Integrating Polyoxometalates and Silver Clusters into Atomically Precise Molecular Heterojunction.

The Ag cluster-POM assemblies have been shown to possess interesting and potentially useful properties. However, there is no precedent example of atomically precise Ag cluster-POM assemblies showing heterojunction effects in photocatalysis. Herein, the synthesis and total structure determination of the periodically distributed molecular heterojunction [Ag12(SCy)6(CH3CN)12(PW12O40)]n (Ag12-PW12) are reported. The assembly of Ag/W clusters into 3D network can endow the resulting binary structure with an aesthetic topology and unique physicochemical properties. More remarkably, the incorporation of Ag12 cluster with PW12 can efficiently facilitate the separation of photogenerated electrons and holes, thus significantly promoting the catalytic efficiency in selective oxidation of sulfides. The Ag12-PW12 heterojunction can be recovered and reused five times with no drastic change in the catalytic performance. This research is expected to assist in the rational design of cluster-based heterojunction catalysts. The increase of catalytic activity of the Ag12-PW12 assembly in comparison with the unassembled Ag12 and PW12 clusters is attributed to the synergistic effect of Ag12 and PW12 clusters, offering the splendid opportunity for deciphering structure-reactivity relationship of heterostructure-coupled photosystem.

A specific inflammatory suppression fibroblast subpopulation characterized by MHCII expression in human dilated cardiomyopathy.

Dilated cardiomyopathy (DCM) is a significant cause of heart failure that requires heart transplantation. Fibroblasts play a central role in the fibro-inflammatory microenvironment of DCM. However, their cellular heterogeneity and interaction with immune cells have not been well identified. An integrative analysis was conducted on single-cell RNA sequencing (ScRNA-Seq) data from human left ventricle tissues, which comprised 4 hearts from healthy donors and 6 hearts with DCM. The specific antigen-presenting fibroblast (apFB) was explored as a subtype of fibroblasts characterized by expressing MHCII genes, the existence of which was confirmed by immunofluorescence staining of 3 cardiac tissues from DCM patients with severe heart failure. apFB highly expressed the genes that response to IFN-γ, and it also have a high activity of the JAK-STAT pathway and the transcription factor RFX5. In addition, the analysis of intercellular communication between apFBs and CD4+T cells revealed that the anti-inflammatory ligand-receptor pairs TGFB-TGFR, CLEC2B-KLRB1, and CD46-JAG1 were upregulated in DCM. The apFB signature exhibited a positive correlation with immunosuppression and demonstrated diagnostic and prognostic value when evaluated using a bulk RNA dataset comprising 166 donors and 166 DCM samples. In conclusion, the present study identified a novel subpopulation of fibroblasts that specifically expresses MHCII-encoding genes. This specific apFBs can suppress the inflammation occurring in DCM. Our findings further elucidate the composition of the fibro-inflammatory microenvironment in DCM, and provide a novel therapeutic target.

A Biodegradable Janus Sponge for Negative Pressure Wound Therapy.

Negative pressure wound therapy (NPWT) is effective in repairing serious skin injury. The dressing used in the NPWT is important for wound healing. In this paper, we develop biodegradable amphiphilic polyurethanes (PUs) and fabricate the PUs into sponges as wound dressings (Bi@e) with Janus pore architectures for NPWT. The Bi@e is adaptive to all the stages of the wound healing process. The Janus Bi@e sponge consists of two layers: the dense hydrophobic upper layer with small pores provides protection and support during negative pressure drainage, and the loose hydrophilic lower layer with large pores absorbs large amounts of wound exudate and maintains a moist environment. Additionally, antibacterial agent silver sulfadiazine (SSD) is loaded into the sponge against Escherichia coli and Staphylococcus aureus with a concentration of 0.50 wt%. The Janus sponge exhibits a super absorbent capacity of 19.53 times its own water weight and remarkable resistance to compression. In a rat skin defect model, the Janus Bi@e sponge not only prevents the conglutination between regenerative skin and dressing but also accelerates wound healing compared to commercially available NPWT dressing. The Janus Bi@e sponge is a promising dressing for the NPWT.

