking of photo-responsive chromophores results in decreased efficiency due to space-confinement effects. Herein we show that σ-platination of pentacenes is a feasible protocol to build single-photon NIR-responsive systems, with advantages including a low HOMO-LUMO energy gap, high photochemical efficiency, and pathway specificity. The pentacene-to-endoperoxidation transformation is accompanied by color and absorbance changes. The high photo-oxygenation efficiency of σ-platinated pentacenes facilitates NIR responsiveness in one-dimensional supramolecular polymers, resulting in the disappearance of supramolecular chirality signals and disruption of self-assembled nanofibers. Overall, the σ-platination strategy opens up new avenues toward NIR photo-responsive materials at the molecular and supramolecular levels.

Bright and Robust Phosphorescence Achieved by Non-Covalent Clipping.

Phosphorescent materials with bright emission in versatile media are important for their practical applications, which require to lower the susceptibility of triplet excitons to surroundings. Herein a non-covalent clipping strategy has been developed to attain this objective, by designing a tweezer receptor to encapsulate PtII -based triplet emitters through two-fold π-stacking interactions. The PtII emitters display robust phosphorescence by virtue of synergistic rigidifying and shielding effects, which are hardly influenced by emitter concentration, oxygen content, and solvent polarity changes. The phosphorescent colors are elaborately modulated by varying ligand substitutes on PtII emitters. Circularly polarized phosphorescence is further amplified for chiral PtII emitters, by taking advantage of dual phosphorescence and chirality enhancement upon non-covalent tweezer complexation. Overall, the clipping approach paves the way for the development of high-performance phosphorescent materials with bright emission, environmental robustness, and facile color tunability.

Supramolecular Chirogenesis Induced by Platinum(II) Tweezers with Excellent Environmental Tolerance.

Supramolecular chirogenesis has emerged as an effective strategy to access symmetry breaking in artificial systems. However, the chirogenic signals suffer from high susceptibility toward environmental variations. An effective strategy has been developed to address this issue by constructing platinum(II)-based tweezer/guest complexes stabilized by two-fold donor-acceptor and PtII -PtII metal-metal interactions. Upon guest encapsulation, the two pincers on the achiral PtII tweezer undergo a stereospecific twist to minimize steric repulsion, thus locking tweezer/guest complexes into the preferred chiral conformations. The induced chiroptical effects display outstanding solvent and temperature tolerance, ascribed to the balance between electrostatic and desolvation effects for the involved non-covalent interactions. Moreover, hierarchical and multi-component supramolecular assembly of tweezer/guest complexes provide a convenient way to modulate chirogeneic signals for their intensities.

Organoplatinum(II)-Based Self-Complementary Molecular Tweezers with Guest-Induced Fluorochromic Behaviors.

Cyclometalated organoplatinum(II) complexes have aroused tremendous interests due to their square-planar geometry and intriguing photophysics. To access multiplatinum systems with more than three cyclometalated organoplatinum(II) units, the traditional covalent synthetic approach suffers from tedious multistep reactions with low overall yield. In comparison, supramolecular assembly can be regarded as an effective strategy toward multiplatinum(II) architectures. Despite the progresses achieved, it is still challenging to fabricate well-ordered supramolecular assemblies with precise numbers of organoplatinum(II) units. Herein, self-complementary dimerized molecular tweezers with four cyclometalated platinum(II) units have been successfully constructed by taking advantage of dual roles of the incorporated 2,2':6',2''-terpyridine unit (serving as the rigid spacer and encapsulated guest). Furthermore, addition of electron-rich carbazoles leads to conversion of the self-complementary structure to molecular tweezer/guest complexes. Such a structural transformation gives rise to the concomitant luminescent color change. The unique guest-induced fluorochromic phenomena, which are seldom reported in the previous host-guest systems, would be promising as tunable luminescent and ratiometric sensing materials.

Task-dependent effects of voluntary space-based and involuntary feature-based attention on visual working memory.

