Lemniscular carbon nanohoops with contiguous conjugation from planar chiral [2.2]paracyclophane: influence of the regioselective synthesis on topological chirality.

We report herein the regioselective synthesis of all-carbon lemniscular nanohoops bis-po-CC and bis-pm-TC by the rational control of ring closures at the different positions of planar chiral tetrasubstituted [2.2]paracyclophane. Topological analyses reveal that bis-pm-TC is topologically chiral while bis-po-CC is topologically achiral. X-ray crystal analysis demonstrates that bis-pm-TC adopts a lemniscular conformation with a contiguous conjugation. CD and CPL measurements further reveal that the chiroptical properties of bis-pm-TC are obviously different from those of bis-po-CC due to their different topological chiralities.

Exhausting T Cells During HIV Infection May Improve the Prognosis of Patients with COVID-19.

T-cell reduction is an important characteristic of coronavirus disease 2019 (COVID-19), and its immunopathology is a subject of debate. It may be due to the direct effect of the virus on T-cell exhaustion or indirectly due to T cells redistributing to the lungs. HIV/AIDS naturally served as a T-cell exhaustion disease model for recognizing how the immune system works in the course of COVID-19. In this study, we collected the clinical charts, T-lymphocyte analysis, and chest CT of HIV patients with laboratory-confirmed COVID-19 infection who were admitted to Jin Yin-tan Hospital (Wuhan, China). The median age of the 21 patients was 47 years [interquartile range (IQR) = 40-50 years] and the median CD4 T-cell count was 183 cells/µl (IQR = 96-289 cells/µl). Eleven HIV patients were in the non-AIDS stage and 10 were in the AIDS stage. Nine patients received antiretroviral treatment (ART) and 12 patients did not receive any treatment. Compared to the reported mortality rate (nearly 4%-10%) and severity rate (up to 20%-40%) among COVID-19 patients in hospital, a benign duration with 0% severity and mortality rates was shown by 21 HIV/AIDS patients. The severity rates of COVID-19 were comparable between non-AIDS (median CD4 = 287 cells/µl) and AIDS (median CD4 = 97 cells/µl) patients, despite some of the AIDS patients having baseline lung injury stimulated by HIV: 7 patients (33%) were mild (five in the non-AIDS group and two in the AIDS group) and 14 patients (67%) were moderate (six in the non-AIDS group and eight in the AIDS group). More importantly, we found that a reduction in T-cell number positively correlates with the serum levels of interleukin 6 (IL-6) and C-reactive protein (CRP), which is contrary to the reported findings on the immune response of COVID-19 patients (lower CD4 T-cell counts with higher levels of IL-6 and CRP). In HIV/AIDS, a compromised immune system with lower CD4 T-cell counts might waive the clinical symptoms and inflammatory responses, which suggests lymphocyte redistribution as an immunopathology leading to lymphopenia in COVID-19.

A bi-component supramolecular gel for selective fluorescence detection and removal of Hg2+ in water.

A bi-component supramolecular gel (RQ) was successfully constructed by the assembly of the gelators 4-aminophenyl functionalized naphthalimide derivative (R) and tri-(pyridine-4-yl)-functionalized trimesic amide (Q) in DMSO-H2O (6.1 : 3.9, v/v) binary solution. The gel RQ exhibits excellent self-healing capacity. Interestingly, the RQ could fluorescently detect and reversibly remove Hg2+ from water through cation-π interactions with high selectivity, efficient adsorption and quick response. The limit of lowest detection (LOD) of the RQ for Hg2+ is 4.52 × 10-8 M and the separation ratio is 91.14%. Moreover, the RQ could be efficiently recycled and regenerated with little loss via a simple treatment by I-. Notably, thin films based on RQ and RQ + Hg2+ were prepared, which could serve as convenient and efficient test tools for the detection of Hg2+ and I-, respectively. This work provided an efficient method and novel supramolecular gel material for the separation and detection of Hg2+.

A novel AIE-based supramolecular polymer gel serves as an ultrasensitive detection and efficient separation material for multiple heavy metal ions.