Effects of hypoxia in cardiac metabolic remodeling and heart failure.

Aerobic cellular respiration requires oxygen, which is an essential part of cardiomyocyte metabolism. Thus, oxygen is required for the physiologic metabolic activities and development of adult hearts. However, the activities of metabolic pathways associated with hypoxia in cardiomyocytes (CMs) have not been conclusively described. In this review, we discuss the role of hypoxia in the development of the hearts metabolic system, and the metabolic remodeling associated with the hypoxic adult heart. Hypoxia-inducible factors (HIFs), the signature transcription factors in hypoxic environments, is also investigated for their potential to modulate hypoxia-induced metabolic changes. Metabolic remodeling existing in hypoxic hearts have also been shown to occur in chronic failing hearts, implying that novel therapeutic options for heart failure (HF) may exist from the hypoxic perspective. The pressure overload-induced HF and diabetes-induced HF are also discussed to demonstrate the effects of HIF factor-related pathways to control the metabolic remodeling of failing hearts.

Unregulated GmAGL82 due to Phosphorus Deficiency Positively Regulates Root Nodule Growth in Soybean.

Nitrogen fixation, occurring through the symbiotic relationship between legumes and rhizobia in root nodules, is crucial in sustainable agriculture. Nodulation and soybean production are influenced by low levels of phosphorus stress. In this study, we discovered a MADS transcription factor, GmAGL82, which is preferentially expressed in nodules and displays significantly increased expression under conditions of phosphate (Pi) deficiency. The overexpression of GmAGL82 in composite transgenic plants resulted in an increased number of nodules, higher fresh weight, and enhanced soluble Pi concentration, which subsequently increased the nitrogen content, phosphorus content, and overall growth of soybean plants. Additionally, transcriptome analysis revealed that the overexpression of GmAGL82 significantly upregulated the expression of genes associated with nodule growth, such as GmENOD100, GmHSP17.1, GmHSP17.9, GmSPX5, and GmPIN9d. Based on these findings, we concluded that GmAGL82 likely participates in the phosphorus signaling pathway and positively regulates nodulation in soybeans. The findings of this research may lay the theoretical groundwork for further studies and candidate gene resources for the genetic improvement of nutrient-efficient soybean varieties in acidic soils.

Coordination-Delayed-Hydrolysis Method for the Synthesis and Structural Modulation of Titanium-Oxo Clusters.

ConspectusAtomically precise titanium-oxo clusters (TOCs) are the structure and reactivity model compounds of technically important TiO2 materials, which could help build structure-property relationships and achieve property modulation at the molecular level. However, the traditional formation of TOCs has relied on the poorly controllable hydrolysis of titanium alkoxide in the solvent for a long time, limiting the development of TOC structural chemistry to a great extent. In addition, easily hydrolyzable alkoxy groups would be still coordinated on the surface of the TOCs generated by this method, making the clusters sensitive and unstable to the moisture. To achieve controllable preparation of TOCs, we believe it is crucial to attenuate the hydrolysis of titanium ions in the formation process of a cluster. To this end, we have recently applied an effective coordination-delayed-hydrolysis (CDH) strategy for TOC synthesis, which provides powerful tools for tuning their structures.In this Account, at the beginning, a brief introduction to the coordination-delayed-hydrolysis strategy is supplied, and its predominant features for constructing novel TOCs are highlighted. In subsequent sections, we discuss how the applied chelating organic/inorganic ligands (named hydrolysis delayed ligands) influence the hydrolysis process of Ti4+ ions to form a large family of TOCs with various nuclearities and core structures. Various hydrolysis delayed ligands have been explored, ranging from common O-donor ligands (carboxylate, phenol, or sulfate) to rarely used N-donor ligands (pyrazole) or bifunctional O/N-donor ones (quinoline, oxime, or alkanolamine). Breakthroughs in the symmetry, configuration, and cluster nuclei of TOCs have been accordingly achieved. Then, we show that this CDH method can be used to tune the surface structure of TOCs by modifying functional organic ligands. As a result, the physicochemical properties of TOCs, especially optical band gaps, can be optimized, and their stability under ambient conditions is significantly improved. In addition, we illustrate that the reversible bonds between hydrolysis delayed ligands and Ti ions further allows us to introduce active heterometal ions or clusters upon or inside the Ti-O cores to prepare heterometallic TOCs with unprecedented structures and properties. In particular, noble metal (Ag ions or clusters) has been incorporated into Ti-O clusters for the first time. As a summary, the coordination-delayed-hydrolysis strategy has realized the controllable hydrolysis of Ti4+ ions to some extent, breaking through the limitations of traditional synthesis methods and producing fruitful results in the field of titanium-oxo clusters. It is believed that this CDH method would also be effective for synthesizing oxo clusters of other easily hydrolyzed metal ions (Al3+, Sn4+, In3+, etc.) to afford significant contribution for the cluster community.

