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An unprecedented cobaloxime-based zirconium metal–organic framework (Zr-TCPCo) is designed and synthesized, which exhibits excellent catalytic activity for aerobic oxidation of arylboronic acids to phenols as a photocatalyst.

By facile calcination, we successfully prepared CDs@MOF composites via self-carbonization in defect-containing MOFs, achieving photoluminescence fine tuning and effective sensing of picric acid.

Through a geometrically guided approach, i.e. with the aid of pyridyl modulators, the long-sought MIL-101(Mn) structure is finally achieved, which features emergent topologically correlated mixed-valence states that are apt for enzymatic catalysis.

Antimony halide hybrids have been recently revealed to show reversible solvent-induced phase transformation along with solvatochromic photoluminescence (PL). However, the effects of guest molecules...

Antimony-based metal halide hybrids have attracted enormous attention due to the stereoactive 5s2 electron pair that drives intense triplet broadband emission. However, energy/charge transfer has been rarely achieved for Sb3+-doped materials. Herein, Sb3+ ions are homogeneously doped into 2D [NH3(CH2)4NH3]CdBr4 perovskite (Cd-PVK) using a wet-chemical method. Compared to the weak singlet exciton emission of Cd-PVK at 380 nm, 0.01% Sb3+-doped Cd-PVK exhibits intense triplet emission located at 640 nm with a near-unity quantum yield. Further increasing the doping concentration of Sb3+ completely quenches singlet exciton emission of Cd-PVK, concurrently with enhanced Sb3+ triplet emission. Delayed luminescence and femtosecond-transient absorption studies suggest that Sb3+ emission originates from exciton transfer (ET) from Cd-PVK host to Sb3+ dopant, while such ET cannot occur with Pb2+-doped Cd-PVK because of the mismatch of energy levels. In addition, density function theory calculations indicate that the introduced Sb3+ likely replace the Cd2+ ions along with the deprotonation of butanediammonium for charge balance, instead of generating Cd2+ vacancies. This work provides a deeper understanding of the ET of Sb3+-doped Cd-PVK and suggests an effective strategy to achieve efficient triplet Sb3+ emission beyond 0D Cl-based hybrids.

Xiao-Chun Huang,1,2 Fei-Xiong Pang,1,2 Sheng-Song Ou,1,2 Xiao-Jiao Wei,1,2 Yu-Ju Xu,1,2 Yan-Hua Lai1,2 1Department of Transplantation, People’s Hospital of Guangxi Zhuang Autonomous Region, Nanning, Guangxi, 530021, People’s Republic of China; 2Guangxi Academy Of Medical Sciences, Nanning, Guangxi, 530021, People’s Republic of ChinaCorrespondence: Yan-Hua LaiDepartment of transplantation, People’s Hospital of Guangxi Zhuang Autonomous Region, No. 6 Taoyuan Road, Nanning, Guangxi Zhuang Autonomous Region, 530021, People’s Republic of ChinaTel +86 13978798471Email 1379771812@qq.comPurpose: Liver transplantation (LT) currently yields the best outcomes for hepatocellular carcinoma (HCC). However, tumor recurrence still occurs in some patients. Identifying markers that predict HCC recurrence after LT is an unmet medical need.Methods: In this study, differential expression analysis was used to identify differentially expressed microRNAs (DEmiRs) between HCC and liver tissues in the The Cancer Genome Atlas database and in data from patients with recurrent or non-recurrent HCC in the GSE64989 dataset. The expression profiles of the overlap DEmiRs were used to construct an miRNA-based risk score to predict prognosis using Cox regression analysis. The target genes of the miRNAs of interest were predicted, and they were analyzed for functional enrichment. Furthermore, we used the miRNAs of interest to construct a competitive endogenous RNA (ceRNA) network of long non-coding RNAs (lncRNAs), miRs and mRNAs.Results: Four up-regulated and three down-regulated miRNAs in HCC and recurrent HCC after LT were considered as candidate miRs. MiR-3200-3p and miR-3690 were selected to construct the miR-based risk score, which was found to be associated with poor overall survival and progression-free survival. Furthermore, it proved to be an independent prognostic factor after adjusting for other clinicopathological factors. The corresponding ceRNA networks of these two miRs that we constructed may help to understand their regulatory mechanisms in HCC.Conclusion: We propose a risk score based on miR-3200-3p and miR-3690 that may be useful as a prognostic marker to predict HCC recurrence after LT. We generated a ceRNA network involving these miRNAs, which may help reveal their regulatory roles in HCC.Keywords: hepatocellular carcinoma, liver transplantation, microRNA, recurrence, ceRNA network

