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Achieving low contact resistivity for the p contact in silicon heterojunction SHJ solar cells is challenging when classic n type transparent conductive oxides TCOs , such as indium tin oxide ITO , are used in the contact stack. Here, we report on SHJ solar cells with interdigitated back contact IBC and a direct aluminium Al metallisation applied to the p contact. We find that carefully annealing an Al a Si H p p type amorphous silicon contact at moderate temperatures leads to a specific contact resistivity that is half as low as its silver Ag ITO counterpart. This is explained by Al diffusing into a Si H p upon temperature treatment, forming a partially crystallised aluminium silicide layer. For a sufficiently high doping level in a Si H p , this enables an efficient tunnel recombination of holes from a Si H p to the Al contact. An estimate for this tunnelling dominated specific contact resistivity is calculated as a function of the interface doping density. Best fabricated IBC SHJ solar cells with Al p contact yield a fill factor of 77.5 and a power conversion efficiency of 22.3 . The main differences to devices with an Ag ITO a Si H p contact stack are a decrease in open circuit voltage by 14 mV and a slightly higher series resistance Rs . While the first aspect can be ascribed to increased interface recombination, the second one is unexpected and requires further investigation. Interestingly, omitting an intermediate TCO does not lead to current losses in devices with Al contacts, which is further investigated by optical simulations. Finally, electrical equivalent circuit simulations are conducted to describe the electrical behaviour of the investigated devices

Materials with aggregation-induced emission (AIE) properties are of growing interest due to their widespread applications. AIEgens, such as tetraphenylethylene units, display varying emission behaviors during their conformational changes. However, the structure-property relationships of the intermediate conformations have rarely been explored. Herein, we show that the conformational restriction on TPE units can affect the structural relaxation in the excited state and the resulting photophysical behaviors. Specifically, three metallacages of different sizes were prepared via the coordination-driven self-assembly of a TPE-based tetrapyridyl donor with length-increasing Pt(II) acceptors. While the metallacages share similar scaffolds, they exhibit a trend of red-shifted fluorescence and attenuated quantum yield with the increase of their sizes. Furthermore, spectroscopic and computational studies together with a control experiment were conducted, revealing that the degree of cage tension imposed on the excited-state conformational relaxation of TPE moieties resulted in their distinct photophysical properties. The precise control of conformation holds promise as a strategy for understanding the AIE mechanism as well as optimizing the photophysical behaviors of materials on the platform of supramolecular coordination complexes.

Two trigonal prismatic metallacages 1 and 2 bearing triphenylamine and anthracene moieties are designed and synthesized to fabricate artificial light-harvesting systems (LHSs). These two cages are prepared via the coordination-driven self-assembly of two anthracene-triphenylamine-based tripyridyl ligand 3, three dicarboxylates, and six 90° Pt(II) acceptors. The design of the anthracene-triphenylamine chromophore makes possible the tunable excited-state property (like the emissive transition energy and lifetime) as a function of the solvent polarity, temperature, and concentration. The synergistic photophysical footprint of these metallacages, defined by their high absorptivity and emission quantum yield (QY) relative to the free ligand 3, signifies them as a superior light sensitizer component in an LHS. In the presence of the fluorescent dye Nile Red (NR) as an energy acceptor, the metallacages display efficient (>93%) excited energy transfer to NR through an apparent static quenching mechanism in viscous dimethyl sulfoxide solvent.

Two quadrilateral metallacycles were prepared by coordination-driven self-assembly of a 90° platinum(II) receptor 6 with a flexible donor 1,3-bis(4,4′-bipyridinium)propane 1a or 1,1-bis(4,4′-bipyridinium)methane 1b, respectively. Three [3]catenanes (3, 4 and 5) were further prepared by in situ addition of crown ethers (DB24C8 or DB30C10) to the yielded metallacycles. By comparing the crystal structures of 1a and 4, it was found that the bite angle change of the flexible bidentate donor 1a (111.0° to 112.3°) is much smaller than that of rigid platinum(II) receptor 6 (90.0° to 83.2°) during metalla-cyclization. The multicomponent [3]catenanes were stabilized by multiple supramolecular interactions, including metal coordination, π–π stacking, charge transfer, and hydrogen bonding.

The accurate control of multicomponent self-assembly to fabricate a single assembly is still a challenge. Herein we describe multicomponent coordination-driven self-assembly with appropriately desi...

Supramolecular copolymers with complex architectures and emergent functions constitute a class of challenging but enticing synthetic targets in polymer science. Individual building blocks can be tailored to endow a resulting supramolecular copolymer with increased structural and functional complexity. Herein, we describe the construction of a linear supramolecular copolymer comprising mechanically interlocked segments with hydrogen-bonding metallorhomboidal units. Specifically, a hierarchical supramolecular polymerization of a crown ether-based [2]rotaxane and a discrete organoplatinum(II) metallacycle driven by 2-ureido-4-pyrimidinone (UPy) quadruple hydrogen bonding provides the impetus for its formation. This system demonstrates enhanced structural complexity accessed by the unification of orthogonal noncovalent interactions: metal coordination, host–guest chemistry, and multiple hydrogen bonding interfaces.