Abyssibius alkaniclasticus gen. nov., sp. nov., a novel member of the family Rhodobacteraceae, isolated from the Mariana Trench.

A Gram-stain-negative bacterium with rod-shaped or irregular cells approximately 0.5-0.9×2.0-3.8 µm in size, designated as 960558T, was isolated from sediment sampled in the Mariana Trench. Strain 960558T grows at 4-37 °C (optimum, 28 °C), pH 6-7 (optimum, pH 7) and in the presence of 1-5 % (w/v) NaCl (optimum, 3 %). Strain 960558T utilizes tetradecane or hexadecane as a sole carbon and energy source, respectively. Phylogenetic trees based on 16S rRNA gene sequences and phylogenomic reconstruction revealed a close phylogenetic relationship between strain 960558T and members of the family Rhodobacteraceae by forming a separate branch within the type species of closely related genera. The validly published species that is most closely related to strain 960558T is Planktotalea lamellibrachiae JAM 119T, which has the highest 16S rRNA gene sequence similarity (93.47 %). Ubiquinone 10 is the predominant ubiquinone, while C16 : 0, 11-methyl C18 : 1 ω7c and C18 : 1 ω7c and/or C18 : 1 ω6c are the predominant fatty acids (>10 %). Additionally, phosphatidylglycerol, glycolipids, diphosphatidylglycerol, unidentified polar lipids and unidentified aminolipids are the major polar lipids. The DNA G+C content of strain 960558T is 61 %. Average nucleotide identity and digital DNA-DNA hybridization results of strain 960558T with other type strains are <70.2 and 22.1 %, respectively. Based on its phylogenetic, chemotaxonomic and other phenotypic properties, strain 960558T is considered to represent a novel genus and species within the family Rhodobacteraceae, for which the name Abyssibius alkaniclasticus gen. nov., sp. nov. is proposed. The type strain of Abyssibius alkaniclasticus is 960558T (=KCTC 82619T=MCCC 1K04727T).

Torpor-like Hypothermia Induced by A1 Adenosine Receptor Agonist: A Novel Approach to Protect against Neuroinflammation.

Hypothermia is a promising clinical therapy for acute injuries, including neural damage, but it also faces practical limitations due to the complexities of the equipment and procedures required. This study investigates the use of the A1 adenosine receptor (A1AR) agonist N6-cyclohexyladenosine (CHA) as a more accessible method to induce steady, torpor-like hypothermic states. Additionally, this study investigates the protective potential of CHA against LPS-induced sepsis and neuroinflammation. Our results reveal that CHA can successfully induce a hypothermic state by activating a neuronal circuit similar to the one that induces physiological torpor. This state is characterized by maintaining a steady core body temperature below 28 °C. We further found that this torpor-like state effectively mitigates neuroinflammation and preserves the integrity of the blood-brain barrier during sepsis, thereby limiting the infiltration of inflammatory factors into the central nervous system. Instead of being a direct effect of CHA, this protective effect is attributed to inhibiting pro-inflammatory responses in macrophages and reducing oxidative stress damage in endothelial cells under systemic hypothermia. These results suggest that A1AR agonists such as CHA could potentially be potent neuroprotective agents against neuroinflammation. They also shed light on possible future directions for the application of hypothermia-based therapies in the treatment of sepsis and other neuroinflammatory conditions.

