Ln3+ Induced Thermally Activated Delayed Fluorescence of Chiral Heterometallic Clusters Ln2Ag28.

A series of TADF-active compounds: 0D chiral Ln-Ag(I) clusters L-/D-Ln2Ag28-0D (Ln = Eu/Gd) and 2D chiral Ln-Ag(I) cluster-based frameworks L-/D-Ln2Ag28-2D (Ln = Gd) has been synthesized. Atomic-level structural analysis showed that the chiral Ag(I) cluster units {Ag14S12} in L-/D-Ln2Ag28-0D and L-/D-Ln2Ag28-2D exhibited similar configurations, linked by varying numbers of [Ln(H2O)x]3+ (x = 6 for 0D, x = 3 for 2D) to form the final target compounds. Temperature-dependent emission spectra and decay lifetimes measurement demonstrated the presence of TADF in L-Ln2Ag28-0D (Ln = Eu/Gd) and L-Gd2Ag28-2D. Experimentally, the remarkable TADF properties primarily originated from {Ag14S12} moieties in these compounds. Notably, {Ag14S12} in L-Eu2Ag28-0D and L-Gd2Ag28-2D displayed higher promote fluorescence rate and shorter TADF decay times than L-Gd2Ag28-0D. Combined with theoretical calculations, it was determined that the TADF behaviors of {Ag14S12} cluster units were induced by 4f perturbation of Ln3+ ions. Specially, while maintaining ΔE(S1-T1) small enough, it can significantly increase k(S1→S0) and reduce TADF decay time by adjusting the type or number of Ln3+ ions, thus achieving the purpose of improving TADF for cluster-based luminescent materials.

The influence of cerebellum on visual selective attention in patients with multiple lacunar cerebral infarction and its neuromodulatory mechanisms.

Objective: This study aims to investigate the influence of the cerebellum on visual selective attention function and its neuromodulatory mechanism in patients with multiple lacunar cerebral infarction (MLCI). Methods: A retrospective analysis was conducted on 210 patients admitted with MLCI from January 2016 to May 2022. Analyzed the electrophysiological characteristics of the P3a and P3b components of vision in both groups, as well as source reconstruction simulations of dipole activation in the brains of the two groups, and analyzed the brain regions with differences in activation strength between the two groups. Results: This study found that there was no significant difference in peak amplitude between the two groups, but compared with the control group, the peak latency of the case group was significantly prolonged. Specifically, the P3a peak latency induced by the novel stimulus was longer than that induced by the target stimulus P3b peak latency. Source reconstruction results showed decreased and increased activation in several brain regions in the case group compared to the control group. Conclusion: The study suggests that the impairment of distracted attention capture is more pronounced in patients with MLCI. The cerebellum indirectly influences the ventral and dorsal frontoparietal attention networks by modulating the levels of excitation and inhibition within the cerebral cortex of the attention network. This may represent a potential mechanism through which the cerebellum regulates visual selective attention information in MLCI patients.

White spot lesion-related perception of aesthetics and treatment satisfaction among orthodontic patients, orthodontists and other dental specialists.

OBJECTIVE: To investigate the impact of various degrees of white spot lesions (WSLs) of maxillary anterior teeth on the aesthetic perception and treatment satisfaction among orthodontic patients, orthodontists and other dental specialists and to evaluate the differences among the three groups. METHODS: A total of 45 orthodontic patients (OP), 45 orthodontists (OR) and 45 other dental specialists (OS) were recruited. Subjective evaluations of perceived aesthetics and treatment satisfaction were performed towards eight digitally generated photographs of maxillary anterior teeth with incremental degrees of WSLs using a numerical visual analogue scale (VAS) from 0 to 100. Data were collected and analysed with descriptive statistics, repeated one-way analysis of variance and multivariable generalized estimating equations. RESULTS: A total of 135 valid questionnaires were collected. Regarding aesthetic scores for WSLs, OP gave more positive scores than OR and OS (p < .05) towards excessive white spot formation without colouration and were more tolerant than OR (p < .05) towards excessive white spot formation with slight colouration. The level of treatment satisfaction for slight to severe WSLs without cavitation was higher in OP than OR. Patients with higher education levels had more negative scores for aesthetic perception and treatment satisfaction (p < .05). Patients who brushed teeth more frequently scored lower in treatment satisfaction (p < .05). CONCLUSIONS: Orthodontists were the most critical when evaluating aesthetics and treatment satisfaction for slight to severe WSLs without cavitation. For orthodontic patients, better oral hygiene habits and higher education levels were associated with more critical attitudes towards WSLs.