A platinum(II) metallacycle-cored supramolecular network based on a metal-salen complex was successfully constructed by two orthogonal noncovalent interactions (host-guest interactions and metal coordination interactions). The obtained metallo-supramolecular polymer could further form gels when the concentration of metallacycle

Chiral metal-organic complexes hold great promise as new functional materials that exhibit unique stereochemical and optical properties. Here, we report the formation of optically pure pillar[5]arene-based platinum chiral metallacycles. By coordination with 60° and 90° Pt(II) acceptors, planar chiral platinum triangles were self-assembled efficiently and characterized by multiple spectroscopic techniques. Optical studies indicated that these metallacycles had chiral properties: pS enantiomers showed a negative Cotton effect, and pR enantiomers exhibited a positive Cotton effect. In addition, these metallacycles also exhibited circularly polarized luminescence.

Poor processability of fullerenes is a major remaining drawback for them to be studied monomolecularly and to find real-life applications. One of the strategies to tackle this problem is to encapsu...

The utilization of structural water in chemical self-assembly has not only effectively eliminated the negative influences of solvents from solutions or gels but has also provided new insight into the fabrication of new materials in bulk. However, up to now, supramolecular polymerization triggered by structural water has been dominated more by serendipity than rational design. After carefully analyzing the chemical structures of artificial monomers and gaining a deep understanding of the water-triggered assembly process, we report herein the bulk formation of polymeric materials from water and low-molecular weight monomers by rational design instead of serendipity.

Hierarchical self-assembly of discrete organoplatinum(II) metallacycles has attracted considerable attention. However, the exact assembly mechanism involving non-covalent interactions has limited the formation and application of self-assembly due to the dynamics of platinum metallacycles. Herein, we report the hierarchical self-assembly of a pyrene-based discrete organoplatinum(II) double-metallacycle that takes advantage of heteroligation-coordination-driven self-assembly and triflate anions' hydrogen bonding, which is extended into a 3-D supramolecular framework by the hydrogen-bonding interactions involving triflate anions. Furthermore, the assembled system displays tunable fluorescence emission and enhanced solid emission. The studies herein disclosed pave the way to prepare platinum(II) metallacycle-based supramolecular functional materials.

The receptor tyrosine kinase HER2 is associated with a number of human malignancies and is an important therapeutic target. The antibody‐drug conjugate trastuzumab emtansine (T‐DM1; Kadcyla®) is recommended as a first‐line treatment for patients with HER2‐positive metastatic breast cancer. T‐DM1 combines the antibody‐induced effects of the anti‐HER2 antibody trastuzumab (Herceptin®) with the cytotoxic effect of the tubulin inhibitor mertansine (DM1). For DM1 to have effect, the T‐DM1‐HER2 complex has to be internalized and the trastuzumab part of T‐DM1 has to be degraded. HER2 is, however, considered endocytosis‐resistant. As a result of this, trastuzumab is only internalized to a highly limited extent, and if internalized, it is rapidly recycled. The exact reasons for the endocytosis resistance of HER2 are not clear, but it is stabilized by heat‐shock protein 90 (Hsp90) and Hsp90 inhibitors induce internalization and degradation of HER2. HER2 can also be internalized upon activation of protein kinase C, and contrary to trastuzumab alone, the combination of two or more anti‐HER2 antibodies can induce efficient internalization and degradation of HER2. With intention to find ways to improve the action of T‐DM1, we investigated how different ways of inducing HER2 internalization leads to degradation of trastuzumab. The results show that although both Hsp90 inhibition and activation of protein kinase C induce internalization of trastuzumab, only Hsp90 inhibition induces degradation. Furthermore, we find that antibody internalization and degradation are increased when trastuzumab is combined with the clinically approved anti‐HER2 antibody pertuzumab (Perjeta®).

Objective This study compares mercury measurements at several community's sites for air, soil and water samples. Method This observational analytic applied accidentally random sampling for communities and environmental samples. Total mercury (THg) contaminated concentration sample derived from surround cement processes. Samples of air, water column and soil were collected in one time. Results it implied that THg concentration value in the air, water and soil range from 1.0126 to 4.1172 μg/m3, 0.0750 to 2.0805 μg/L−1 and 11.057 to 32.036 μg/kg−1 dw, respectively. In the average, the magnitude of Hg level was in the surface soils > Air > surface water, respectively. The value of ecological risks was range from 3.0–4.4, 0.16–0.22 in the air, 3.0–4.4, 0.16–0.22 in water and 3.0–4.4, 0.16–0.22 in surface soil, respectively. Conclusion Mercury Risk values are still lower than standard and ecological risks still low hazard, those value however may increase due to occurrence of accumulation on those sites.

Stimuli-responsive complexes have attracted significant interest in supramolecular chemistry and material science. In this study, a new organoplatinum-crown supramolecular complex has been successfully constructed via the coordination of benzo-21-crown-7 (B21C7) units and cis-Pt(PEt3)2(OTf)2. The resulting complex displays intriguing lower critical solution temperature (LCST) and anion-sensitive deassembly behavior. This organoplatinum-crown ether complex with dual-responsive behavior is a promising candidate for stimuli-responsive materials.

