Metal-free directed sp2-C-H borylation.

Organoboron reagents are important synthetic intermediates that have a key role in the construction of natural products, pharmaceuticals and organic materials1. The discovery of simpler, milder and more efficient approaches to organoborons can open additional routes to diverse substances2-5. Here we show a general method for the directed C-H borylation of arenes and heteroarenes without the use of metal catalysts. C7- and C4-borylated indoles are produced by a mild approach that is compatible with a broad range of functional groups. The mechanism, which is established by density functional theory calculations, involves BBr3 acting as both a reagent and a catalyst. The potential utility of this strategy is highlighted by the downstream transformation of the formed boron species into natural products and drug scaffolds.

A Green Environmental Protection Photocatalytic Molecular Reactor for Aerobic Oxidation of Sulfide to Sulfoxide.

The design and synthesis of metal-organic frameworks (MOFs) as photocatalytic molecular reactors for varied reactions have drawn great attention. In this work, we designed a novel photoactive perylenediimides-based (PDI) carboxylate ligand N,N'-di(3',3",5',5"-tetrakis(4-carboxyphenyl))-1,2,6,7-tetrachloroperylene-3,4,9,10-tetracarboxylic acid diimide (Cl-PDI-TA) and use it to successfully synthesize a novel Zr(IV)-based MOF 1 constructed from [Zr6 O8 (H2 O)8 ]8+ clusters bridged by Cl-PDI-TA ligands. Structural analysis revealed that Zr-MOF 1 manifests a 3D framework with (4,8)-connected csq topology and possesses triangular channels of ~17 Šand mesoporous hexagonal channels of ~26 Šalong c-axis. Moreover, the synthesized Zr-MOF 1 exhibits visible-light absorption and efficient photoinduced free radical generation property, making it a promising photocatalytic molecular reactor. When Zr-MOF 1 was used as a photocatalyst for the aerobic oxidation of sulfides under irradiation of visible light, it could afford the corresponding sulfoxides with high yield and selectivity. Experimental results demonstrated that the substrate sulfides could be fixed in the pores of 1 and directly transformed to the products sulfoxides in the solid state. Furthermore, the mechanism for the photocatalytic transformation was also investigated and the results revealed that the singlet oxygen (1 O2 ) and superoxide radical (O2 ⋅- ) generated by the energy transfer and electron transfer from the photoexcited Zr-MOF to oxidants were the main active species for the catalytic reactions. This work offers a perceptive comprehension of the mechanism in PDI-based MOFs for further study on photocatalytic reactions.

Palladium catalyzed stereoselective intramolecular [3 + 2] cycloaddition reactions of (E) & (Z)-ene-vinylidenecyclopropanes.

A palladium-catalyzed ring-opening cyclization of (E) & (Z)-ene-vinylidenecyclopropanes has been developed via an intramolecular [3 + 2] cycloaddition process in the presence of a sterically bulky biaryl phosphine ligand, stereoselectively affording fused cis- & trans-bicyclo[4.3.0] skeletal products in good yields with a broad substrate scope and good functional tolerance. A plausible reaction mechanism was proposed on the basis of previous work and the DFT calculations.

A FRET-based multifunctional fluorescence probe for the simultaneous detection of sulfite and viscosity in living cells.

Viscosity and sulfur dioxide derivatives were significant indicators for the assessment of health threat and even cancers, therefore, on-site and real time detection of viscosity and sulfur dioxide derivatives has obtained considerable attentions. An FRET-based fluorescence probe JZX was designed and synthesized based on a novel energy donor of N,N-diethyl-4-(1H-phenanthro[9,10-d]imidazol-2-yl)benzamide fluorophore. JZX exhibited a large Stokes shift (230 nm), high energy transfer efficiency, wide emission channel gap (135 nm) and excellent stability and biocompatibility. JZX detected sulfur dioxide with low detection limit (55 nM), fast responding (16 min), high selectivity and sensitivity. Additionally, JZX tend to target endoplasmic reticulum of which normal metabolism will be disturbed by the abnormal levels of viscosity and sulfur dioxide derivatives. Prominently, JZX could concurrently detect viscosity and sulfur dioxide derivatives depending on different fluorescence signals in living cells for the screening of cancer cells. Hence, probe JZX will be a promising candidate for the detection of viscosity and sulfur dioxide derivatives, and even for the diagnosis of liver cancers.