Manganese Intoxication Recovery and the Expression Changes of Park2/Parkin in Rats.

Occupational overexposure to manganese (Mn) produces Parkinson's disease-like manganism. Acute Mn intoxication in rats causes dopaminergic neuron loss, impairment of motor activity and reduction of the expression of Park2/Parkin. The expression of Park2/Parkin is also reduced. Whether these changes are reversible after cessation of Mn exposure is unknown, and is the goal of this investigation. Adult male rats were injected with Mn2+ at doses 1 mg/kg and 5 mg/kg in the form of MnCl2·4H2O, every other day for one-month to produce acute Mn neurotoxicity. For a half of rats Mn exposure was suspended for recovery for up to 5 months. Mn neurotoxicity was evaluated by the accumulation of Mn in blood and brain, behavioral activities, dopaminergic neuron loss, and the expression of Park2/Parkin in the blood cells and brain. Dose-dependent Mn neurotoxicity in rats was evidenced by Mn accumulation, rotarod impairments, reduction of tyrosine hydroxylase (TH)-positive neurons in the substantia nigra, decreased level of Park2 mRNA in the blood and brain, and decreased Parkin protein in the brain. After cessation of Mn exposure, the amount of Park2 mRNA in the blood started to increase one month after the recovery. After 5-month of recovery, blood and brain Mn returned to normal, rotarod activity recovered, the reduction of TH-positive dopaminergic neurons ameliorated, and the level of Park2 mRNA in the blood and Park2/Parkin in the midbrain and striatum were returned to the normal. Mn neurotoxicity in rats is reversible after cessation of Mn exposure. The level of Park2 mRNA in the blood could be used as a novel biomarker for Mn exposure and recovery.

Moniezia benedeni infection enhances neuromedin U (NMU) expression in sheep (Ovis aries) small intestine.

BACKGROUND: Neuromedin U (NMU) plays an important role in activating the group 2 innate lymphoid cells (ILC2s) and initiating the host's anti-parasitic immune responses. It is aimed to explore the distribution characteristics of NMU in the sheep small intestine and the influence of Moniezia benedeni infection on them. In the present study, the pET-28a-NMU recombinant plasmids were constructed, and Escherichia coli. BL21 (DE3) were induced to express the recombinant protein. And then, the rabbit anti-sheep NMU polyclonal antibody was prepared and immunofluorescence staining was performed with it. The expression levels of NMU in the intestine of normal and Moniezia benedeni-infected sheep were detected by ELISA. RESULTS: The results showed that the molecular weight of the obtained NMU recombinant protein was consistent with the expected molecular (13 kDa) and it was expressed in the form of inclusion body. The titer and specificity of obtained rabbit anti-sheep NMU polyclonal antibody were good. The results of immunofluorescence analysis showed that the nerve fibers which specifically expressed NMU mainly extended from the ganglion in the submucosal to lamina propria (LP) in the sheep small intestine, and the expression level was relatively high; especially on the nerve fibers of LP around the intestinal glands. The expression levels were gradually increased from the duodenum to the ileum, and the levels in the jejunum and ileum were significantly higher than that in the duodenum (P < 0.05). In addition, scattered NMU positive cells were distributed in the epithelium of the jejunal crypts. Moniezia benedeni infection increased the expression of NMU in each intestinal segment, especially in the jejunum and ileum there were significant increase (P < 0.05). CONCLUSIONS: It was suggested that Moniezia benedeni infection could be detected by the high expression of NMU in sheep enteric nervous, and which laid the foundation for further studies on whether NMU exerts anti-parasitic immunity by activating ILC2s. In addition, NMU was expressed in some intestinal gland epitheliums, which also provided a basis for studying its roles in regulation of the immune homeostasis. The present study laid the foundation for further revealing the molecular mechanism of sheep's neural-immune interaction network perceiving the colacobiosis of parasites.

Renoprotective activity of a new amide and a new hydroxycinnamic acid derivative from the fresh roots of Rehmannia glutinosa.