Introducing self-assembly strategies into the construction of catalysts has been proven to have great advantages in asymmetric catalysis. We constructed two chiral metalla-triangles by highly efficient coordination-driven self-assembly from a chiral 3,3'-dipyridyl-substituted BINOL donor. They were successfully applied in asymmetric conjugate addition of a series of α,β-unsaturated ketones with trans-styrylboronic acids. The use of these metalla-triangles as supramolecular catalysts is obviously conducive to the enhancement of catalytic activity and stereoselectivity in the presented addition reactions. Under induction of the chiral metalla-triangles, an array of α,β-enones were converted to chiral γ,δ-unsaturated ketones in medium to quantitative yields (40-98%) with high enantioselectivities (87-96% ee).

Post-assembly modification is a useful tool for producing discrete metallasupramolecular structures. However, the simple structural transformation by facile covalent reactions greatly impedes the d...

Control over the stimuli-responsive behavior of smart molecular systems can influence their capability to execute complex functionalities. Herein, we report the development of a suite of spiropyran-based multi-stimuli-responsive self-assembled platinum(II) macrocycles (5-7), rendering coordination-assisted enhanced photochromism relative to the corresponding ligands. 5 showed shrinking and swelling during photoreversal, while 6 and 7 are fast and fatigue-free supramolecular photoswitches. 6 turns out to be a better fatigue-resistant photoswitch and can retain an intact photoswitching ability of up to 20 reversible cycles. The switching behavior of the macrocycles can also be precisely controlled by tuning the pH of the medium. Our present strategy for the construction of rapid stimuli-responsive supramolecular architectures via coordination-driven self-assembly represents an efficient route for the development of smart molecular switches.

Singlet oxygen (1O2), as an important active reagent, has found wide applications in photodynamic therapy (PDT), synthetic chemistry, and materials science. Organic conjugated aromatics serving as hosts to capture and release singlet oxygen have been systematically investigated over the last decades. Herein, we present a [6 + 6] organoplatinum(II) metallacycle by using ∼180° dipyridylanthracene donor and ∼120° Pt(II) acceptor as the building blocks, which enables the capture and release of singlet oxygen with relatively high photooxygenation and thermolysis rate constants. The photooxygenation of the metallacycle to the corresponding endoperoxide was performed by sensitized irradiation, and the resulting endoperoxide is stable at room temperature and can be stored under ambient condition over months. Upon simple heating of the neat endoperoxide under inert atmosphere at 120 °C for 4 h, the resulting endoperoxide can be reconverted to the corresponding parent form and singlet oxygen. The photooxygenation and thermolysis products were characterized by NMR spectroscopy and electrospray ionization time-of-flight mass spectrometric analysis. Density functional theory calculations were conducted in order to reveal the frontier molecular orbital interactions and reactivity. This work provides a new material platform for singlet oxygen related promising applications.

Coordination-driven suprastructures have attracted much interest due to their unique properties. Among these structures, platinum-based architectures have been broadly studied due to their facile preparation. The resultant two- or three-dimensional (2D or 3D) systems have many advantages over their precursors, such as improved emission tuning, sensitivity as sensors, and capture and release of guests, and they have been applied in biomedical diagnosis as well as in catalysis. Herein, we review the recent related to platinum-based coordination-driven self-assembly (CDSA), and the text is organized to emphasizes both the synthesis of new metallacycles and metallacages and their various applications. We review the recent developments in the growing field of platinum-based, coordination-driven self-assembly, and bringing together the key results.

Chronic lymphocytic leukemia (CLL) is the most common leukemia of adults in western countries. Therapy is indicated in symptomatic and advanced stages and has changed fundamentally since 2010 when rituximab, an anti-CD20 antibody, has been approved for treatment of CLL. Until then therapy had been based on chemotherapy drugs. This study investigates whether survival in CLL patients improved at the population level after the introduction of combined chemoimmunotherapy. Data from the cancer registry North-Rhine Westphalia was used to calculate relative survival (RS) by applying period analyses. Age-standardized 5-year RS increased from 79% in 1998–2002 (75% in 2003–2007) to 81% in the calendar period 2008–2012 and 88% in 2013–2016 for men and continuously from 71% in 1998–2002 to 92% in 2013–2016 for women. In CLL patients aged 15–69 years 5-year RS increased from 83% to 90% for men and from 82% to 94% for women after adding an anti-CD20-antibody to chemotherapy while in the older age group of 70–79-year-old CLL patients an increase by 20 percentage points was observed. These findings show marked improvements in the survival of CLL patients at the population level subsequently to the approval of anti-CD 20 antibodies like rituximab, ofatumumab or obinutuzumab for CLL treatment.