Recently, ultrasensitive stimuli-responsive materials have received extensive attention due to their high sensitivity and wide applications. Herein, we report a novel approach to design ultrasensitive responsive materials by rationally introducing the aggregation-induced emission (AIE) effect into supramolecular polymer gels. According to this approach, by rationally introducing self-assembly moieties and a fluorophore, the obtained gelator DNS can act as an AIEgen; it showed strong AIE after aggregating into the supramolecular polymer gel GDNS. More interestingly, because the aggregation of DNS led to amplification of the detective signal, the AIE-based supramolecular polymer gel GDNS could ultrasensitively detect the heavy metal ions Hg2+, Cu2+, and Fe3+ by a signal amplification mechanism; the lowest detection limits reached 10-11 M. In addition, the xerogel of GDNS could adsorb and separate Hg2+, Cu2+, and Fe3+ from aqueous solution with favourable adsorption properties, and the adsorption rates ranged from 94.70% to 99.37%. Furthermore, the gel GDNS could act as a convenient test kit for Hg2+, Cu2+, and Fe3+ as well as a smart fluorescent display material.

Aggregation-induced emission supramolecular organic framework (AIE SOF) gels constructed from tri-pillar[5]arene-based foldamer for ultrasensitive detection and separation of multi-analytes.

In this study, a novel aggregation-induced emission supramolecular organic framework (AIE SOF) with ultrasensitive response, termed FSOF, was constructed using a tri-pillar[5]arene-based foldamer. Interestingly, benefiting from the noise signal shielding properties of FSOF as well as the competition between the cationπ and ππ interactions, the FSOF shows an ultrasensitive response for multi-analytes, such as Fe3+, Hg2+ and Cr3+. The limits of detection (LODs) of the FSOF for Fe3+, Hg2+ and Cr3+ are in the range of 9.40 × 10-10-1.86 × 10-9. More importantly, the xerogel of FSOF exhibits porous mesh structures, which could effect high-efficiency separation above metal ions from their aqueous solution, with adsorption percentages in the range 92.39-99.99%. In addition, by introducing metal ions into the FSOF, a series of metal ions coordinated supramolecular organic frameworks (MSOFs) were successfully constructed. Moreover, MSOFs show selective fluorescence "turn on" ultrasensitive detection CN- (LOD = 2.12 × 10-9) and H2PO4- (LOD = 1.78 × 10-9). This is a novel approach to construct SOFs through a tri-pillar[5]arene-based foldamer, and also provides a new way to achieve ultrasensitive detection and high-efficiency separation.

A novel supramolecular AIE π-gel for fluorescence detection and separation of metal ions from aqueous solution.

A novel supramolecular aggregation induced emission (AIE) π-gel (ONT) was constructed by using a functionalized trimesic amide (TCP) molecule assembled with a bis-pyridine functionalized naphthalene diimide (ND) molecule using a non-covalent interaction. The ONT showed strong AIE at 468 nm. Furthermore, the ONT could detect and adsorb ferric (Fe3+) or cupric (Cu2+) ions from water. Meanwhile, a thin film based on supramolecular AIE π-gel ONT was prepared, which could be used as a fluorescent security display material for detecting Fe3+ or Cu2+. Thus, the AIE π-gel ONT shows potential for practical applications in efficient multi-analyte detection and separation and as a fluorescent display material.

A novel bis-component AIE smart gel with high selectivity and sensitivity to detect CN-, Fe3+ and H2PO4.

A novel bis-component AIE-gel TG was facilely constructed from two "easy-to-synthesize" tripodal gelators by a simple host-guest self-assembly process. Interestingly, the TG shows strong aggregation-induced emission (AIE) and could be used for highly efficient and sensitive detection and separation of ions (CN-, Fe3+ and H2PO4-). The LODs (limits of lowest detection) of TG for CN-, Fe3+ and H2PO4- are in the range of 4.93 × 10-9-7.80 × 10-8 M. Meanwhile, the xerogel of TG could adsorb and separate Fe3+ from aqueous solutions, and the adsorption rate is 96%. In addition, a thin film based on the TG could act as a convenient test kit for the detection of CN- and Fe3+. What is more, the TG-Fe film could not only be used as an erasable secure fluorescent display material, but also as a convenient reversible H2PO4- test kit.

Novel cyanide supramolecular fluorescent chemosensor constructed from a quinoline hydrazone functionalized-pillar[5]arene.