CURRENT NEURAL NETWORKS DEMONSTRATE POTENTIAL IN AUTOMATED CERVICAL VERTEBRAL MATURATION STAGE CLASSIFICATION BASED ON LATERAL CEPHALOGRAMS.

ARTICLE TITLE AND BIBLIOGRAPHIC INFORMATION: Neural networks for classification of cervical vertebrae maturation: a systematic review. Mathew R, Palatinus S, Padala S, Alshehri A, Awadh W, Bhandi S, Thomas J, Patil S. Angle Orthod. 2022 Nov 1;92(6):796-804. SOURCE OF FUNDING: No financial support was reported. TYPE OF STUDY/DESIGN: Systematic review.

In vitro evaluation of an easy-to-remove orthodontic adhesive with photochromic property.

OBJECTIVES: To develop a photochromic bracket adhesive (PCA) with modification using photochromic material and evaluate the biocompatibility, bond strength, photochromic property, and adhesive removal efficiency. MATERIALS AND METHODS: The resin-modified glass ionomer powder was mixed with the photochromic material and then blended with the liquid agent to form PCA. Biocompatibility was evaluated by CCK-8 kit, and shear bond strength (SBS) was measured. Stereoscopic microscopy and quantitative color analysis were used to assess the photochromic property. Bracket bonding and debonding procedures were performed on a head simulator with the assistance of an ultraviolet radiator. The effectiveness of adhesive removal during bonding and debonding procedures was assessed using a stereomicroscope. Removal time was recorded, and the enamel damage index after debonding was analyzed. RESULTS: CCK-8 assay and SBS test indicated that 5wt.% mixing ratios of the photochromic material did not compromise the biocompatibility and SBS of the adhesive (PCA5). PCA5 showed photochromic properties and could help the operator remove adhesive more thoroughly without increasing enamel damage. CONCLUSIONS: Photochromic adhesive (PCA5) can be good for orthodontic adhesive removal and therefore has good clinical translation potential.

Chiral lanthanide-silver(I) cluster-based metal-organic frameworks exhibiting solvent stability, and tunable photoluminescence.

Due to the lack of effective synthetic strategies, the preparation of chemically stable chiral Ag(I) cluster-based materials for assembly remains challenging. Here, we have developed an approach to synthesize three pairs of chiral Ln-Ag(I) cluster-based metal-organic frameworks (MOFs) named l-LnAg5-3D (Ln = Gd for 1-L, Eu for 2-L, and Tb for 3-L) and d-LnAg5-3D (Ln = Gd for 1-D, Eu for 2-D, and Tb for 3-D) by employing a chiral Ag(I) cluster ({Ag5S6}) as the node and Ln3+ ion as the inorganic linker. Structural analysis revealed that the chiral ligands induced chirality through the entire structure, resulting in a chiral helix arrangement of the C3-symmetric chiral {Ag5S6} nodes and Ln3+ ions. These compounds showed high solvent stability in various polar organic solvents. The solid-state circular dichroism (CD) spectra of compounds l-LnAg5-3D and d-LnAg5-3D exhibited obvious mirror symmetrical peaks. The emission spectra in the solid state revealed that compound 1-L only exhibited the emission peak of {Ag5S6}, while compounds 2-L and 3-L exhibited overlapping peaks of Ln3+ and {Ag5S6} at different excitation wavelengths. This demonstrates the tunable photoluminescence from {Ag5S6} to Ln3+ by introducing different Ln3+ ions and manipulating the excitation wavelengths. The study underscores the enhanced stability of Ag(I) cluster-based MOFs achieved through the incorporation of Ln3+ ions and establishes chiral Ln-Ag(I) cluster-based MOFs as promising candidates for advanced materials with tunable photoluminescence.

