Pyrene-Functionalized Ru-Catenated Metallacycles: Conversion of Catenated System to Monorectangle through Aging.

Molecular transformation behavior within a mechanically interlocked system is often assisted by chemical manipulation, such as the inclusion of guest molecules, variation in the solution concentration, or swapping of solvents. We present in this report the synthesis of ruthenium metal and π-conjugated pyrene-based (2 + 2) catenated rectangles. Additionally, we discuss the structural conversion of these catenated rectangles into monorectangles through adjustments in concentration and solvent composition.

A NIR-Light-Activated and Lysosomal-Targeted Pt(II) Metallacycle for Highly Potent Evoking of Immunogenic Cell Death that Potentiates Cancer Immunotherapy of Deep-Seated Tumors.

Though platinum (Pt)-based complexes have been recently exploited as immunogenic cell death (ICD) inducers for activating immunotherapy, the effective activation of sufficient immune responses with minimal side effects in deep-seated tumors remains a formidable challenge. Herein, we propose the first example of a near-infrared (NIR) light-activated and lysosomal targeted Pt(II) metallacycle (1) as a supramolecular ICD inducer. 1 synergistically potentiates immunomodulatory response in deep-seated tumors via multiple-regulated approaches, involving NIR light excitation, boosted reactive oxygen species (ROS) generation, good selectivity between normal and tumor cells, and enhanced tumor penetration/retention capabilities.

Association between inflammatory joint disease and severe or treatment-resistant depression: population-based cohort and case-control studies in Sweden.

Objective: To investigate whether the association between depression and inflammatory joint disease (IJD; rheumatoid arthritis [RA], psoriatic arthritis [PsA], ankylosing spondylitis/spondyloarthropathies [AS], and juvenile idiopathic arthritis [JIA]) is affected by the severity or treatment-resistance of depression.

Method: Parallel cohort studies and case-control studies among 600,404 patients with a depressive episode identified in Swedish nationwide administrative registers. Prospective and retrospective risk for IJD in patients with depression was compared to matched population comparators, and the same associations were investigated in severe or treatment-resistant depression.

Highly robust supramolecular polymer networks crosslinked by a tiny amount of metallacycles.

Supramolecular polymeric materials have exhibited attractive features such as self-healing, reversibility, and stimuli-responsiveness. However, on account of the weak bonding nature of most noncovalent interactions, it remains a great challenge to construct supramolecular polymeric materials with high robustness. Moreover, high usage of supramolecular units is usually necessary to promote the formation of robust supramolecular polymeric materials, which restrains their applications.

Supramolecular Coordination Complexes for Synergistic Cancer Therapy.

Supramolecular coordination complexes (SCCs) are predictable and size-tunable supramolecular self-assemblies constructed through directional coordination bonds between readily available organic ligands and metallic receptors. Based on planar and 3D structures, SCCs can be mainly divided into two categories: metallacycles (e.g.

Supramolecular coordination platinum metallacycle-based multilevel wound dressing for bacteria sensing and wound healing.

The exploitation of novel wound healing methods with real-time infection sensing and high spatiotemporal precision is highly important for human health. Pt-based metal-organic cycles/cages (MOCs) have been employed as multifunctional antibacterial agents due to their superior Pt-related therapeutic efficiency, various functional subunits and specific geometries. However, how to rationally apply these nanoscale MOCs on the macroscale with controllable therapeutic output is still challenging.

Metallacage-based enhanced PDT strategy for bacterial elimination via inhibiting endogenous NO production.

Antibiotics are among the most used weapons in fighting microbial infections and have greatly improved the quality of human life. However, bacteria can eventually evolve to exhibit antibiotic resistance to almost all prescribed antibiotic drugs. Photodynamic therapy (PDT) develops little antibiotic resistance and has become a promising strategy in fighting bacterial infection.

Platinum Metallacycle-Based Molecular Recognition: Establishment and Application in Spontaneous Formation of a [2]Rotaxane with Light-Harvesting Property.

Macrocyclic molecule-based host-guest systems, which provide contributions for the design and construction of functional supramolecular structures, have gained increasing attention in recent years. In particular, platinum(II) metallacycle-based host-guest systems provide opportunities for chemical scientists to prepare novel materials with various functions and structures due to the well-defined shapes and cavity sizes of platinum(II) metallacycles. However, the research on platinum(II) metallacycle-based host-guest systems has been given little attention.