Corydecusines A-H, new phthalideisoquinoline hemicetal alkaloids from the bulbs of Corydalis decumbens inhibit Tau pathology by activating autophagy mediated by AMPK-ULK1 pathway.

Twelve phthalideisoquinoline hemiacetal alkaloids including eight new ones (1-8) and one natural alkaloid characterized by an aziridine moiety with unassigned NMR data (9), were isolated and identified from the bulbs of Corydalis decumbens. Their structures were established by comprehensive analyses of HRESIMS, NMR, X-ray crystallography, and ECD analyses. The unambiguously established structures of the phthalideisoquinoline hemiacetal alkaloids indicated that the absolute configurations of C-1, C-9, and C-7' were confusable only relied on coupling constants. A summary of their ECD spectra was concluded and provided an insight for C-1, C-9, and C-7' absolute configuration assignment. These new compounds were evaluated to induce autophagy flux through flow cytometry analysis. Moreover, compounds 2 and 6 could significantly induce autophagy and inhibit Tau pathology by AMPK-ULK1 pathway activation, which provided an avenue for anti-AD lead compounds discovery.

The impact of long-term care interventions on healthcare utilisation among older persons: a scoping review of reviews.

BACKGROUND: As the ageing population grows, the demand for long-term care (LTC) services will rise, concurrently amplifying healthcare utilisation. This review aims to examine and consolidate information on LTC interventions that influence healthcare utilisation among older persons. METHODS: A scoping review was performed through a systematic search in PubMed, EBSCO CINAHL, EBM Reviews - Cochrane Database of Systematic Reviews, Embase, APA PsycInfo, EBM Reviews - Health Technology Assessment, and EBM Reviews - NHS Economic Evaluation Database. Systematic reviews with meta-analyses published between 1 January 2010 and 2 June 2022 among older persons aged 60 and above were included. The characteristics of LTC interventions were mapped to the World Health Organization (WHO) Healthy Ageing Framework. The effect sizes of healthcare utilisations for LTC interventions were recalculated using a random-effects model. The methodological quality was assessed with the AMSTAR-2 checklist, while the quality of evidence for each association was evaluated using GRADE. RESULTS: Thirty-seven meta-analyses were included. The most prominent domain of the healthy ageing framework was managing chronic conditions. One hundred twelve associations between various LTC interventions and healthcare utilisations were identified, with 22 associations impacting healthcare utilisation. Four interventions were supported by suggestive or convincing evidence. Preventive home visits were found to reduce hospital admission (OR: 0.73, 95% CI: 0.59, 0.91, p = 0.005), caregiver integration during discharge planning (OR: 0.68, 95% CI: 0.57, 0.81, p < 0.001), and continuity of care (OR: 0.76, 95% CI: 0.61, 0.95, p = 0.018) reduced hospital readmission, and perioperative geriatric interventions reduced the length of hospital stay (MD: -1.50, 95% CI: -2.24, -0.76, p < 0.001). None of the associations impacted emergency department visits, medication use, and primary care utilisations with convincing evidence. Most reviews received low methodological quality. CONCLUSION: The findings suggest that LTC interventions could benefit from transitioning to a community-based setting involving a multidisciplinary team, including carers. The spectrum of services should incorporate a comprehensive assessment to ensure continuous care.

Factors influencing presentation delay among cancer patients: a cross-sectional study in Malaysia.