The knowledge, experience, and attitude on artificial intelligence-assisted cephalometric analysis: Survey of orthodontists and orthodontic students.

INTRODUCTION: Artificial intelligence (AI) developed rapidly in orthodontics, and AI-based cephalometric applications have been adopted. This study aimed to assess AI-assisted cephalometric technologies related knowledge, experience, and attitude among orthodontists and orthodontic students; describe their subject view of the applications and related technologies in orthodontics; and identify associated factors. METHODS: An online cross-sectional survey based on a professional tool (www.wjx.cn) was performed from October 11-17, 2022. Participants were recruited with a purposive and snowball sampling approach. Data was collected and analyzed with descriptive statistics, chi-square tests, and multivariable generalized estimating equations. RESULTS: Four hundred eighty valid questionnaires were collected and analyzed; 68.8% of the respondents agreed that AI-based cephalometric applications would replace manual and semiautomatic approaches. Practitioners using AI-assisted applications (87.5%) spent less time in cephalometric analysis than the other groups using other approaches, and 349 (72.7%) respondents considered AI-based applications could assist in obtaining more accurate analysis results. Lectures and training programs (56.0%) were the main sources of respondents' knowledge about AI. Knowledge level was associated with experience in AI-related clinical or scientific projects (P <0.001). Most respondents (88.8%) were interested in future AI applications in orthodontics. CONCLUSIONS: Respondents are optimistic about the future of AI in orthodontics. AI-assisted cephalometric applications were believed to make clinical diagnostic analysis more convenient and straightforward for practitioners and even replace manual and semiautomatic approaches. The education and promotion of AI should be strengthened to elevate orthodontists' understanding.

In vitro evaluation of a novel fluoride-coated clear aligner with antibacterial and enamel remineralization abilities.

OBJECTIVE: To investigate the antibacterial and enamel remineralization performances as well as physicochemical properties and biocompatibility of a fluoride-coated clear aligner plastic (FCAP). MATERIALS AND METHODS: FCAP and normal clear aligner plastic (CAP) was bought from the manufacturer (Angelalign Technology Inc, China). The FCAP was observed under scanning electron microscopy. Its element composition, resistance to separation, contact angle, and protein adhesion performance were characterized. Colony-forming unit (CFU) count and 3-(4,5)-dimethylthiazol(-z-y1)-3,5-diphenyltetrazolium bromide (MTT) assay were used to evaluate the antibacterial ability of Streptococcus mutans. Fluoride release-recharge patterns were obtained. Apatite formation was evaluated after immersing FCAP in artificial saliva. Enamel remineralization capability was evaluated in the demineralization model (immersing samples in demineralization solution for 36 h) and pH cycling model (immersing samples in demineralization solution and remineralization solution in turns for 14 days). Cell Counting Kit-8 (CCK-8) and live/dead cell staining kits were used for cytotoxicity assay. RESULTS: The FCAP showed uniformly distributed fluoride and did not compromise protein adhesion performance. CFU count (5.47 ± 0.55 for CAP, 3.63 ± 0.38 for FCAP) and MTT assay (0.41 ± 0.025 for CAP, 0.28 ± 0.038) indicated that the FCAP had stronger antibacterial activity compared with normal CAP (P < 0.05 for both evaluations). The FCAP could release fluoride continuously for 14 days and could be recharged after immersing in NaF solution. The FCAP could induce the formation of hydroxyapatite in artificial saliva and could reduce the microhardness decrease, color change, and mineral loss of enamels in both two models (P < 0.05 for all evaluations). CCK-8 and live/dead cell staining analyses showed that the coating did not compromise the biocompatibility of the clear aligner (P > 0.05 for CCK-8 evaluation). CONCLUSIONS: The FCAP had antibacterial, fluoride recharge, and enamel remineralization abilities while it did not compromise physicochemical properties and biocompatibility. CLINICAL RELEVANCE: The FCAP has the potential to prevent enamel demineralization during clear aligner treatment.