The aim of this investigation is, to utilize coordination-driven self-assembly reactions of 4, 4′-dibromobenzophenone with tetrakis(triethyl phosphine) platinum to construct platinum-containing supramolecular metallacycle, 4, 4′-bis[trans-Pt(PEt3)2Br]benzophenone with exploitable properties for application in catalysis, energy storage, and biomedicine. The process was monitored by 1H NMR and C NMR. A 4, 4’-dibromobenzophenone and tetrakis(triethyl phosphine) platinum in the ratio 1:2 in toluene were utilized in the synthesis. In the structure, platinum ions are coordinated through the bridging ligand molecules forming polymeric chains with a four atomic environment. The coordination environment was that of a square planar geometry with two phosphorus atoms of triethyl phosphine in apical positions. The optimized geometry evaluated by DFT B3LYP-6-311G, Gaussian09W, and Avogadro models support the crystal structure of this molecule. The compound offers high reversible binding properties that can be used for designing smart surfaces for applications in catalysis, energy storage, and biomedicine. The results from the experimental investigation and computer-aided design provide insight into the best strategies, by design, and binding mode. Future works are recommended for developing this discrete supramolecular metallacycle into supramolecular metallacages for its application in the drug delivery system.

BackgroundMaternal nutrition during pregnancy and lactation has profound effects on the development and lifelong health of the child. Long-chain PUFAs are particularly important for myelination and the development of vision during the perinatal period.ObjectivesWe conducted a systematic review to examine the relationship between supplementation with omega-3 fatty acids during pregnancy and/or lactation and neurodevelopment in children, to inform the Scientific Report of the 2020 Dietary Guidelines Advisory Committee.MethodsWe identified articles on omega-3 fatty acid supplementation in pregnant and lactating women that included measures of neurodevelopment in their children (0-18 y) by searching PubMed, CENTRAL, Embase, and CINAHL Plus. After dual screening articles for inclusion, we qualitatively synthesized and graded the strength of evidence using pre-established criteria for assessing risk of bias, consistency, directness, precision, and generalizability.ResultsWe included 33 articles from 15 randomized controlled trials (RCTs) and 1 prospective cohort study. Of the 8 RCTs that delivered omega-3 fatty acid dietary supplements during pregnancy alone (200-2200mg/d DHA and 0-1100mg/d EPA for approximately 20 wk), 5 studies reported ≥1 finding that supplementation improved measures of cognitive development in the infant or child by 6%-11% (P0.05) result. There was inconsistent or insufficient evidence for other outcomes (language, social-emotional, physical, motor, or visual development; academic performance; risks of attention deficit disorder, attention-deficit/hyperactivity disorder, autism spectrum disorder, anxiety, or depression) and for supplementation during lactation or both pregnancy and lactation. Populations with a lower socioeconomic status and adolescents were underrepresented and studies lacked racial and ethnic diversity.ConclusionsLimited evidence suggests that omega-3 fatty acid supplementation during pregnancy may result in favorable cognitive development in the child. There was insufficient evidence to evaluate the effects of omega-3 fatty acid supplementation during pregnancy and/or lactation on other developmental outcomes.

International audience; Bacterial infection is one of the greatest threats to public health. In vivo real-time monitoring and effective treatment of infected sites through non-invasive techniques, remain a challenge. Herein, we designed a Pt(II) metallacycle-based supramolecular photosensitizer through the host-guest interaction between a pillar[5]arene-modified metallacycle and 1-butyl-4-[4-(diphenylamino)styryl]pyridinium. Benefit from this design, such supramolecular photosensitizer, with aggregation-induced emission properties, demonstrated improved fluorescence performance and efficient photodynamic inactivation (PDI) of bacteria. In vivo studies revealed that it displayed precise fluorescence tracking of S. aureus-infected sites, and in situ performed image-guided efficient PDI of S. aureus without noticeable side effects. These results demonstrated that metallacycle combined with host-guest chemistry could provide a paradigm for the development of powerful photosensitizers for biomedicine.

International audience; Polycyclic aromatic hydrocarbons (PAHs) continue to attract increasing interest with respect to their applications as luminescent materials. The ordered structure of the metal−organic complex facilitates the selective integration of PAHs that can be tuned to function cooperatively. Here, a unique highly twisted anthracene-based organoplatinum metallacycle was prepared via coordination-driven self-assembly. Single-crystal X-ray diffraction analysis revealed that the metallacycle was twisted through the cooperation of strong π···π stacking interactions and steric hindrance between two anthracene-based ligands. Notably, the intramolecular twist and aggregation behavior introduced restrictions to the conformational change of anthracenes, which resulted in increased emission intensity of the metallacycle in solution. The emission behaviors and suprastructures based on the highly twisted metallacycle can be modulated by the introduction of different solvents. This study demonstrates that this metallacycle with highly twisted structure is a promising candidate for sensing and bioimaging applications.

Since the first metallacycle was prepared by Verkade in 1983, various metallacycles and metallacages with controllable nanoscale shapes and sizes have been created by modular design and synthesis, showing unique properties that enable applications in catalysis, sensors, and biomedicine. Everything from their photophysical properties to their antitumor activities and catalysis was found to be influenced by their suprastructures. Thus, it is necessary and helpful to develop a systematic understanding of the relationships among the micro/nanostructures, the resultant photophysical/chemical properties, and the corresponding applications. In this review, we summarized the latest progress in this area in approximately the past 5 years.