A new amide, named rehmagluamide (1), and a new hydroxycinnamic acid derivative, named nepetoidin F (2), together with six known compounds, 2'-O-methyluridine (3), puroglutamic acid (4), biliverdic acid (5), peterolactam (6), nicotinic acid (7), nicotinamide (8), were isolated from the fresh roots of Rehmannia glutinosa. All the structures of compounds were identified by the interpretation of their spectroscopic data and comparison with those reported in the literatures. The protective effects of compounds 1-7 on normal rat kidney tubule epithelioid (NRK-52e) cells injury induced by LPS were investigated. The results indicated that compounds 1, 2, and 7 exhibited protective effects against LPS-induced NRK 52e cells injury.

A survey regarding orthodontic treatment among contemporary college freshmen in China.

BACKGROUND: A growing number of Chinese residents are seeking orthodontic treatment. The aim of the study was to investigate rates of orthodontic publicity, orthodontic treatment history and related factors among college freshmen in China, to preliminarily understand the current situation of orthodontic publicity and treatment in China, especially after the 2020s. METHODS: Referred to previous studies, a self-designed online questionnaire of Chinese college freshmen was conducted. The questionnaire was divided into two parts, after collecting basic information, we investigated orthodontic publicity rate and orthodontic treatment history with starting age, relapse phenomenon, satisfaction score and willingness to re-treatment. Factors hindering first-time and second-time treatment were also collected. The statistical analysis was performed using the Chi-square test, t-test, Kruskal-Wallis test and logistic regression analysis. RESULTS: The response rate was 100% and 3308 responses were included. The male to female ratio was 1524:1784 with a mean age of 18.43 years (SD 0.91 years). Statistically significant of economic administrative regions, age, major and orthodontics engagement of relatives or friends were found on prevalence and rate of orthodontic treatment (P < 0.05). Average opinion on orthodontic treatment was "satisfied" and most claimed a phenomenon of relapse (slight relapse: 38.22%, obvious relapse: 23.12%), where age, major and orthodontics engagement of relatives or friends showed statistically significant. Retreatment willingness was correlation with start age and relapse phenomenon. For those who refused first-time treatment, except for good tooth arrangement condition, pain, long-time span, and cost weighted, while for those who refused re-treatment, the fair of discomfort and long-time span ranked at the top. CONCLUSIONS: In contemporary China, the prevalence and rate of orthodontic treatment had been greatly promoted. Earlier age for receiving orthodontic treatment was also discovered. Subjective factors regarding psychology, self-requirement affected the need of orthodontic treatment. Contemporary Chinese college freshmen had a high ability of judging dental alignment, while improve of overall orthodontic care level is still required.

Protection of Ag Clusters by Metal-Oxo Modules.

Monodisperse and atomically precise Ag nanoclusters have attracted considerable recent research interest. A conventional silver cluster usually consists of a silver metallic kernel and an organic peripheral ligand shell. Nevertheless, the present inevitable problem is the unsatisfied stability of such nanoclusters. In this concept, we will give an introduction to Ag clusters protected by metal-oxo modules, which exhibit enhanced stability and unique properties. Accordingly, three different types of clusters are summarized: (1) Ag clusters protected by mononuclear oxometallates; (2) Ag clusters protected by block-like metal-oxo clusters; (3) Ag clusters protected by hollow-like metal-oxo clusters. The aim of this concept is to offer possible general guidance and insight into future rational design of more metal-oxo clusters protected silver clusters or even other coinage metal nanoclusters.

Transcriptome analysis and physiological indicators reveal the role of sulfur in cadmium accumulation and transportation in water spinach (Ipomoea aquatica Forsk.).