The cerebellum and cognitive neural networks.

Cognitive function represents a complex neurophysiological capacity of the human brain, encompassing a higher level of neural processing and integration. It is widely acknowledged that the cerebrum plays a commanding role in the regulation of cognitive functions. However, the specific role of the cerebellum in cognitive processes has become a subject of considerable scholarly intrigue. In 1998, Schmahmann first proposed the concept of "cognitive affective syndrome (CCAS)," linking cerebellar damage to cognitive and emotional impairments. Since then, a substantial body of literature has emerged, exploring the role of the cerebellum in cognitive neurological function. The cerebellum's adjacency to the cerebral cortex, brainstem, and spinal cord suggests that the cerebral-cerebellar network loops play a crucial role in the cerebellum's participation in cognitive neurological functions. In this review, we comprehensively examine the recent literature on the involvement of the cerebellum in cognitive functions from three perspectives: the cytological basis of the cerebellum and its anatomical functions, the cerebellum and cognitive functions, and Crossed cerebellar diaschisis. Our aim is to shed light on the role and mechanisms of the cerebellum in cognitive neurobrain networks.

Phosphine-based metal-organic layers to construct single-site heterogeneous catalysts for arene borylation.

Metal-organic layers (MOLs) are versatile platforms for creating single-site heterogeneous catalysts. Incorporating molecular functionalities into MOLs is crucial for catalysis. In this study, we synthesized phosphine-containing MOLs constructed from Hf6-oxo secondary building units (SBUs) and phosphine ligands. The mono(phosphine)-Ir complexes generated by the metalation of TPP-MOL were highly active as heterogeneous catalysts for the C(sp2)-H borylation of a range of arenes. This research expands the diversity of MOL-based catalysts.

Antibacterial and fluorescent clear aligner attachment resin modified with chlorhexidine loaded mesoporous silica nanoparticles and zinc oxide quantum dots.

OBJECTIVES: To develop an antibacterial and fluorescent clear aligner attachment resin via the incorporation of chlorhexidine loaded pore-expanded mesoporous silica nanoparticles (CHX@pMSN) and amino-silane functionalized zinc oxide quantum dots (aZnOQDs), and to evaluate its antibacterial activity, fluorescence capability, esthetic properties, mechanical performance and biocompatibility. METHODS: CHX@pMSN and aZnOQDs were incorporated into the commercial resin composites (Filtek Z350 XT, 3M) at different mass fractions, control group: Filtek; fluorescent attachment resin (FAR): Filtek + 3 wt% aZnOQDs; antibacterial and fluorescent attachment resin (AFAR)-1: Filtek + 3 wt% aZnOQDs + 1 wt% CHX@pMSN; AFAR-2: Filtek + 3 wt% aZnOQDs + 3 wt% CHX@pMSN; AFAR-3: Filtek + 3 wt% aZnOQDs + 5 wt% CHX@pMSN. CHX release, antibacterial activity, fluorescence capability, color change, stain resistance, degree of conversion, depth of cure, polymerization shrinkage, water sorption and solubility, softening in solvent, flexural strength, flexural modulus, shear bond strength, and cytotoxicity were evaluated comprehensively. RESULTS: CHX could be continuously released from the AFAR groups for up to 30 days. CFU, MTT, lactic acid production, SEM and CLSM evaluation showed AFAR-2 and AFAR-3 could effectively inhibit S. mutans biofilms even after 1-month aging. Only AFAR-3 showed clinically perceptible color change and all the experimental groups were not more susceptible to staining. AFAR-1 and AFAR-2 could suppress polymerization shrinkage and enhance the resistance to degradation without compromising other properties, including degree of conversion, water sorption and solubility, flexural strength, flexural modulus, and shear bond strength. Depth of cure of all the four experimental groups was significantly decreased (p < 0.05) but still within the ISO standard. CCK-8 assay and live/dead cell staining denied the cytotoxicity of experimental resins. Fluorescence intensity tests showed that FAR and AFAR-2 could emit strong yellowish fluorescence under the excitation of ultraviolet for up to six months. CONCLUSIONS: AFRA-2 possessed long-term antibiofilm activity, strong fluorescence capability and satisfying biocompatibility without compromising esthetic and mechanical properties. This study proposed a new strategy for reducing bacteria accumulation around the attachment, which is also promising in helping orthodontists to remove the attachment thoroughly and precisely.