OBJECTIVES: To inform the Dietary Guidelines for Americans, 2020–2025, the USDA and HHS identified important public health questions to be examined by the 2020 Dietary Guidelines Advisory Committee. The Committee conducted a systematic review with support from the USDA's Nutrition Evidence Systematic Review (NESR) team to answer the question: What is the relationship between dietary patterns consumed during lactation and human milk composition and quantity? METHODS: The Committee developed protocols to describe how they would use NESR's SR methodology to examine the evidence related to dietary patterns (DP) during lactation and human milk (HM). NESR librarians conducted a literature search and NESR analysts dual-screened the results using pre-defined inclusion and exclusion criteria to identify articles published between 2000 and 2019. NESR analysts extracted data from and assessed the risk of bias of included studies. The Committee synthesized the evidence, developed conclusion statements, and graded the strength of the evidence. RESULTS: This systematic review included 7 articles. Three articles from 2 cross-sectional studies examined DP and HM, while 4 articles from 3 randomized controlled trials examined diets based on macronutrient distributions and HM. The body of evidence was limited by small sample sizes, risk of bias concerns, heterogeneous methods, and study populations with limited racial/ethnic and socioeconomic diversity. CONCLUSIONS: Limited evidence suggests that maternal consumption of diets higher in fat (>35% fat) and lower in carbohydrate during lactation is related to higher total fat in HM collected in the maternal postprandial period. Limited evidence suggests that certain maternal DP during lactation, including diets based on macronutrient distributions, are related to the relative proportions of saturated fat and monounsaturated fatty acids in HM, and of polyunsaturated fatty acids in HM collected in the maternal postprandial period. Insufficient or no evidence was available to assess the association between DP during lactation and HM quantity, as well as total protein, water- and fat-soluble vitamins, minerals, human milk oligosaccharides, and bioactive proteins in HM. FUNDING SOURCES: USDA, Food and Nutrition Service, Center for Nutrition Policy and Promotion.

Antibiotic resistance has become one of the major threats to global health. Photodynamic inactivation (PDI) develops little antibiotic resistance; thus, it becomes a promising strategy in the control of bacterial infection. During a PDI process, light-induced reactive oxygen species (ROS) damage the membrane components, leading to the membrane rupture and bacteria death. Due to the short half-life and reaction radius of ROS, achieving the cell-membrane intercalation of photosensitizers is a key challenge for PDI of bacteria. In this work, a tetraphenylethylene-based discrete organoplatinum(II) metallacycle (1) acts as a photosensitizer with aggregation-induced emission. It self-assembles with a transacting activator of transduction (TAT) peptide-decorated virus coat protein (2) through electrostatic interactions. This assembly (3) exhibits both ROS generation and strong membrane-intercalating ability, resulting in significantly enhanced PDI efficiency against bacteria. By intercalating in the bacterial cell membrane or entering the bacteria, assembly 3 decreases the survival rate of gram-negative Escherichia coli to nearly zero and that of gram-positive Staphylococcus aureus to ∼30% upon light irradiation. This study has wide implications from the generation of multifunctional nanomaterials to the control of bacterial infection, especially for gram-negative bacteria.

The dianthracene-based rhomboidal organoplatinum(II) metallacycle 1 was successfully obtained via coordination-driven self-assembly involving the combination of diplatinum(II) acceptor 2 and dipyri...

In this work, we present the formation of two open-ended hexagonal-prism tubular macrocycles by the [6+12] self-assembly of the symmetric ~120° organic ligand donor with ~90° Pt(II) acceptor in a 1:2 ratio. The assembled structures were characterized by multinuclear NMR ((1)H NMR, (31)P{(1)H} NMR, and (1)H−(1)H COSY NMR), electrospray ionization mass spectrometry (ESI-TOF-MS), traveling wave ion mobility-mass spectrometry (TWIM-MS), and transmission electron microscopy. Molecular modeling was further conducted to get insight into their structured characteristics. We also examined their photophysical properties.

International audience; Light-harvesting is one of the key steps in photosynthesis, but developing artificial light-harvesting systems (LHSs) with high energy transfer efficiencies has been a challenging task. Here we report fluorescent hexagonal Pt(II) metallacycles as a new platform to fabricate artificial LHSs. The metallacycles (4 and 5) are easily accessible by coordination-driven self-assembly of a triphenylamine-based ditopic ligand 1 with di-platinum acceptors 2 and 3, respectively. They possess good fluorescence properties both in solution and in the solid state. Notably, the metallacycles show aggregation-induced emission enhancement (AIEE) characteristics in a DMSO-H2O solvent system. In the presence of the fluorescent dye Eosin Y (ESY), the emission intensities of the metallacycles decrease but the emission intensity of ESY increases. The absorption spectrum of ESY and the emission spectra of the metallacycles show a considerable overlap, suggesting the possibility of energy transfer from the metallacycles to ESY, with an energy transfer efficiency as high as 65% in the 4a+ESY system. © 2019 American Chemical Society.