[Effectiveness of Four-Week Mindfulness-Based Training on Life Satisfaction].

The training of the present work was designed based on the study by Demarzo and colleagues (2017), in which a four-week mindfulness-based intervention showed a similar effectiveness as the eight-week mindfulness-based stress reduction training. A sample of 120 participants was divided into an experimental group (n=80) and a control group (n=40) which filled out questionnaires about their mindfulness (Mindful Attention and Awareness Scale (MAAS)) and life satisfaction (Fragebogen zur allgemeinen Lebenszufriedenheit (FLZ), Kurzskala Lebenszufriedenheit-1 (L-1)) at two measurement times. It was shown that the mindfulness ability of the experimental group increased after the training and differed significantly (p=0,05) both from the first measurement point and from the control group at both measurement points.

Acceptor engineering of metallacycles with high phototoxicity indices for safe and effective photodynamic therapy.

Although metallacycle-based photosensitizers have attracted increasing attention in biomedicine, their clinical application has been hindered by their inherent dark toxicity and unsatisfactory phototherapeutic efficiency. Herein, we employ a π-expansion strategy for ruthenium acceptors to develop a series of Ru(ii) metallacycles (Ru1-Ru4), while simultaneously reducing dark toxicity and enhancing phototoxicity, thus obtaining a high phototoxicity index (PI). These metallacycles enable deep-tissue (∼7 mm) fluorescence imaging and reactive oxygen species (ROS) production and exhibit remarkable anti-tumor activity even under hypoxic conditions.

Host-Guest Encapsulation to Promote the Formation of a Multicomponent Trigonal-Prismatic Metallacage.

An inclusion complex of a trigonal-prismatic metallacage with two coronene guests was constructed by multicomponent coordination-driven self-assembly from a 90° platinum(II) acceptor [-Pt(PEt)(OTf)], disodium terephthalate, and 2,4,6-tri(4-pyridyl)-1,3,5-triazine in the presence of excess coronene. This platinum(II)-based trigonal prism was found to be a highly matched host to simultaneously encapsulate two coronene molecules. The encapsulation of coronene can effectively promote the formation of a pure single-prismatic metallacage and can stabilize the self-assembled structure via strong π-π-stacking interactions between coronene and the metallacage.

Long wavelength-emissive Ru(II) metallacycle-based photosensitizer assisting in vivo bacterial diagnosis and antibacterial treatment.

Ruthenium (Ru) complexes are developed as latent emissive photosensitizers for cancer and pathogen photodiagnosis and therapy. Nevertheless, most existing Ru complexes are limited as photosensitizers in terms of short excitation and emission wavelengths. Herein, we present an emissive Ru(II) metallacycle (herein referred to as 1) that is excited by 808-nm laser and emits at a wavelength of ∼1,000 nm via coordination-driven self-assembly.

Phenylthiol-BODIPY-based supramolecular metallacycles for synergistic tumor chemo-photodynamic therapy.

The development of more effective tumor therapy remains challenging and has received widespread attention. In the past decade, there has been growing interest in synergistic tumor therapy based on supramolecular coordination complexes. Herein, we describe two triangular metallacycles (1 and 2) constructed by the formation of pyridyl boron dipyrromethene (BODIPY)-platinum coordination.

Platinum(II)-Metallaclip-Based Theranostics for Cell Imaging and Synergetic Chemotherapy-Photodynamic Therapy.

Supramolecular coordination complexes formed by coordination-induced assembly not only avoid the loss of activity of precursors but also provide an efficient way for controlled release, which can be further used in various fields of biology such as drug delivery, cell imaging, and tumor treatment. In this work, a Pt metallaclip () was prepared from 4-[4-(1,2,2-triphenylvinyl)phenyl]pyridine (), 5,10,15-triphenyl-20-(pyridin-4-yl)porphyrin (), , and glycol-chain-modified isophthalic acid () in an acetone/water mixture through the "coordination-driven self-assembly" method. P and H NMR spectroscopy and high-resolution mass spectrometry were used to characterize the obtained metallaclip .

Development of a machine learning model to predict mild cognitive impairment using natural language processing in the absence of screening.

Background: Patients and their loved ones often report symptoms or complaints of cognitive decline that clinicians note in free clinical text, but no structured screening or diagnostic data are recorded. These symptoms/complaints may be signals that predict who will go on to be diagnosed with mild cognitive impairment (MCI) and ultimately develop Alzheimer's Disease or related dementias. Our objective was to develop a natural language processing system and prediction model for identification of MCI from clinical text in the absence of screening or other structured diagnostic information.