Previous research has shown that visual working memory (VWM) can be modulated by space-based or feature-based attentional selection. However, it remains unclear how the two modes of attention operate jointly to affect VWM, and in particular, if involuntary feature-based attention plays a role in VWM. In this study, a pre-cued change detection paradigm was employed to investigate the concurrent effects of space- and feature-based attention on VWM. Space-based attention was manipulated by informative spatial cueing and by varying the proximity between the test item and the cued (fixated) memory item, while feature-based attention was induced in an involuntary manner by having the test item to share the same color or shape with the cued item on a fraction of trials. The results showed that: (1) the memory performance for the cued items was always better than the uncued items, suggesting a beneficial effect of voluntary spatial attention; (2) with a brief duration of the memory array (250 ms), cue-test proximity benefited VWM in the shape judgment task but not in the color judgment task, whereas with a longer duration (1200 ms), no proximity effect was found for either task; (3) VWM was improved for the same-colored items regardless of the task and duration; (4) VWM was improved for the same-shaped items only in the shape judgment task with the longer duration of the memory array. A discrimination task further showed that the proximity effect associated with VWM reflects a perceptual bottleneck in memory encoding for shape but not for color with a brief display. Our results suggest that involuntary feature-based attention could be triggered by spatial cueing to modulate VWM; involuntary color-based attention facilitates VWM independently of task, whereas shape-based facilitation is task-dependent, i.e., confined only to the shape judgment task, presumably reflecting different attention-guiding potencies of the two features.

Multicomponent Assembled Systems Based on Platinum(II) Terpyridine Complexes.

Platinum(II) terpyridine complexes have received tremendous attention in recent years because of their square-planar geometry and fascinating photophysics. Bottom-up self-assembly represents an intriguing approach to construct well-ordered supramolecular architectures with tunable optical and electronic properties. Until now, much effort has been devoted to the fabrication of monocomponent platinum(II) terpyridine-based assemblies. The next step is to develop multicomponent coassembled systems via the combination of platinum(II) terpyridine complexes with other π-organic and -organometallic molecules. The implementation of electron/energy transfer processes renders advanced functionality to the resulting coassemblies. For the fabrication of discrete multicomponent architectures, a feasible protocol is to construct preorganized molecular tweezers and macrocycles with the involvement of platinum(II) terpyridine complexes as the panel units. In view of their planar surface and positively charged character, such supramolecular receptors are capable of encapsulating electron-rich polyaromatic hydrocarbons and organometallic guests via donor-acceptor charge-transfer and/or metal-metal interactions. Intermolecular hydrogen bonds can be further incorporated between the molecular tweezers receptor and the polyaromatic hydrocarbon guests, giving rise to the strengthened binding affinity and sensitive stimuli-responsiveness. On this basis, multilayer donor-acceptor stacks have been obtained via the precise control over the number of pincers, which feature enhanced complexation strength and superior functionality. Moreover, platinum(II) terpyridine-based macrocycles are more suitable for guest accommodation than the corresponding molecular tweezers receptors in light of their definite size and constrained environment. Stimuli-responsive elements can be conveniently implemented into the rigid spacers of the molecular tweezers and macrocyclic receptors, facilitating the capture and release of the sandwiched guests in a highly controlled manner. On the other hand, long-range-ordered supramolecular polymers have been successfully fabricated with linear, hyperbranched, and cross-linked topologies by employing platinum(II) terpyridine-based molecular tweezers/guest recognition motifs as the non-covalent connecting unit. The degree of polymerization of the resulting donor-acceptor-type supramolecular polymers can be efficiently modulated by incorporating intermolecular hydrogen bonds between the molecular tweezers receptor and the complementary guest unit. An alternative approach toward extended multicomponent donor-acceptor assemblies is to mimic the structure of Magnus' green salt. A delicate balance of non-covalent driving forces between homo- and heterocomplexation processes and a deeper understanding of thermodynamic and kinetic behaviors play the decisive roles in the final arrangement of the coassembled structures. Overall, multicomponent coassembly of platinum(II) terpyridine complexes into well-ordered nanostructures would open up a new avenue toward functional supramolecular materials that are especially promising for sensing, optoelectronics, and catalytic applications.