Diverse metal-organic complexes (MOCs), shaped as rectangles, triangles, hexagons, prisms, and cages, can be formed by coordination between metal ions (Pt, Pd, Ru, Rh, Ir, Zn, Co, and Cd) and organic ligands, with potential applications as alternatives to conventional biomedical materials for therapeutic, sensing, and imaging purposes. MOCs have been investigated as anticancer drugs in the treatment of malignant tumors in lung, cervical, breast, colon, liver, prostate, ovarian, brain, stomach, bone, skin, mouth, thyroid, and other cancers. MOCs with one, two, and three cavities have also been investigated as drug carriers and prepared for the loading and release of different drugs. In addition, MOCs can target proteins by the shape effect and recognize sugars and DNA by electrostatic interactions, as well as estradiol by host-guest interactions, etc. This Perspective mainly covers achievements in the biomedical application of MOCs. We aim to identify some key trends in the reported MOC structures in relation to their biomedical activity and potential applications.

Coordination-driven self-assembly (CDSA) is increasingly used to synthesize coordination complexes containing metal-centered electron acceptors and typically nitrogen-containing electron donors. Characterization of the structures obtained from CDSA via crystallographic or spectroscopic means is limited due to difficulties in forming single crystals for X-ray studies and overlapping precursor and product signals in NMR. Here, we employ ion mobility-mass spectrometry (IM-MS), which provides a direct measure of size and shape of the CDSA complexes, to study the intact reaction products of a rhomboid-shaped complex. This approach negates the need for product isolation and crystallization and allows for tracking of the product distribution as a function of time. A potential challenge of IM-MS is that the size/shape of the observed CDSA complexes can vary with internal energy; however, we show that proper tuning of the instrument reduces the effects of collisional activation thereby allowing for retention of ion conformations that reflect solution-phase ion structures. Graphical Abstract.

Pancreatic ductal adenocarcinoma (PDAC) is associated with robust activity of the coagulation system. To determine mechanisms by which clotting factors influence PDAC tumor progression, we generated and characterized C57Bl/6-derived KPC (KRasG12D, TRP53R172H) cell lines. Tissue factor (TF) and protease-activated receptor-1 (PAR-1) were highly expressed in primary KPC pancreatic lesions and KPC cell lines similar to expression profiles observed in biopsies of patients with PDAC. In allograft studies, tumor growth and metastatic potential were significantly diminished by depletion of TF or Par-1 in cancer cells or by genetic or pharmacologic reduction of the coagulation zymogen prothrombin in mice. Notably, PAR-1–deleted KPC cells (KPC-Par-1KO) failed to generate sizable tumors, a phenotype completely rescued by restoration of Par-1 expression. Expression profiling of KPC and KPC-Par-1KO cells indicated that thrombin–PAR-1 signaling significantly altered immune regulation pathways. Accordingly, KPC-Par-1KO cells failed to form tumors in immune-competent mice but displayed robust tumor growth comparable to that observed with control KPC cells in immune-compromised NSG mice. Immune cell depletion studies indicated that CD8 T cells, but not CD4 cells or natural killer cells, mediated elimination of KPC-Par-1KO tumor cells in C57Bl/6 mice. These results demonstrate that PDAC is driven by activation of the coagulation system through tumor cell–derived TF, circulating prothrombin, and tumor cell–derived PAR-1 and further indicate that one key mechanism of thrombin/PAR-1–mediated tumor growth is suppression of antitumor immunity in the tumor microenvironment. Significance: The tissue factor–thrombin–PAR-1 signaling axis in tumor cells promotes PDAC growth and disease progression with one key mechanism being suppression of antitumor immunity in the microenvironment.

A double metallacycle was prepared via the size-selective integrative self-sorting of four different building blocks driven by a reversible metal-ligand coordination interaction. A hydrophobic dendron was placed on a metallacycle and a hydrophilic dendron was attached to the other metallacycle, producing a two-faced Janus-type supramolecule with two distinct functionalities. In aqueous media, hierarchical self-assembly of the supramolecular system was induced by the combination of coordination interactions and hydrophobic-hydrophilic interactions resulting in the formation of micrometer-sized fiber-like structures, a morphology distinct from metallacycles bearing only one type of functionality. This study provides a versatile approach for the construction of Janus-type molecules and demonstrates that integrative self-sorting of a supramolecular coordination system can be utilized for the preparation of complex supramolecular systems with pre-designed functionalities and morphologies

A supramolecular polymeric adhesive was prepared from non-viscous, non-polymeric materials by water-participant hydrogen bonds. Pt-pyridine coordination and water-crown ether hydrogen bonding combine to effect the supramolecular polymerization. The supramolecular polymeric adhesive displays strong, reversible adhesion to hydrophilic surfaces, a property that forecasts the application of hydrogen bonding in advanced supramolecular materials.