Cadmium (Cd) contamination of croplands has become a threat to crop food safety and human health. In this study, we investigated the effect of sulfur on the growth of water spinach under Cd stress and the amount of Cd accumulation by increasing the soil sulfate content. We found that the biomass of water spinach significantly increased after the application of sulfur while the shoot Cd concentration was considerably reduced (by 31%). The results revealed that sulfur could promote the expression of PME and LAC genes, accompanied by an increase in PME activity and lignin content. Also, the cell wall Cd content of water spinach roots was significantly increased under sulfur treatment. This finding suggests that sulfur could enhance the adsorption capacity of Cd by promoting the generation of cell wall components, thereby inhibiting the transportation of Cd via the apoplastic pathway. In addition, the higher expression of Nramp5 under the Cd1S0 (concentration of Cd and sulfur are 2.58 and 101.31 mg/kg respectively) treatment led to increased Cd uptake. The CAX3 and ABC transporters and GST were expressed at higher levels along with a higher cysteine content and GSH/GSSR value under Cd1S1 (concentration of Cd and sulfur are 2.60 and 198.36 mg/kg respectively) treatment, which contribute to the Cd detoxification and promotion of Cd compartmentalization in root vacuoles, thereby reducing the translocation of Cd to the shoot via the symplastic pathway.

Threefold Collaborative Stabilization of Ag14 -Nanorods by Hydrophobic Ti16 -Oxo Clusters and Alkynes: Designable Assembly and Solid-State Optical-Limiting Application.

Ag nanoclusters have received increasing attention due to their atomically precise and diverse structures and intriguing optical properties. Nevertheless, the inherent instability of Ag nanoclusters has seriously hindered their practical application. In this work, for the first time, Ag clusters are collaboratively protected by hydrophobic Ti-oxo clusters and alkyne ligands. Initially, a pyramidal Ag5 cluster terminated with t BuC≡C- and CH3 CN was inserted into the cavity of a Ti8 -oxo nanoring to form Ag5 @Ti8 . To overcome the instability of acetonitrile-terminated silver site, such two Ag5 @Ti8 clusters could sandwich an Ag4 unit to form Ag14 -nanorod@Ti16 -oxo-nanoring (Ag14 @Ti16 ), which is peripherally protected by fluorophenyl groups and alkyne caps. This threefold protected (hydrophobic fluorinated organic layer, Ti-O shell, and terminal alkyne ligands) Ag14 @Ti16 exhibits superhydrophobicity and excellent ambient stability, endowing it with solid-state optical limiting characteristics.

Snijders Blok-Campeau syndrome caused by CHD3 gene mutation: a case report. / CHD3åŸºå› çªå˜è‡´Snijders Blok-Campeau综合征1例报告.

A one-year and two-month old girl indicated large head circumference, widely spaced eyes, narrow palpebral fissures, strabismus on the right eye, broad and low nasal bridge and low-set ears. She had knee over extension and foot eversion on both sides while standing with help. She also had hypotonia and was not able to stand or walk independently. She can say "ma ma" unconsciously. In the neuropsychological developmental assessment, delayed development was shown on gross motor function, fine movement, adaptive capacity, speech and social behavior function. A de novo heterozygous mutation, c.3872G>A(p.G1291D), likely pathogenic, was detected in the CHD3 gene via the next generation sequencing. Snijders Blok-Campeau syndrome was confirmed. It is an extremely rare disease with only 60 cases reported globally. This case expands the CHD3 gene mutation sites and suggests that rare diseases need to be considered and genetic tests should be performed in children with intellectual developmental delay and abnormal facial features, so as to help early diagnosis. Citation.

Chronic Manganese Administration with Longer Intervals Between Injections Produced Neurotoxicity and Hepatotoxicity in Rats.

Subacute exposure to manganese (Mn) produced Parkinson's disease-like syndrome called Manganism. Chronic onset and progression are characteristics of Manganism, therefore, this study aimed to examine Mn toxicity following chronic exposures. Male Sprague-Dawley rats were injected Mn2+ 1 and 5 mg/kg, every 10 days for 150 days (15 injections). Animal body weight and behavioral activities were recorded. At the end of experiments, the brain and liver were collected for morphological and molecular analysis. Chronic Mn exposure did not affect animal body weight gain, but the high dose of Mn treatment caused 20% mortality after 140 days of administration. Motor activity deficits were observed in a dose-dependent manner at 148 days of Mn administration. Immunofluorescence double staining of substantia nigra pars compacta (SNpc) revealed the activation of microglia and loss of dopaminergic neurons. The chronic neuroinflammation mediators TNFα, inflammasome Nlrp3, Fc fragment of IgG receptor IIb, and formyl peptide receptor-1 were increased, implicating chronic Mn-induced neuroinflammation. Chronic Mn exposure also produced liver injury, as evidenced by hepatocyte degeneration with pink, condensed nuclei, indicative of apoptotic lesions. The inflammatory cytokines TNFα, IL-1ß, and IL-6 were increased, alone with stress-related genes heme oxygenase-1, NAD(P)H:quinone oxidoreductase-1 and metallothionein. Hepatic transporters, such as multidrug resistant proteins (Abcc1, Abcc2, and Abcc3) and solute carrier family proteins (Slc30a1, Slc39a8 and Slc39a14) were increased in attempt to eliminate Mn from the liver. In summary, chronic Mn exposure produced neuroinflammation and dopaminergic neuron loss in the brain, but also produced inflammation to the liver, with upregulation of hepatic transporters.