Methane, as the main component of natural gas, shale gas, and marsh gas, is regarded as an ideal clean energy to replace traditional fossil fuels and reduce carbon emissions. Porous materials with superior methane storage capacities are the key to the wide application of adsorbed natural gas technology in vehicle transportation. In this work, we applied a ligand tailoring strategy to a metal-organic framework (NOTT-101) to fine-tune its pore geometry, which was well characterized by gas and dye sorption measurements. High-pressure methane sorption isotherms revealed that the methane storage performance of the modified NOTT-101 can be effectively improved by decreasing the unusable uptake at 5 bar and increasing the total uptake under high pressures, achieving a substantially high volumetric methane storage working capacity of 190 cm

Low-dimensional hybrid lead halide perovskites (LHPs) with broadband emission (BE) have been developed as promising candidates for single-source white-light-emitting diodes. However, the underlying origin of such BE is poorly understood. Herein, dual-emissive [NH3(CH2)8NH3]PbBr4 perovskite microsheets (PMSs) with good dispersibility are successfully prepared. Besides the general narrowband emission (NE) originating from free excitons, BE (∼522 nm) is generated under a Br-poor condition, which is not observed in the single-crystal sample. Unlike self-trapped exciton emission, the BE observed in PMSs is experimentally determined to be related to bromide vacancies (VBr), thereby exhibiting quasisaturation under high excitation intensity. Femtosecond transient absorption spectroscopy first shows that the trapping time of the photogenerated electrons by acceptor-like VBr- is ∼15 ps, slower than that by surface defects (

Antimony-based metal halide hybrids have attracted enormous attention due to the stereoactive 5s

Here it is demonstrated that the tetraphenylethene moiety, a typical AIE luminogen, can act as a receptor instead of a transducer in a MOF to enable turn-on ammonia detection. The CuI-based MOF, normally vulnerable to ammonia attack, is protected by network entanglement and shows good stability, selectivity and recyclability. Moreover, it is demonstrated that the AIE phenomenon usually active in solution is also valid at the solid–liquid interface, and the AIEgen works even better in a MOF than in solution for calibrating solvent viscosity with a favorable linear response.

The practical value of metal–organic frameworks (MOFs) which harness great momentum in influencing various fields will be significantly increased if the materials are inexpensive, eco-friendly and can be manufactured at a large scale. Calcium MOFs that satisfy such demands but remain rarely studied in terms of the general applicability of their scale-up synthesis have been investigated in this work. A convenient, low-cost and eco-friendly method for rapid, large-scale synthesis (ca. 80% yield, over 50 000 kg m−3 per day within 1 min) has been proposed for the production of seven Ca–MOFs with diverse rod/layer-like building units and overall topologies, including a new one (ROD-94) with a rare underlying net. Moreover, one of the products (ROD-95) has been demonstrated to be capable of detecting and quantitatively measuring the water contents in commercial organic solvents (DMF, EtOH and THF) with LOD values of around 1%, and a fluorescent test paper has been implemented accordingly.

In this work, a new two-dimensional Cd-based (F2CHCH2NH3)2CdBr4 perovskite (Cd–P) with indirect bandgap and a direct Pb-based (F2CHCH2NH3)2PbBr4 (Pb–P) are successfully synthesized with isostructur...

In the evolution of metal-organic frameworks (MOFs) for carbon capture, a lasting challenge is to strike a balance between high uptake capacity/selectivity and low energy cost for regeneration. Meanwhile, these man-made materials have to survive from practical demands such as stability under harsh conditions and feasibility of scale-up synthesis. Reported here is a new MOF, Zn(imPim) (aka. MAF-stu-1), with an imidazole derivative ligand, featuring binding pockets that can accommodate CO2 molecules in a fit-like-a-glove manner. Such a high degree of shape complementarity allows direct observation of the loaded CO2 in the pockets, and warrants its optimal carbon capture performances exceeding the best-performing MOFs nowadays. Coupled with the record thermal (up to 680 °C) and chemical stability, as well as rapid large-scale production, both encoded in the material design, Zn(imPim) represents a most competitive candidate to tackle the immediate problems of carbon dioxide capture.

In this work, Mn2+ has been efficiently and homogeneously doped into two-dimensional (2D) distorted single-layered EA2PbBr4 (EA: ethylammonium) via a reprecipitation method. Both the doped and undo...

Shape complementarity is a biological craft for precisely binding substrates at protein-protein interfaces. An analogy to such a function can be drawn conceptually for crystalline porous solids; yet the manifested entities are rare in reticular chemistry. The bottleneck-shaped pores carved out of a metal-organic framework, Zn(MIBA)2 (aka. MAF-stu-13), can perfectly accommodate benzene molecules. Remarkably, its framework adapts to the optimal guest binding-the enhanced host-guest interactions in the neck in turn minimize the guest-guest repulsion in the pore to the extent it turns into attraction-as demonstrated by the combined X-ray structural and DFT computational studies. This adaptive material can be used for liquid-phase production of ultrahigh-purity (≥99 %) cyclohexane, achieving a balance between uptake capacity and separation selectivity and surpassing the performances of other porous and nonporous crystals reported recently (e.g. product purity 99.4 % vs. 97.5 % to date).