Effects of silica fume powder modified by oleic acid on the settleability of bulking sludge.

Modified silica fume powder with oleic acid through coupling agent was prepared based on the in situ utilizing long-chain fatty acids (LCFA) properties of Microthrix parvicella (M. parvicella) in the activated sludge system. The modification was confirmed by XRD and infrared spectrum. The contact angle analysis showed that the modification gave the silica fume powder a hydrophobic surface. The modified silica fume powder had a good combination with M. parvicella from the SEM and Gram staining measurements. The addition of modified silica powder has a certain effect on the settling capacity of sludge, but has little effect on the sludge treatment capacity, while the SVI dropped from 400.1 to 100.0 mL/g. These suggested that the modified silica fume powder could be used as an excellent weight-increasing agent to inhibit sludge bulking.

Modified constraint-induced movement therapy enhances cortical plasticity in a rat model of traumatic brain injury: a resting-state functional MRI study.

Modified constraint-induced movement therapy (mCIMT) has shown beneficial effects on motor function improvement after brain injury, but the exact mechanism remains unclear. In this study, amplitude of low frequency fluctuation (ALFF) metrics measured by resting-state functional magnetic resonance imaging was obtained to investigate the efficacy and mechanism of mCIMT in a control cortical impact (CCI) rat model simulating traumatic brain injury. At 3 days after control cortical impact model establishment, we found that the mean ALFF (mALFF) signals were decreased in the left motor cortex, somatosensory cortex, insula cortex and the right motor cortex, and were increased in the right corpus callosum. After 3 weeks of an 8-hour daily mCIMT treatment, the mALFF values were significantly increased in the bilateral hemispheres compared with those at 3 days postoperatively. The mALFF signal values of left corpus callosum, left somatosensory cortex, right medial prefrontal cortex, right motor cortex, left postero dorsal hippocampus, left motor cortex, right corpus callosum, and right somatosensory cortex were increased in the mCIMT group compared with the control cortical impact group. Finally, we identified brain regions with significantly decreased mALFF values at 3 days postoperatively. Pearson correlation coefficients with the right forelimb sliding score indicated that the improvement in motor function of the affected upper limb was associated with an increase in mALFF values in these brain regions. Our findings suggest that functional cortical plasticity changes after brain injury, and that mCIMT is an effective method to improve affected upper limb motor function by promoting bilateral hemispheric cortical remodeling. mALFF values correlate with behavioral changes and can potentially be used as biomarkers to assess dynamic cortical plasticity after traumatic brain injury.

DEEP LEARNING ALGORITHMS HAVE HIGH ACCURACY FOR AUTOMATED LANDMARK DETECTION ON 2D LATERAL CEPHALOGRAMS.

ARTICLE TITLE AND BIBLIOGRAPHIC INFORMATION: Deep learning for cephalometric landmark detection: systematic review and meta-analysis. Schwendicke F, Chaurasia A, Arsiwala L, Lee JH, Elhennawy K, Jost-Brinkmann PG, Demarco F, Krois J. Clin Oral Investig. 2021 Jul;25(7):4299-4309. SOURCE OF FUNDING: This study was self-funded by the authors and their institutions. TYPE OF STUDY/DESIGN: Systematic review and meta-analysis.

Study protocol of a randomized controlled trial for the synergizing effects of rTMS and Tui Na on upper limb motor function and cortical activity in ischemic stroke.