BACKGROUND: Cancer represents a significant global public health challenge, with escalating incidence rates straining healthcare systems. Malaysia, like many nations, has witnessed a rise in cancer cases, particularly among the younger population. This study aligns with Malaysia's National Strategic Plan for Cancer Control Programme 2021-2025, emphasizing primary prevention and early detection to address cancer's impact. Therefore, we aim to describe the timeliness of cancer care for symptom presentation, socio-demographic, patient, as well as organizational-related factors among patients in Malaysia diagnosed with breast, colorectal, nasopharyngeal, and cervical cancer. METHODS: This cross-sectional study enrolled adult cancer patients diagnosed with breast, cervical, colorectal, or nasopharyngeal cancer from 2015 to 2020 in seven public hospitals/oncology centres across Malaysia. Data were collected through patient-administered surveys and medical records. Presentation delay, defined as the duration between symptom onset and the patient's first visit to a healthcare professional exceeding 30 days, was the primary outcome. Statistical analysis included descriptive statistics and chi-square tests. RESULTS: The study included 476 cancer patients, with breast cancer (41.6%), colorectal cancer (26.9%), nasopharyngeal cancer (22.1%), and cervical cancer (9.5%). Over half (54.2%) experienced presentation delays with a median interval of 60 days. Higher proportions of presentation delay were observed among nasopharyngeal cancer patients, employed patients with lower socioeconomic statuses, and those without family history of cancer. Most patients self-discovered their first cancer symptoms (80%), while only one-third took immediate action for medical check-ups. Emotional and organizational factors, such as long waiting times during doctor's visits (47%), were potential barriers to seeking cancer care. CONCLUSION: This study highlights the significant problem of presentation delay among cancer patients in Malaysia. The delay is influenced by various factors encompassing sociodemographic characteristics, health-seeking behaviours, and healthcare system-related issues. A comprehensive approach addressing both individual barriers and institutional obstacles is imperative to mitigate this presentation delay and improve cancer outcomes.

Mechanistic Studies on Rhodium-Catalyzed Chemoselective Cycloaddition of Ene-Vinylidenecyclopropanes: Water-Assisted Proton Transfer.

Rhodium-catalyzed cycloaddition reactions are a powerful tool for the construction of polycyclic compounds. Combined experimental and DFT studies were used to investigate the temperature-controlled chemoselectivity of cationic rhodium-catalyzed intramolecular cycloaddition reactions of ene-vinylidenecyclopropanes. After a series of mechanistic studies, it was found that trace amounts of water in the reaction system play an important role in generating the product with endo double bond located on a five-membered ring and revealed that trace amounts of water in the reaction system, including the rhodium catalyst, substrate and solvent, were sufficient to promote the formation of the product with endo double bond located on a five-membered ring, and additional water could not further accelerate the reaction. DFT calculation results show that the addition of water indeed significantly lowers the energy barrier of the proton transfer step, making the formation of the product with endo double bond located on a five-membered ring more likely to occur and confirming the rationality of water-assisted proton transfer occurring in the selective access to the product with endo double bond located on a five-membered ring.

Visible-Light-Mediated Activation of Remote C(sp3)-H Bonds by Carbon-Centered Biradical via Intramolecular 1,5- or 1,6-Hydrogen Atom Transfer.

In this study, we introduce a novel intramolecular hydrogen atom transfer (HAT) reaction that efficiently yields azetidine, oxetane, and indoline derivatives through a mechanism resembling the carbon analogue of the Norrish-Yang reaction. This process is facilitated by excited triplet-state carbon-centered biradicals, enabling the 1,5-HAT reaction by suppressing the critical 1,4-biradical intermediates from undergoing the Norrish Type II cleavage reaction, and pioneering unprecedented 1,6-HAT reactions initiated by excited triplet-state alkenes. We demonstrate the synthetic utility and compatibility of this method across various functional groups, validated through scope evaluation, large-scale synthesis, and derivatization. Our findings are supported by control experiments, deuterium labeling, kinetic studies, cyclic voltammetry, Stern-Volmer experiments, and density functional theory (DFT) calculations.