One-Pot and Postsynthetic Phenol-Thermal Synthesis toward Highly Stable Titanium-Oxo Clusters.

The synthetic approach plays a crucial role for the exploration and optimization of functional materials. As the molecular models of titanium dioxide, polyoxo-titanium clusters have undergone rapid development over past decade. Unfortunately, many of them are unstable, especially in aqueous environments, greatly limiting their applications in catalysis and environmental fields. In this work, we report a novel phenol-thermal approach toward the construction of highly stable polyoxo-titanium clusters. In addition to the traditional one-pot procedure, the phenol-thermal synthesis can also be used as a postsynthetic pathway to modify the alcohol terminated titanium-oxo clusters. During the modification in phenol, Ti-O core structures consisting entirely of 6-coordinated TiIV centers can be retained. Nevertheless, isopropanol terminated 5-coordinated TiIV centers are not stable and reconstructed to 6-coordinated TiIV centers during the phenol-thermal modification to form new Ti-O clusters. Physical attribute studies confirm that the obtained phenolic clusters generally display much better stability and stronger visible light absorption than isopropanol stabilized clusters with identical or similar cores. Therefore, phenol can not only offer a suitable solution environment for the construction of new cluster structures but also provide robust protection for the cluster cores and also an efficient method to enhance their visible light responses.

Isomerism in Titanium-Oxo Clusters: Molecular Anatase Model with Atomic Structure and Improved Photocatalytic Activity.

Phase isomerism is a common and important phenomenon in inorganic materials, but the molecular isomerism of their nanocluster models is still rare. In this work, we report the first pair of isomeric titanium-oxo clusters. Through combining pentagonal {Ti(Ti5 )} building units in corner-sharing or edge-sharing forms, the two obtained Ti20 -oxo clusters take vertical and horizontal core configurations, respectively, which are both functionalized by the same organic ligands. More interestingly, the vertical type Ti20 -oxo core contains an identical {Ti8 O14 } moiety as anatase, making it the first molecular model of anatase TiO2 . As a result, the vertical type cluster exhibits better photocatalytic H2 evolution activity, higher photocurrent response and faster charge transfer to external acceptors than its horizontal isomer. Thus, this work provides a cluster isomer method to understand the structure-property relationship of import titanium oxide materials.

Dicarboxylate Ligands Oriented Assembly of {Ti3(µ3-O)} Units: From Dimer to Coordination Triangles and Rectangles.

A series of dicarboxylates bridged titanium-oxo clusters with {Ti3(µ3-O)} building units have been synthesized through facile one-step solvothermal reactions. It is interesting to find that the geometric characteristics of the obtained supramolecular structures highly depend on the configuration of the applied dicarboxylate ligands. A linear dimeric [Ti3O]2L2 complex can be constructed using flexible cyclohexanedicarboxylic acid, while the introduction of rigid 2-nitro-1,4-benzenedicarboxylic acid gives rise to a triangular [Ti3O]3L3 structure. Moreover, unusual [Ti3O]4L4 rectangles have been achieved with more symmetric 5-nitro-1,3-benzenedicarboxylic acid or terephthalic acid. Furthermore, a photochromic effect is observed on the obtained complexes upon UV-vis light irradiation in the presence of alcohol.