Photoresponsiveness of Anthracene-Based Supramolecular Polymers Regulated via a σ-Platinated 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene Photosensitizer.

Anthracene and its derivatives have attracted tremendous interest in recent years because of their intriguing photoresponsive behaviors. Our research group has previously constructed anthracene-based supramolecular polymers, which display multicycle anthracene-endoperoxide photoswitching in a macroscopic manner. However, high-energy light excitation (λ = 365-460 nm) is required for anthracene-to-endoperoxide photooxygenation, giving rise to severe photodegradation problems. In this work, we have developed an effective approach to addressing this issue, by encapsulating a σ-platinated 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) photosensitizer into anthracene-based supramolecular polymeric systems. The platination effect enhances π-electron delocalization, while promoting intersystem crossing from singlet to triplet excited states. Accordingly, the σ-platinated BODIPY photosensitizer displays excellent 1O2 production capability, facilitating anthracene-to-endoperoxide transformation under low-energy irradiation conditions (λ = 520-590 nm). This leads to the breakup of supramolecular polymers and gels, which can be restored at room and elevated temperatures because of the reversible endoperoxide-to-anthracene deoxygenation process. Overall, the rational design of a σ-metalated photosensitizer opens up a new avenue to regulating the photoresponsiveness of supramolecular polymers under mild and nondestructive conditions.

Donor-acceptor-type supramolecular polymers on the basis of preorganized molecular tweezers/guest complexation.

The bottom-up self-assembly of donor-acceptor (D-A) units has received tremendous attention in recent years. Charge-transfer interactions, which are inherently embedded in D-A pairs, have suffered from some disadvantages such as erratic arrangements and weak binding affinity, thus hampering the precise arrangement of D-A units into long-range-ordered supramolecular polymers. To address this issue, a feasible protocol is to incorporate D-A units into molecular tweezers/guest recognition motifs, which concurrently feature high complexation directionality, strong binding affinity and stimuli-responsiveness. In this tutorial review, we have summarized the recent advances on the tweezering directed formation of D-A-type supramolecular polymers, with particular emphasis on the design principles of monomers and macroscopic behaviors of supramolecular polymers, together with future challenges in this research field.

Readily functionalized AAA-DDD triply hydrogen-bonded motifs.

Herein we present a new, readily functionalized AAA-DDD hydrogen bond array. A novel AAA monomeric unit (3a-b) was obtained from a two-step synthetic procedure starting with 2-aminonicotinaldehyde via microwave radiation (overall yield of 52-66%). 1H NMR and fluorescence spectroscopy confirmed the complexation event with a calculated association constant of 1.57 × 107 M-1. Likewise, the usefulness of this triple hydrogen bond motif in supramolecular polymerization was demonstrated through viscosity measurements in a crosslinked supramolecular alternating copolymer.

Re-emerging of rabies in Shaanxi province, China, from 2009 to 2015.

To explore the epidemiological, phylogeographic, and migration characteristics of human rabies in Shaanxi province, China from 2009 to 2015. The collected data were described and the sequenced glycoprotein (G) and nucleoprotein (N) genes were implemented to estimate the evolutionary rates and phylogeographic patterns using BEAST v.1.8.2. A total of 269 rabies cases were reported and 70.26% of the cases were male and 61.71% were between the ages of 19-59. The majority of the cases were farmers (83.27%). The estimated evolutionary rate of the N genes was 2.4 × 10-4 substitutions/site/year and the G genes was 3.4 × 10-4 . The time of the most recent common ancestor (TMRCA) was estimated around 1990. We detected viral migration paths from Sichuan, Guizhou, and Hunan to Hanzhong prefecture of Shaanxi and then spreaded to Xi'an and other prefectures. The main population affected by rabies virus was male adult farmers. The evolution rate of rabies viruses in Shaanxi was similar with the prior results reported by others and the ancestor virus should be circulating in neighboring province Sichuan around 1990 and then transmitted to Shaanxi. Promptly standard wound treatment and timely post-exposure prophylaxis should be compulsory for the dog-bitten victims.