High-nuclearity Luminescent Lanthanide Nanocages for Tumor Drug Delivery.

There is an unmet need for easy-to-visualize drug carriers that can deliver therapeutic cargoes deep into solid tumors. Herein, we report the preparation of ultrasmall luminescent imine-based lanthanide nanocages, Eu60 and Tb60 (collectively Ln60 ), designed to encapsulate anticancer chemotherapeutics for tumor therapy. The as-prepared nanocages possess large cavities suitable for the encapsulation of doxorubicin (DOX), yielding DOX@Ln60 nanocages with diameters around 5 nm. DOX@Ln60 are efficiently internalized by breast cancer cells, allowing the cells to be visualized via the intrinsic luminescent property of Ln(III). Once internalized, the acidic intracellular microenvironment promotes imine bond cleavage and the release of the loaded DOX. DOX@Ln60 inhibits DNA replication and triggers tumor cell apoptosis. In a murine triple negative breast cancer (TNBC) model, DOX@Ln60 was found to inhibit tumor growth with negligible side effects on normal tissues. It proved more effective than various controls, including DOX and Ln60 . The present nanocages thus point the way to the development of precise nanomedicines for tumor imaging and therapy.

Humanized mouse models with endogenously developed human natural killer cells for in vivo immunogenicity testing of HLA class I-edited iPSC-derived cells.

Human induced pluripotent stem cells (hiPSCs) genetically depleted of human leucocyte antigen (HLA) class I expression can bypass T cell alloimmunity and thus serve as a one-for-all source for cell therapies. However, these same therapies may elicit rejection by natural killer (NK) cells, since HLA class I molecules serve as inhibitory ligands of NK cells. Here, we focused on testing the capacity of endogenously developed human NK cells in humanized mice (hu-mice) using MTSRG and NSG-SGM3 strains to assay the tolerance of HLA-edited iPSC-derived cells. High NK cell reconstitution was achieved with the engraftment of cord blood-derived human hematopoietic stem cells (hHSCs) followed by the administration of human interleukin-15 (hIL-15) and IL-15 receptor alpha (hIL-15Rα). Such "hu-NK mice" rejected HLA class I-null hiPSC-derived hematopoietic progenitor cells (HPCs), megakaryocytes and T cells, but not HLA-A/B-knockout, HLA-C expressing HPCs. To our knowledge, this study is the first to recapitulate the potent endogenous NK cell response to non-tumor HLA class I-downregulated cells in vivo. Our hu-NK mouse models are suitable for the non-clinical evaluation of HLA-edited cells and will contribute to the development of universal off-the-shelf regenerative medicine.

Single-Site Metal-Organic Framework and Copper Foil Tandem Catalyst for Highly Selective CO2 Electroreduction to C2 H4.

Tandem catalysis is a promising way to break the limitation of linear scaling relationship for enhancing efficiency, and the desired tandem catalysts for electrochemical CO2 reduction reaction (CO2 RR) are urgent to be developed. Here, a tandem electrocatalyst created by combining Cu foil (CF) with a single-site Cu(II) metal-organic framework (MOF), named as Cu-MOF-CF, to realize improved electrochemical CO2 RR performance, is reported. The Cu-MOF-CF shows suppression of CH4 , great increase in C2 H4 selectivity (48.6%), and partial current density of C2 H4 at -1.11 V versus reversible hydrogen electrode. The outstanding performance of Cu-MOF-CF for CO2 RR results from the improved microenvironment of the Cu active sites that inhibits CH4 production, more CO intermediate produced by single-site Cu-MOF in situ for CF, and the enlarged active surface area by porous Cu-MOF. This work provides a strategy to combine MOFs with copper-based electrocatalysts to establish high-efficiency electrocatalytic CO2 RR.