Self-Healing Metallacycle-Cored Supramolecular Polymers Based on a Metal-Salen Complex Constructed by Orthogonal Metal Coordination and Host-Guest Interaction with Amino Acid Sensing.

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 was 160.0 mM.

Self-assembled Pt(II) metallacycles enable precise cancer combination chemotherapy.

Combination chemotherapy, which involves the simultaneous use of multiple anticancer drugs in adequate combinations to disrupt multiple mechanisms associated with tumor growth, has shown advantages in enhanced therapeutic efficacy and lower systemic toxicity relative to monotherapy. Herein, we employed coordination-driven self-assembly to construct discrete Pt(II) metallacycles as monodisperse, modular platforms for combining camptothecin and combretastatin A4, two chemotherapy agents with a disparate mechanism of action, in precise arrangements for combination chemotherapy. Formulation of the drug-loaded metallacycles with folic acid–functionalized amphiphilic diblock copolymers furnished nanoparticles with good solubility and stability in physiological conditions.

An Organoplatinum(II) Metallacycle-Based Supramolecular Amphiphile and Its Application in Enzyme-Responsive Controlled Release.

Enzyme-responsive nanomaterials are emerging as important candidates for bioanalytical and biomedical applications due to their good biocompatibilities and sensitivities. However, the lack of promising operation platforms compatible with enzyme responsiveness greatly limits the scope and functionality of smart materials. Herein, we report the design and synthesis of a naphthalene-functionalized organoplatinum(II) metallacycle by means of coordination-driven self-assembly, which is subsequently exploited as the organometallic platform to enable enzyme-responsive supramolecular materials.

Metal-organic cycle-based multistage assemblies.

It is well known that chemical compositions and structural arrangements of materials have a great influence on their resultant properties. Diverse functional materials have been constructed by using either biomolecules (peptides, DNA, and RNA) in nature or artificially synthesized molecules (polymers and pillararenes). The relationships between traditional building blocks (such as peptides) have been widely investigated, for example how hydrogen bonds work in the peptide multistage assembly process.

Emissive Platinum(II) Macrocycles as Tunable Cascade Energy Transfer Scaffolds.

Developing artificial light-harvesting scaffolds with a cascade energy transfer process is significant for better understanding of photosynthesis. Here, we report [3+3] self-assembled Pt fluorescent macrocycles (3 a and 3 b) as light-harvesting platforms with cascade energy transfer. The Pt macrocycles aggregate into nanospheres and show emission-enhancement characteristics upon increasing water content in acetone medium.

BODIPY based Metal-Organic Macrocycles and Frameworks: Recent Therapeutic Developments.

Boron dipyrromethene, commonly known as BODIPY, based metal-organic macrocycles (MOCs) and metal-organic frameworks (MOFs) represent an interesting part of materials due to their versatile tunability of structure and functionality as well as significant physicochemical properties, thus broadening their applications in various scientific domains, especially in biomedical sciences. With increasing concern over the efficacy of cancer drugs versus quality of patient's life dilemma, scientists have been trying to fabricate novel comprehensive therapeutic strategies along with the discovery of novel safer drugs where research with BODIPY metal complexes has shown vital advancements. In this review, we have exclusively examined the articles involving studies related to light harvesting and photophysical properties of BODIPY based MOCs and MOFs, synthesized through self-assembly process, with a special focus on biomolecular interaction and its importance in anti-cancer drug research.

Self-assembled NIR-II Fluorophores with Ultralong Blood Circulation for Cancer Imaging and Image-guided Surgery.

Complete excision of the last remaining 1-2% of tumor tissue without collateral damage remains particularly challenging. Herein, we report thiophenthiadiazole (TTD)-derived fluorophores ( = 1, 2, 5) as new-generation NIR-II (1000-1700 nm) probes with exceptional nonfouling performance and significantly high fluorescence quantum yields in water. can self-assemble into vesicular micelles and exhibited minimal immunogenicity, low binding affinities, ultralong blood circulation ( = 59.

Design of a Metallacycle-Based Supramolecular Photosensitizer for In Vivo Image-Guided Photodynamic Inactivation of Bacteria.

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 metallacycle-based supramolecular photosensitizer through the host-guest interaction between a pillar[5]arene-modified metallacycle and 1-butyl-4-[4-(diphenylamino)styryl]pyridinium.