Herein, we report a simple and novel approach for the design of fluorescent chemosensor through the self-assembly of functionalized monomer molecules. According to these approach, a novel supramolecular fluorescent chemosensor (SPMS) was successfully constructed by self-assembly of a quinoline hydrazone functionalized pillar[5]arene monomer PM. Interestingly, upon the addition of CN-, the solution of SPMS instantly shows dramatic fluorescent enhancement and emitting bright blue emission. Meanwhile, the fluorescence quantum yields show distinct increase from 0.0582 of SPMS to 0.3952 of SPMS + CN-. The detection limit (LOD) of SPMS for CN- is 9.70 × 10-8 M, which indicated high sensitivity. Moreover, the SPMS is selective for CN- even in the presence of other anions, the fluorescent detection process of SPMS for CN- was not interfered by other competitive anions (F-, Cl-, Br-, I-, N3-, OH-, SCN-, HSO4-, AcO-, H2PO4- and ClO4-). Notably, in the CN- sensing process, the self-assembly structure of the supramolecular chemosensor SPMS didn't show any disassembly. This work provides a novel approach for instant detection of CN- through a self-assembled supramolecular fluorescent chemosensor in aqueous system. Moreover, the test strips based on SPMS were fabricated, which could serve as convenient and efficient CN- test kits.

Rationally introduce AIE into chemosensor: A novel and efficient way to achieving ultrasensitive multi-guest sensing.

Recently, ultrasensitive detection and multi-guest sensing have received extensive attention due to their high sensitivity and efficiency. Herein, we report a novel approach to achieve ultrasensitive detection of multi-analyte. This approach is concluded as "rationally introduce Aggregation-Induced Emission (AIE) into chemosensor". According to this approach, by rationally introducing self-assembly moiety, the obtained chemosensor DNS could serve as a novel AIEgen and show strong AIE in DMSO/H2O (water fraction 80%) binary solution. Interestingly, a simple fluorescent sensor array based on the DNS has been developed. This sensor array could selectively sense Fe3+, Al3+, H2PO4- and L-Arg in water solution. More importantly, this sensor array shows ultrasensitive detection for Fe3+, Al3+ and L-Arg. The LODs of the sensor array for Fe3+, Al3+ and L-Arg are in the range of 3.54×10-9M to 9.42×10-9M. Moreover, H2PO4- could realize the reversible detection of Fe3+ in the DMSO/H2O (water fraction 80%) solution. Meanwhile, DNS-based test papers and thin films were prepared, which could serve as test kits for convenient detection Fe3+, Al3+, and L-Arg in water. In addition, they could also act as efficient erasable fluorescent display materials.

Pillar[5]arene-based spongy supramolecular polymer gel and its properties in multi-responsiveness, dye sorption, ultrasensitive detection and separation of Fe3.

Herein, a novel way to design and construct multi-functional spongy supramolecular polymer gels through an easy to make tripodal guest (TA) and a naphthalimide functionalized-pillar[5]arene host (AP5) has been developed. According to this approach, a novel pillar[5]arene-based supramolecular polymer gel (SHG) was constructed via multi-non-covalent interactions such as host-guest inclusion, C-Hπ, ππ and hydrogen bonds and so on. Interestingly, the SHG exhibits a spongy structure and strong aggregation induced emission (AIE). Furthermore, the SHG also exhibited multi-responsiveness toward outer stimuli such as heating-cooling, pH, competitive agents and mechanical. More importantly, the SHG xerogel shows separation properties for Fe3+, methyl orange, methylene blue and sudan I dyes. The separation rates of SHG xerogel for Fe3+ ions and organic dyes can reach up to 99.8%. Simultaneously, the SHG could ultrasensitively detect Fe3+ (LOD is 0.9 nM). In addition, a thin film based on SHG was also prepared, which was confirmed to be a convenient test kit for detecting Fe3+.

Anion induced supramolecular polymerization: a novel approach for the ultrasensitive detection and separation of F.

A novel approach for the ultrasensitive detection and separation of F- has been successfully developed. F- could induce a tripodal naphthalene imide sensor (TNA) to result in supramolecular polymerization, leading to strong AIEE. The TNA could act as an excellent recyclable material for F- detection and separation.

Super metal hydrogels constructed from a simple tripodal gelator and rare earth metal ions and its application in highly selective and ultrasensitive detection of histidine.

A series of stable super metal hydrogels (TP-Ms, M = Tb3+, Eu3+, La3+ and Ce3+) with a low critical gelation concentration (2.28 × 10-3 M, 0.1%) was successfully constructed by forming hierarchical assemblies of a tripodal gelator (TP) with rare earth metal ions (Tb3+, Eu3+, La3+ and Ce3+). Interestingly, the super metal hydrogels TP-Eu and TP-La show a specific and ultrasensitive response to histidine (His). The addition of a series of amino acids into the metal hydrogels TP-Eu and TP-La showed that only His could induce distinct fluorescent enhancement for TP-Eu and TP-La, while other amino acids did not significantly interfere with the His sensing process. The LODs of super metal-hydrogel TP-Eu and TP-La for His are (1.83-1.94) × 10-9 and (1.83-1.85) × 10-9 M, respectively. In addition, constructing super supramolecular metal hydrogels by hierarchical assemblies of an easily synthesized tripodal gelator and rare earth metal ions is a novel and efficient approach to the design and development of multi-functional super supramolecular metal hydrogel-based materials.