Upper limb motor dysfunction after stroke is a serious threat to the living quality of patients and their families. Recovery of upper limb motor function after stroke largely relies on the activation and remodeling of neural circuits. rTMS (repetitive transcranial magnetic stimulation) has been proved to promote the reconstruction of neural synapses and neural circuits. However, there are still a large number of patients who cannot fully recover and leave behind varying degrees of dysfunction. Considering the systemic pathology after stroke, in addition to focal brain injury, stroke can also cause extensive dysfunction of peripheral organs. The rehabilitation strategy for stroke should combine the treatment of primary brain lesions with the intervention of secondary systemic damage. The aim of this trial is to verify the efficacy of rTMS synergize with Tui Na (Chinese Massage) on upper limb motor function after ischemic stroke, and to explore the mechanism of activation and remodeling of sensorimotor neural circuits with functional near-infrared spectroscopy. Ninety patients will be randomly assigned to either rTMS + Tui Na + conventional rehabilitation group (the experimental group) or rTMS + conventional rehabilitation group (the control group) in 1:1 ratio. Intervention is conducted five sessions a week, with a total of twenty sessions. The primary outcome is Fugl-Meyer Assessment, and the secondary outcomes include Muscle Strength, Modified Ashworth Assessment, Modified Barthel Index Assessment, motor evoked potentials and functional near-infrared spectroscopy. There are four time points for the evaluation, including baseline, 2 weeks and 4 weeks after the start of treatment, and 4 weeks after the end of treatment. This study is a randomized controlled trial. This study was approved by Institutional Ethics Committee of Shanghai Third Rehabilitation Hospital Affiliated to Shanghai University of Traditional Chinese Medicine (approval No. SH3RH-2021-EC-012) on December, 16th, 2021. The protocol was registered with Chinese Clinical Trial Registry (ChiCTR2200056266), on February 3th, 2022. Patient recruitment was initiated on February 10th, 2022, and the study will be continued until December 2023.

Atom-Precise Chiral Lanthanide-Silver(I) Heterometallic Clusters Ln3Ag5.

Three pairs of chiral Ln-Ag(I) clusters d/l-Ln3Ag5 with C3 symmetry were prepared by d/l-penicillamine as multidentate ligand bridged Ln3+ and Ag(I) ions. The chiral ligand induced the molecular cluster to be chiral, and the CD spectra of the chiral compounds d/l-Ln3Ag5 were slightly blue-shifted due to the lanthanide contraction. The studies of optical properties indicated that tunable photoluminescence from {AgS}-to-Ln3+ was achieved by introducing Ln3+ ions with different emission bands or regulating various excitation light.

Observation of formation and local structures of metal-organic layers via complementary electron microscopy techniques.

Metal-organic layers (MOLs) are highly attractive for application in catalysis, separation, sensing and biomedicine, owing to their tunable framework structure. However, it is challenging to obtain comprehensive information about the formation and local structures of MOLs using standard electron microscopy methods due to serious damage under electron beam irradiation. Here, we investigate the growth processes and local structures of MOLs utilizing a combination of liquid-phase transmission electron microscopy, cryogenic electron microscopy and electron ptychography. Our results show a multistep formation process, where precursor clusters first form in solution, then they are complexed with ligands to form non-crystalline solids, followed by the arrangement of the cluster-ligand complex into crystalline sheets, with additional possible growth by the addition of clusters to surface edges. Moreover, high-resolution imaging allows us to identify missing clusters, dislocations, loop and flat surface terminations and ligand connectors in the MOLs. Our observations provide insights into controllable MOL crystal morphology, defect engineering, and surface modification, thus assisting novel MOL design and synthesis.

Multifunctional modification of orthodontic adhesives with ZnO quantum dots.