Supramolecular coordination has been developed as an efficient tool to construct a variety of discrete metallacycles and metallacages with well-defined shapes and sizes. However, its application in framework construction has been barely exploited. In this paper, we report the direct synthesis of two diamondoid frameworks from a simple tetrahedral precursor, tetra(4-(4-pyridinyl)phenyl)methane, and two linear difunctional platinum(II) ligands via one-step supramolecular coordination. Controlled by the specific angularity and geometry of the tetrahedral and linear subunits, these frameworks possess a well-defined diamondoid topology with highly regulated periodicity and three-dimensional porosity. Moreover, these rigid frameworks can be directly changed into a metallogel when prepared in DMSO at high concentrations. Interestingly, these diamondoid frameworks exhibit a cationic nature and stimuli-responsive behavior, which potentially endow them with the selective adsorption and controlled release for anionic dyes and drugs in aqueous environments. Thus, this study demonstrates that supramolecular coordination is a facile and efficient approach for the preparation of functional framework materials containing predesigned and well-defined supramolecular coordination assemblies as molecular skeletons.

Although platinum-based anticancer drugs prevail in cancer treatment, their clinical applications are limited by the severe side effects as well as their ineffectiveness against drug resistant cancers. A precise combination of photodynamic therapy (PDT) and chemotherapy can synergistically improve the therapeutic outcome and thereby may overcome drug resistance through a multipronged assault. Herein, we employ the well-defined cavity of a discrete organoplatinum(II) metallacage (M) to encapsulate octaethylporphine (OEP), a photosensitizer, forming a dual-functionalized system M⊃OEP that is wrapped into the hydrophobic core of the nanoparticles (MNPs) self-assembled from an amphiphilic diblock copolymer. Using a copper-free click reaction, a targeting ligand is conjugated on the surface of the MNPs, aiming to specifically deliver a chemotherapeutic drug and a photosensitizer to cancer cells. Benefiting from the enhanced permeability and retention effect and active targeting capability, high tumor accumulation of MNPs is achieved, leading to an improved therapeutic outcome and reduced side effects. In vivo studies demonstrate that the combination of chemotherapy and PDT exhibits a superior antitumor performance against a drug-resistant tumor model attributed to their synergistic anticancer efficacy.

A series of platinum (II) metallacycles were prepared via the coordination-driven self-assembly of a phenazine-cored dipyridyl donor with a 90° Pt(II) acceptor and various dicarboxylate donors in a 1:1:2 ratio. While the metallacycles display similar absorption profiles, they exhibit a trend of blue-shifted fluorescence emission with the decrease in the bite angles between the carboxylate building blocks. Comprehensive spectroscopic and dynamic studies, as well as a computational approach were conducted, revealing that the difference in the degree of constraint imposed on the excited-state planarization of the phenazine core within these metallacycles results in the distinct photophysical behaviors. As such, a small initial difference in the dicarboxylate building blocks is amplified into distinct photophysical properties of the metallacycles, which is reminiscent of the efficient functional tuning observed in natural systems. In addition to the pre-assembly approach, the photophysical properties of a metallacycle can also be modulated using a post-assembly modification to the dicarboxylate building block, suggesting another strategy for functional tuning. This research illustrated the potential of coordination-driven self-assembly for the preparation of materials with precisely tailored functionalities at the molecular level.

Core-shell electrospun nanofibers constitute a vehicle enabling novel uses for phosphorescent oxygen-sensitive molecules. In this work, we investigate compositional parameters and other factors governing fiber design appropriate to long-term sensor applications. These nanofibers contain an oxygen-sensitive palladium (II) porphyrin species within a polysulfone core; an outer polycaprolactone shell protects the core from the surrounding environment. The presence of a core-shell architecture was confirmed using advanced time-of-flight secondary ion mass spectrometry (ToF-SIMS). Although these sensors exhibit excellent photostability in the short-term, long-term exposures (up to 1000 h) are shown to detrimentally impact performance via photobleaching phenomenon. We also investigated higher porphyrin concentrations to determine whether the resulting sensors are predisposed to photobleaching. High porphyrin loadings (up to 10 wt%) could be successfully incorporated into the core. While increased probe content should logically enhance emission intensity, we sought to investigate the balance between a stronger signal and the potential for decreased photostability. The resulting behavior is rationalized by (1) establishing the spacing associated with a ‘perfect’ molecular dispersion and (2) invoking five distinct populations of porphyrin agglomeration. Populations that are not molecularly dispersed experience varying degrees of agglomeration-catalyzed photobleaching. The photobleaching rate increases with the extent of agglomeration and, therefore, the initial porphyrin content. Although it is demonstrated that low porphyrin loadings exhibit improved photobleaching resistance, the initial brightness is inadequate. In contrast, enhanced brightness via increased porphyrin content also leads to diminishing returns due to the apparent emergence of a self-quenched population. For a given application, selection of an appropriate porphyrin concentration is critical to achieving a compromise between initial brightness and photobleaching resistance. Detector sensitivity and anticipated duration of use must be considered when weighing the relative benefits of these attributes and selecting a specific porphyrin content.