Synergistic Visible Light Photocatalysis with Organocatalysis.

In recent years, the strategy of merging visible light photocatalysis and organocatalysis has been utilized and applied in a wide range of reactions. Taking advantage of synergistic visible light photocatalysis with organocatalysis, remarkable progress has recently been achieved in modern chemical synthesis. In these dual catalytic systems, photocatalysts or photosensitizers absorb visible light to induce their photo-excited states which can activate unreactive substrates via electron or energy transfer mechanisms, and organocatalysts are usually employed to control the chemical reactivities of the other substrates. This review mainly focuses on the recent development of cooperative catalysis by the combination of organocatalysis and photocatalysis in recent organic synthesis.

Exploring the Advantages of Quantum Generative Adversarial Networks in Generative Chemistry.

De novo drug design with desired biological activities is crucial for developing novel therapeutics for patients. The drug development process is time- and resource-consuming, and it has a low probability of success. Recent advances in machine learning and deep learning technology have reduced the time and cost of the discovery process and therefore, improved pharmaceutical research and development. In this paper, we explore the combination of two rapidly developing fields with lead candidate discovery in the drug development process. First, artificial intelligence has already been demonstrated to successfully accelerate conventional drug design approaches. Second, quantum computing has demonstrated promising potential in different applications, such as quantum chemistry, combinatorial optimizations, and machine learning. This article explores hybrid quantum-classical generative adversarial networks (GAN) for small molecule discovery. We substituted each element of GAN with a variational quantum circuit (VQC) and demonstrated the quantum advantages in the small drug discovery. Utilizing a VQC in the noise generator of a GAN to generate small molecules achieves better physicochemical properties and performance in the goal-directed benchmark than the classical counterpart. Moreover, we demonstrate the potential of a VQC with only tens of learnable parameters in the generator of GAN to generate small molecules. We also demonstrate the quantum advantage of a VQC in the discriminator of GAN. In this hybrid model, the number of learnable parameters is significantly less than the classical ones, and it can still generate valid molecules. The hybrid model with only tens of training parameters in the quantum discriminator outperforms the MLP-based one in terms of both generated molecule properties and the achieved KL divergence. However, the hybrid quantum-classical GANs still face challenges in generating unique and valid molecules compared to their classical counterparts.

Construction of an early warning model of hepatic encephalopathy in patients with liver cirrhosis based on psychological testing.

AIMS AND OBJECTIVES: To establish an early warning model of hepatic encephalopathy in patients with liver cirrhosis based on psychological testing. METHODS: Data including patient demographics, number connection test-A (NCT-A), digit symbol test (DST), Model for End-Stage Liver Disease (MELD) scores were collected for patients admitted to a tertiary hospital in Shanghai with liver cirrhosis between January and December 2019. Patients were divided into two groups based on the development of hepatic encephalopathy (the hepatic encephalopathy group and non-hepatic encephalopathy group). Risk factors for hepatic encephalopathy in patients with liver cirrhosis were determined by using the binary logistic regression. We developed a predictive model in accordance with the STARD statement criteria (Supplementary File S1) with a cut-off value determined by receiver operating characteristic (ROC) curve analysis and calculation of the Youden index. RESULTS: A total of 417 patients with liver cirrhosis were included in the present study. Of these, 33 out of 66 patients with abnormal psychological tests had hepatic encephalopathy during hospitalisation. In contrast, 6 out of 317 patients with normal psychological tests had hepatic encephalopathy. Logistic regression analysis identified age, MELD score, and abnormal psychological tests as risk factors for hepatic encephalopathy in patients with liver cirrhosis. The area under the ROC curve for our prediction model for hepatic encephalopathy in patients with liver cirrhosis was 0.950 and the largest calculated Youden index was 0.804, which corresponds to a cut-off value is 0.0307. CONCLUSION: Greater age, higher MELD score and abnormal psychological tests were significantly associated with increased risk of hepatic encephalopathy indicating early warning systems and identification of abnormal psychological tests are important components of the clinical nursing care process for cirrhotic patients. Our early warning model based on psychological testing can provide a basis for nursing observation and prevention of hepatic encephalopathy. RELEVANCE TO CLINICAL PRACTICE: Risk assessments for hepatic encephalopathy according to liver function and psychological tests, in addition to traditional neurological observations and dietary guidance, have utility in decreasing the incidence of hepatic encephalopathy.