Porous Hydrogen-Bonded Organic Frameworks.

Ordered porous solid-state architectures constructed via non-covalent supramolecular self-assembly have attracted increasing interest due to their unique advantages and potential applications. Porous metal-coordination organic frameworks (MOFs) are generated by the assembly of metal coordination centers and organic linkers. Compared to MOFs, porous hydrogen-bonded organic frameworks (HOFs) are readily purified and recovered via simple recrystallization. However, due to lacking of sufficiently ability to orientate self-aggregation of building motifs in predictable manners, rational design and preparation of porous HOFs are still challenging. Herein, we summarize recent developments about porous HOFs and attempt to gain deeper insights into the design strategies of basic building motifs.

Cooperative Supramolecular Polymerization of Fluorescent Platinum Acetylides for Optical Waveguide Applications.

One-dimensional organic structures with well-oriented π-aggregation, strong emission, and ease of processability are desirable for optoelectronic waveguiding devices. Herein, a strategy is developed to attain this objective by self-assembling platinum(II) acetylides into fluorescent supramolecular polymers via cooperative mechanism. The resulting high-molecular-weight supramolecular polymers are capable of forming electrospun microfibers with uniform geometry and smooth surface, which enable light propagation with extremely low scattering loss (0.008 dB µm-1 ). With the elaborate combination of bottom-up supramolecular polymerization and top-down electrospinning techniques, this work offers a novel and versatile avenue toward high-performance optical waveguiding materials.

An AAA-DDD triply hydrogen-bonded complex easily accessible for supramolecular polymers.

For a complementary hydrogen-bonded complex, when every hydrogen-bond acceptor is on one side and every hydrogen-bond donor is on the other, all secondary interactions are attractive and the complex is highly stable. AAA-DDD (A=acceptor, D=donor) is considered to be the most stable among triply hydrogen-bonded sequences. The easily synthesized and further derivatized AAA-DDD system is very desirable for hydrogen-bonded functional materials. In this case, AAA and DDD, starting from 4-methoxybenzaldehyde, were synthesized with the Hantzsch pyridine synthesis and Friedländer annulation reaction. The association constant determined by fluorescence titration in chloroform at room temperature is 2.09×10(7) M(-1) . The AAA and DDD components are not coplanar, but form a V shape in the solid state. Supramolecular polymers based on AAA-DDD triply hydrogen bonded have also been developed. This work may make AAA-DDD triply hydrogen-bonded sequences easily accessible for stimuli-responsive materials.

Sleep Quality and Subjective Cognitive Decline among Older Adults: The Mediating Role of Anxiety/Depression and Worries.

Background: Subjective cognitive decline (SCD) in older individuals has been implicated as a possible precursor to Alzheimer's disease. Poor sleep quality and anxiety/depressive symptoms have been linked to the progression of SCD, but these associations and older adults' worries have yet to be fully established in the Chinese older adult population, which is one of the largest in the world. The aim of this study was to explore the relationship between sleep quality, anxiety/depression symptoms, and worries, and SCD prevalence among Chinese community-dwelling older individuals. Methods: A total of 707 adults aged between 60 and 99 from Shanghai, China, completed self-report questionnaires that covered their cognitive and mental well-being, as well as demographic information. Subjective cognitive decline (SCD) was evaluated using the memory/cognition syndromes of the old adult self-report (OASR). Sleep quality, anxiety/depression, and worries were measured from their respective sections of the OASR. Results: The general linear regression models showed that poorer sleep quality was associated with an increased prevalence of anxiety/depression symptoms, worries, and SCD among older adults. As suggested by the mediation analysis, anxiety/depression and worries were significant mediators in the relationship between sleep quality and SCD prevalence, and these two factors also have a serial mediation effect between sleep quality and SCD prevalence. Conclusions: Poorer sleep quality is associated with a higher rate of SCD among older adults, and a higher prevalence of anxiety/depression and worries mediate this relationship, suggesting possible mechanism pathways that lead to SCD. These factors may provide the basis for early, targeted interventions for older adults' mental health preservation and improved quality of life.