The selective oxidation of primary thioethers to sulfoxides is an important reaction in the production of pharmaceuticals, agrochemicals, and other valuable fine chemicals. However, the achievement of high conversion and selectivity towards sulfoxide during thioether oxidation under mild conditions still remains a great challenge. In this study, we found a new method to overcome the abovementioned challenge by applying the C60@PCN-222 composite as a catalyst in the photo-oxidation of thioethers. The C60@PCN-222 composite was obtained by the integration of guest C60 molecules and a porous porphyrin-based metal–organic framework (MOF), PCN-222; we proposed that the photogenerated electron–hole separation of PCN-222 could be significantly enhanced through the encapsulation of C60 molecules with a large, highly delocalized π-conjugation, which provided a great contribution to the high conversion and selectivity of this type of reaction. Under air and low optical power (50 mW cm−2) conditions at room temperature, the composite exhibited excellent catalytic performance; we further explored the underlying mechanism of action of this photocatalyst by investigating the reactive oxygen species via ESR spectral analysis and adjusting the experimental conditions. It has been revealed that superoxide radicals, generated by electron transfer from a photoexcited MOF to the C60 molecules, serve as the main active species for the oxidation.

Phosphorus with concentration above a few ppm in waters can easily cause eutrophication and poor water quality (e.g. algal blooming). In this study, we synthesized a non-porous gadolinium terephthalic acid (Gd-PTA) metal-organic framework (MOF) for efficient and rapid removal of phosphorus. Gd-PTA was prepared with gadolinium as the core metal center and terephthalic acid as the organic ligand, by which a well defined structure of new MOF was established. The adsorption isotherm and kinetics were well described by Langmuir isotherm equation and the intraparticle surface diffusion model, respectively. The maximum adsorption capacity was as high as 206.13- PO

Metal nanoparticles (NPs) stabilized by MOFs are very promising for catalysis, whereas introduction of C60 into MOFs has been very rarely used, and there was no report for their cooperative catalysis in organic syntheses. In this work, C60 @UiO-67 was synthesized by a one-pot method, so that C60 is uniformly distributed on UiO-67 in molecular form. Pd NPs coordinating with C60 have been successfully embedded into the framework. The obtained multifunctional C60 Pdn @UiO-67 catalyst exhibits remarkable synergistic catalytic activity in cascade reactions under mild conditions, where UiO-67 affords Lewis acidity and C60 Pdn offers higher hydrogenation activity relative to solely Pd NPs.

The title MOF features a potential uninodal zeolite net, uks, which has never been found for real zeolites or zeolite-like MOFs. This rare structure exhibits specific anion binding of N3- over SCN- in water, which reverses the Hofmeister series.

A series of Cu4I4 clusters (1–5) supported by two pyrazolate-type zwitterionic ligands N-methyl-[4-(5-R-pyrazolyl)]pyridinium (1: R = tert-butyl; 2: R = trifluoromethyl; 3, 4, 5: R = phenyl) have been prepared and fully characterized. These compounds all exhibit a distorted “octahedral” geometry and their luminescence behavior is quite distinct from those of previously reported tetranuclear copper halide clusters. The crystalline powders of all five clusters only show a single broad low-energy (LE) emission band from 300 to 80 K. Cluster 1 shows temperature-independent orange phosphorescence despite a slight blue-shift of the low-energy flank upon cooling. Intriguingly, for clusters 2–5, a hypsochromic phenomenon is clearly observed by decreasing the temperature. Using DFT/TDDFT calculations, we find that the nature of the electronic transitions responsible for the LE emission is dominated by the steric demand and/or electronic characteristics of the substituents on the pyrazolyl moiety. Specially, contribution of cuprophilic interactions in the lowest triplet excited states is ruled out by the rigid ligands. The single LE emission of 1 and 2 is attributed to pure 3ILCT and 3(M + X)LCT transitions, respectively, while the emission of 3 and 4 is assigned to a mixed 3ILCT and 3(M + X)LCT transition with different proportions.