Androgen Receptor Upregulates Mucosa-Associated Lymphoid Tissue 1 to Induce NF-κB Activity via Androgen-Dependent and -Independent Pathways in Prostate Carcinoma Cells.

The androgen-dependent or -independent pathways are regarded as primary therapeutic targets for the neoplasm of the prostate. Mucosa-associated lymphoid tissue 1 (MALT1) acting as a paracaspase in the regulation of nuclear factor κB (NF-κB) signal transduction plays a central role in inflammation and oncogenesis in cancers. This study confirmed the potential linkages between androgen and NF-κB activation by inducing MALT1 in the androgen receptor-full length (ARFL)-positive LNCaP and 22Rv1 prostate cancer cells. Although androgen did not stimulate MALT1 expression in AR-null or ectopic ARFL-overexpressed PC-3 cells, the ectopic overexpression of the AR splicing variant 7 (ARv7) upregulated MALT1 to activate NF-κB activities in 22Rv1 and PC-3 cells. Since the nuclear translocation of p50 and p65 was facilitated by ARv7 to motivate NF-κB activity, the expressions of MALT1, prostate-specific antigen (PSA), and N-myc downstream regulated 1 (NDRG1) were therefore induced in ectopic ARv7-overexpressed prostate cancer cells. Ectopic ARv7 overexpression not only enhanced 22Rv1 or PC-3 cell growth and invasion in vitro but also the tumor growth of PC-3 cells in vivo. These results indicate that an androgen receptor induces MALT1 expression androgen-dependently and -independently in ARFL- or ARv7-overexpressed prostate cancer cells, suggesting a novel ARv7/MALT1/NF-κB-signaling pathway may exist in the cells of prostate cancer.

Effect on muscle strength after blood flow restriction resistance exercise in early in-patient rehabilitation of post-chronic obstructive pulmonary disease acute exacerbation, a single blinded, randomized controlled study.

BACKGROUND: Early commencement of rehabilitation might counteract the loss of muscle strength due to a chronic obstructive pulmonary disease acute exacerbation (COPDAE). Blood flow restriction resistance exercise (BFR-RE) using a low intensity of training load has demonstrated muscle strength gain in varieties of clinical populations. This trial aimed at studying the efficacy and acceptability of BFR-RE in patients with post-COPDAE which was not reported before. METHOD: A prospective, assessor blinded, randomized controlled study with 2-week in-patient rehabilitation program with BFR-RE was compared to a matched program with resistance exercise without BFR in patients with post-COPDAE. The primary outcome was the change of muscle strength of knee extensor of dominant leg. The secondary outcomes included changes of hand grip strength (HGS), 6-minute walk test (6MWT) distance, short physical performance battery (SPPB) scores, COPD assessment test (CAT) scores; acceptability and feasibility of BFR-RE; and 1-month unplanned re-admission rate. RESULTS: Forty-Five post-COPDAE patients (mean age = 76 ± 10, mean FEV1%=49% ± 24%) were analyzed. After training, BFR-RE group and control group demonstrated a statistically significant median muscle strength gain of 20 (Interquartile range (IQR) 3 to 38) Newton(N) and 12 (IQR -9 to 30) N respectively. BFR-RE group showed a significant change in SPPB scores, but not in 6MWT distance and HGS after training. Between groups did not have statistically significant different in all primary and secondary outcomes, though with similar acceptability. Drop-out rate due to training-related discomfort in BFR-RE group was 3.7%. CONCLUSION: BFR-RE is feasible and acceptable in patients with post-COPDAE. A 2-week inpatient pulmonary rehabilitation with BFR-RE improved muscle strength of knee extensors, but not a greater extent than the same rehabilitation program with resistance exercise without BFR. Further studies could be considered with a longer training duration and progression of resistance load. [ClinicalTrials.gov Identifier: NCT04448236].