OBJECTIVES: To develop a multifunctional orthodontic adhesive (QDA) using ZnO quantum-dots (ZnQDs) as modifier and investigate the antibacterial capability, fluorescence property as well as biocompatibility and bonding property. METHODS: ZnQDs were synthesized using sol-gel method. XPS, XRD, FT-IR, HRTEM, SAED, DLS and spectrofluorimetry were used to characterize ZnQDs. ZnQDs were incorporated into Transbond XT adhesive paste with 20 %, 30 %, 40 % mass fraction, respectively, to form the multifunctional adhesives (QDAs). Antibacterial capability was evaluated with MTT kit, CFU count and Live/Dead Bacterial Staining Kit. Ultraviolet photography and spectrofluorimetry were used to confirm the fluorescence property of QDAs. Biocompatibility assay was performed on gingival fibroblasts and subcutaneous tissue of rats. Softening in solvent rate, shear bond strength and degree of conversion (DC) were measured. RESULTS: The synthesized ZnQDs presented excellent crystallinity and fluorescence properties. MTT assay, CFU count and CLSM analysis indicated that QDAs had significant antibacterial activity compared with Transbond XT adhesive paste. CCK-8 assay and Live/Dead cell staining analysis denied the cytotoxicity of QDAs and histological analysis proved that QDAs all had no inflammatory irritation to subcutaneous tissue. Softening in solvent, shear bond strength and DC evaluations indicated that 20 % mixing ratio of ZnQDs could enhance the resistance to degradation without influencing the bond strength and DC. Ultraviolet photography and spectrofluorimetry analysis proved the fluorescence capability of QDAs. SIGNIFICANCE: ZnQDs can impart antibacterial and fluorescence properties to orthodontic adhesives without affecting biocompatibility and bonding performance. QDAs can be multifunctional orthodontic adhesives to reduce bacterial adhesion around brackets and help orthodontists remove residual adhesives precisely when needed.

Two-dimensional metal-organic layers constructed from Hf6/Hf12-oxo clusters and a trigonal pyramidal phosphine oxide ligand.

Metal-organic layers (MOLs), a category of two-dimensional materials, have attracted wide interest due to their molecular tunability and the ease of surface modification. Herein, we reported the synthesis and structural determination of a free-standing MOL, {[Hf6O8H4(HCOO)2(H2O·OH)4]3[Hf12O16H8(HCOO)6.8(H2O·OH)11.2](TPO)8}n, constructed from Hf6-oxo and Hf12-oxo clusters as secondary building units (SBUs) and the tris(4-carboxylphenyl)phosphine oxide (TPO) ligand. We establish a structure model of this new MOL based on the combined information from different characterization methods.

Family of Nanoclusters, Ln33 (Ln = Sm/Eu) and Gd32, Exhibiting Magnetocaloric Effects and Fluorescence Sensing for MnO4.

A family of nanoclusters, [Ln33(EDTA)12(OAc)2(CO3)4(µ3-OH)36(µ5-OH)4(H2O)38]·OAc·xH2O (x ≈ 50, Ln = Sm for 1; x ≈ 70, Ln = Eu for 2) and [Gd32(EDTA)12(OAc)2(C2O4)(CO3)2(µ3-OH)36(µ5-OH)4(H2O)36]·x(H2O) (x ≈ 70 for 3; H4EDTA = ethylene diamine tetraacetic acid), was prepared through the assembly of repeating subunits under the action of an anion template. The analysis of the structures showed that compounds 1 and 2 containing 33 Ln3+ ions were isostructural, which were constructed by three kinds of subunits in the presence of CO32- as an anion template, while compound 3 had a slightly different structure. Compound 3 containing 32 Gd3+ ions was formed by three types of subunits in the presence of CO32- and C2O42- as a mixed anion template. The CO32- anions came from the slow fixation of CO2 in the air. Meanwhile, one kind of high-nuclearity lanthanide clusters showed high chemical stability. The quantum Monte Carlo (QMC) calculation suggested that weak antiferromagnetic interactions were dominant between Gd3+ ions in 3. Magnetocaloric studies showed that compound 3 had a large entropy change of 43.0 J kg-1 K-1 at 2 K and 7 T. Surprisingly, compound 2 showed excellent recognition and detection effects for permanganate in aqueous solvents based on the fluorescence quenching phenomenon.