Acylhydrazone functionalized benzimidazole-based metallogel for the efficient detection and separation of Cr3.

Chromium(iii) is a kind of microelement and can be converted to the more toxic chromium(vi), which is a carcinogen, by redox cycling. Thus, the development of novel materials for the detection and removal of Cr3+ is a very important issue. A novel metallogel chemosensor (BMG-Fe) based on functionalized benzimidazole (BM) and Fe3+ was constructed, which could fluorescently detect and separate Cr3+. The detection limit of BMG-Fe for Cr3+ is 2.62 × 10-8 M, and it exhibited high sensitivity and selectivity for Cr3+. Meanwhile, the absorbing percentage of BMG-Fe for Cr3+ is 96.36%, indicating a high separation rate. Interestingly, the sensitivity and ingestion capacity of BMG-Fe for Cr3+ are better than that of the simple organogel (BMG). So, the metallogel BMG-Fe could be utilized for the efficient removal of heavy metal ions from waste water.

Pillar[5]arene-Based Supramolecular Organic Framework with Multi-Guest Detection and Recyclable Separation Properties.

The selective detection and separation of target ions or molecules is an intriguing issue. Herein, a novel supramolecular organic framework (SOF-THBP) was constructed by bis-thioacetylhydrazine functionalized pillar[5]arenes. The SOF-THBP shows a fluorescent response for Fe3+ , Cr3+ , Hg2+ and Cu2+ ions. The xerogel of SOF-THBP shows excellent recyclable separation properties for these metal ions and the absorption rates were up to 99.29 %. More interestingly, by rationally introducing these metal ions into the SOF-THBP, a series of metal-ion-coordinated SOFs (MSOFs) such as MSOF-Fe, MSOF-Hg and MSOF-Cu were constructed. These metal ions coordinated MSOFs could selectively sense F- , Br- , and l-Cys, respectively. The detection limits of these MSOFs for F- , Br- and l-Cys were about 10-8  m.

Novel multi-analyte responsive ionic supramolecular gels based on pyridinium functionalized-naphthalimide.

A novel ionic supramolecular gel (is-G) is synthesized using N-(pyridinium-4-yl)-naphthalimide (G1) and n-pentanoic acid. By rationally introducing competitive coordination into is-G, two ion coordinated ionic supramolecular gels is-IG and is-FeG (coordinated with I- and Fe3+, respectively) are obtained. is-IG could fluorescently "turn-on" detect Hg2+ and l-Arg with specific selectivity, whereas, is-FeG could accurately identify l-Ser via fluorescence in water. Moreover, ion or amino acid responsive films based on these ionic supramolecular gels are prepared. These ionic supramolecular gels and films could act as multi-analyte detection materials as well as fluorescent display materials.

A novel supramolecular polymer gel based on naphthalimide functionalized-pillar[5]arene for the fluorescence detection of Hg2+ and I- and recyclable removal of Hg2+via cation-π interactions.

The development of novel materials for the detection and removal of Hg2+ is a very important issue due to the acute toxicity of Hg2+. Herein, a novel supramolecular polymer P5BD-DPHB has been constructed by the collaboration of a naphthalimide functionalized-pillar[5]arene host (P5BD) and a bis-bromohexane functionalized-pillar[5]arene guest (DPHB). P5BD-DPHB could form a stable supramolecular gel (P5BD-DPHB-G). Interestingly, P5BD-DPHB-G shows selective fluorescent "turn-on" detection for Hg2+via cation-π interactions with high selectivity and sensitivity. Furthermore, the Hg2+ coordinated supramolecular gel P5BD-DPHB-HgG can detect I- successively. The detection limits for Hg2+ and I- are 1.65 × 10-9 and 1.84 × 10-8 mol L-1, respectively. Even more significantly, the xerogel of P5BD-DPHB-G could remove Hg2+ from aqueous solution with excellent recyclability and ingestion capacity, and with a Hg2+ removal rate of 98%.