Inspired by assemblies in the natural world, researchers have prepared diverse suprastructures with distinct spatial arrangements by artificial self-assembly, including micelles, vesicles, ribbons, films, fibers, and tubes. The field of assembly is undergoing a transition from single-component to multicomponent assembly and single-step to multistep processing. Control over the size, shape, and composition of these building blocks has enabled the formation of suprastructures with substantial structural diversity. More importantly, harnessing noncovalent interactions to create suprastructures in a controlled manner will lead to a better understanding of the formation of complex self-organized patterns. However, for the construction of multiscale self-assemblies with controllable shapes and functions, the selection of a suitable protocol remains challenging. Coordination-driven self-assembly provides a bottom-up approach to construct various metal-organic complexes (MOCs), which could be further used as building blocks with controllable shapes and sizes. Despite the tremendous progress made in the design of MOC-based supramolecular materials, most of these MOCs have dimensions of only several nanometers, and investigations of these structures rely on the characterization of their crystal structure. However, most of the functional suprastructures in living organisms have dimensions ranging from microns to centimeters and have the form of soft materials. Thus, obtaining MOC-based highly ordered materials of larger size remains a challenge. This Account focuses on our recent advances in the construction of soft suprastructure materials with MOCs. A series of functionalized MOCs were first constructed through coordination-driven self-assembly. Then, further self-assembly of the as-prepared MOCs gave rise to the formation of higher-order structures. By changing the functional groups in the acceptors and donors in the MOCs, different suprastructures, including nanospheres, nanodiamonds, nanorods, nanofibers, membranes, films, and gels, were prepared. These studies suggest that using MOCs as building blocks is a highly efficient strategy to achieve complex architectures and functional materials for the development of desired MOC-based soft materials with high precision and fidelity.

The local environment surrounding luminophores can significantly influence their photophysical properties. Herein, we report the self-assembly of a highly emissive platinum(II)-based metallacage. In order to accommodate the connectivity of the platinum(II) building block used in the self-assembly process, the luminophore-containing building block adopts a highly twisted geometry relative to its free form, leading to the emergence of an emissive transition with a radiative rate constant an order of magnitude higher than that of the free luminophore. This increased rate constant is the primary driver for the 10-fold increase in quantum yield from 4.2% to 40%. Model complexes with platinum or methyl groups bound to the nitrogen were synthesized. These complexes had lower quantum yields (10% and non-emissive, respectively) due mainly to decreases in radiative rate constants. Computational studies were conducted and indicated that the excited state of the ensembles, as well as the model complexes, is a result of charge transfer to the pyridyl groups, in contrast to the free luminophore, which involves the diphenyl sulfone moiety. The differences in quantum yields can be explained by a twist in the chromophore upon coordination of platinum or methylation on the pyridyl group, leading to intersystem crossing to a triplet state. This state then becomes more emissive with the addition of platinum, which increases the radiative rate constant via the heavy atom effect. The formation of a metallacage also decreases the non-radiative rate constant by inhibiting the intramolecular motions of the incorporated luminophore.

Constructing polycyclic aromatics-based highly emissive fluorophores with good solubility, tunable aggregated structures and properties is of great importance for film fabrication, solution processing and relevant functionality studies. Herein, we describe a general strategy to endow conventional organic fluorophores with enhanced solubility and modulated fluorescent properties via the incorporation into coordination-driven self-assembled metallacycles. A widely used fluorophore, pyrene, was decorated with two pyridyl groups to yield functionalized pyrene (4). Mixing 4 with three aromatic dicarboxylates with different lengths and a 90° Pt(II) metal acceptor in a 2:2:4 stoichiometric ratio resulted in the formation of three metallacycles (1, 2, and 3). The metallacycles display good solubility in polar organic solvents, highly aggregation-dependent fluorescence, and size-dependent emissions at higher concentrations. Moreover, metallacycle 2- based, silica-gel supported film as fabricated is not only more emissive than the ligand, 4-based one, but also displays much improved sensing properties for amines in the vapor state as demonstrated by significantly increased response speed and decreased recovery time. The enhanced solubility, unique fluorescence behavior and multi-factor modulation character show that coordination-driven self-assembly can be utilized for the development of new fluorophores through simple modification of conventional fluorophores. The fluorophores synthesized this way possess not only complex topological structures but also good modularity and tunability in fluorescence behavior, which are important for grafting multi-stage energy transfer systems, both important for the development of high performance sensing materials.

Parastichy, the spiral arrangement of plant organs, is an example of the long-range apparent order seen in biological systems. These ordered arrangements provide scientists with both an aesthetic challenge and a mathematical inspiration. Synthetic efforts to replicate the regularity of parastichy may allow for molecular-scale control over particle arrangement processes. Here we report the packing of a supramolecular truncated cuboctahedron (TCO) into double-helical (DH) nanowires on a graphite surface with a non-natural parastichy pattern ascribed to the symmetry of the TCOs and interactions between TCOs. Such a study is expected to advance our understanding of the design inputs needed to create complex, but precisely controlled, hierarchical materials. It is also one of the few reported helical packing structures based on Platonic or Archimedean solids since the discovery of the Boerdijk-Coxeter helix. As such, it may provide experimental support for studies of packing theory at the molecular level.