Designing Heteroatom-Codoped Iron Metal-Organic Framework for Promotional Photoreduction of Carbon Dioxide to Ethylene.

Rational engineering active sites and vantage defects of catalysts are promising but grand challenging task to enhance photoreduction CO2 to high value-added C2 products. In this study, we designed an N,S-codoped Fe-based MIL-88B catalyst with well-defined bipyramidal hexagonal prism morphology via a facile and effective process, which was synthesized by addition of appropriate 1,2-benzisothiazolin-3-one (BIT) and acetic acid to the reaction solution. Under simulated solar irradiation, the designed catalyst exhibits high C2 H4 evolution yield of 17.7 µmol g-1 ⋅h, which has been rarely achieved in photocatalytic CO2 reduction process. The synergistic effect of Fe-N coordinated sites and reasonable defects in the N,S-codoped photocatalyst can accelerate the migration of photogenerated carriers, resulting in high electron density, and this in turn helps to facilitate the formation and dimerization of C-C coupling intermediates for C2 H4 effectively.

Epidemiological investigation of multiple sclerosis and related medical utilisation in Taiwan.

BACKGROUND: The increasing trend in the prevalence of multiple sclerosis (MS) cannot be neglected. Long-term epidemiological investigations of MS patients who have been registered in Taiwan are very scarce. OBJECTIVE: The aim of this study was to investigate the epidemiology of MS and medical utilisation among MS patients in Taiwan. METHODS: The National Health Insurance Research Database was used as the source of the research population; the time period investigated was 2001-2015. A descriptive statistical analysis of the number of MS patients was conducted. For newly diagnosed MS patients, the frequencies of emergency visits and hospitalisations and changes in their temporal distributions were calculated. RESULTS: The standardised incidence of MS peaked at 0.50/100,000 in 2003, and the highest standardised prevalence was 7.14/100,000 in 2015. The highest standardised mortality was 0.11/100,000 in 2015, with an overall mortality rate of 13.34/1000 person-years. The number of annual emergency visits for MS patients peaked at 0.9 ± 3.5 in 2011, and the longest annual length of hospital stays was 19.2 ± 40.1 days in 2001, which decreased to 5.6 ± 23.5 days in 2015. CONCLUSION: The standardised prevalence of MS steadily increased, and its incidence slightly decreased from 2001 to 2015.

Coordination Polymers with 2,2':6',2″-Terpyridine Earth-Abundant Metal Complex Units for Selective CO2 Photoreduction.

Combining molecular metal complexes into coordination polymers (CPs) is an effective strategy for developing photocatalysts for CO2 reduction; however, most such reported catalysts are noble metal-containing CPs. Herein, two novel Zr-containing bimetallic CPs, Co-Zr and Ni-Zr, were designed and successfully synthesized by connecting 2,2':6',2″-terpyridine-based molecular earth-abundant metal (Co or Ni) complexes with ZrO8 nodes. Both CPs were applied as catalysts for CO2 photoreduction to selectively produce CO. The catalytic performance of Co-Zr is better than that of Ni-Zr with a yield of 3654 µmol (g of catalyst)-1 for CO in 6 h (TON = 18.2). The difference between these two catalysts was analyzed with respect to band structure and charge migration ability. This work provides an effective way to introduce molecular earth-abundant metal complexes into coordination polymers for the construction of efficient noble metal-free CO2 photocatalysts.