As the main organic pollutants in wastewater, antibiotics and organic dyes are harmful to the environment and public health, and their removal is important but challenging. In this work, highly porous 3D metal-organic frameworks (MOFs) [M2 (PDAD)(H2 O)]n (PCN-124-stu; M=Cu, Zn; H4 PDAD = 5,5'-(pyridine-3,5-dicarbonyl)bis(azanediyl)diisophthalic acid) were synthesized, and PCN-124-stu(Cu) shows excellent chemical and thermal stability. PCN-124-stu(Cu) was used as a host for efficient extraction of various organic dyes, especially the large-molecule dye Coomassie brilliant blue, and fluoroquinolones from water, in comparison with five common MOFs, zeolite 13X, and activated carbon. PCN-124-stu(Cu) exhibits absolute predominance for fluoroquinolone adsorption among these microporous materials because of the H-bonds between fluoroquinolone molecules and the amide groups in the frameworks, except for MIL-100(Cr), which is a mesoporous MOF. Moreover, PCN-124-stu(Cu) could release fluoroquinolones slowly in physiological saline and retained its framework structure after four adsorption/desorption cycles. In addition, PCN-124-stu(Cu) can be used as a platform for selective adsorption of CO2 /CH4.

In this work, a new two-dimensional Cd-based (F

In this work, four kinds of two-dimensional single-layered F-substituted ethylammonium lead halide perovskites (LHPs, (FxCH3–xCH2NH3)2PbBr4, x = 0, 1, 2, and 3) are successfully synthesized. The in...

In this paper, we will discuss how to calculate Floquet multipliers of non-smooth dynamical systems which are continuous or discontinuous. The saltation matrix of discontinuous system plays an important role when computing the Floquet multipliers. In addition, a special periodic solution, semi-limit cycle, will be presented. We find that the stability of this periodic solution cannot be analyzed by the classical Floquet theory. More investigation is needed to enrich the theory of Floquet multipliers to non-smooth systems.

A family of three-periodic nets formed from intersecting helical ladders (double helices) is described. Tilings and ring sizes are analyzed. Removal of the rungs of the ladders results in periodic patterns of linked rings (three-periodic “chain mail”). A related family of nets formed from triple helices leads similarly to interwoven threads.

It is still a very challenging work to develop new and more effective methods for detecting Hepatitis B virus (HBV). In this work, a new simple electrochemical biosensor with high sensitivity and stability was constructed for detecting HBV DNA by combining the electroactive Cu-MOF as a signal nanoprobe and multi-site matrix and electroreduced graphene oxide (ErGO) as signal amplification material. Cu-MOF exhibits good affinity to probe DNA through covalent attachment, which can further stabilize DNA probe. The probe DNA density and the hybridization efficiency of this electrochemical DNA biosensor was 9.48 × 1013 molecules cm−2 and 89.9%, respectively. Under optimal conditions, the electrochemical DNA biosensor had an excellent performance toward HBV DNA determination with a wide linear range of 50.0 fM to 10.0 nM, and a low limit of detection (LOD) of 5.2 fM, more sensitive than other reported electrochemical HBV DNA biosensors. Moreover, the new sensor was used to measure HBV DNA in human serum and urine samples with sound results. This work also provides some insights for the construction of other electrochemical DNA biosensors.

Metal nanoparticles (NPs) stabilized by MOFs are very promising for catalysis, whereas introduction of C

As the main organic pollutants in wastewater, antibiotics and organic dyes are harmful to the environment and public health, and their removal is important but challenging. In this work, highly porous 3D metal-organic frameworks (MOFs) [M

A tetradecanuclear copper(I) cluster compound, namely [Cu6L3(Cu2I2)Cu6L3] (H2L = 3,5-bis((3,5-dimethyl-pyrazol-4-yl)methyl)-2,6-dimethylpyridine), is synthesized. The high thermal stability, well-resolved blue/red dual emissions and two-way luminescent thermochromism warrant its self-calibrated temperature sensing ability, covering a wide range (120-450 K). These promising results are supported by combined structural, spectral and computational studies.

Ethnopharmacological relevance Tripterygium hypoglaucum (levl.) Hutch ( Celastraceae ) (THH) root is a traditional Chinese medicinal herb commonly used for treating autoimmune diseases and cancer. Alkaloid is one of the most bioactive components of THH extract. To evaluate the in vitro and in vivo antitumor properties of the total alkaloids of THH (THHta). Materials and methods THHta was extracted in pilot-scale. HCT116 cells were chose to establish human colon cancer xenograft model. The in vitro anti-tumor activity of THHta was tested by Cell malignant transformation test, Soft agar colony formation assay and MTT assay. The in vivo anti-tumor effect of THHta was confirmed by xenograft mouse model. THHta-induced apoptosis was examined by flow cytometry. The levels of apoptosis-related proteins were investigated by Western blot. Results TPA-induced cell transformation was significantly inhibited by THHta in JB6 Cl41 cells. THHta inhibits the growth of colon cancer cells in vitro in a significant dose-dependent manner. Compared to the control set, i.p. administration of THHta to xenograft mice significantly reduced both tumor weight and volume. Apoptosis induction of THHta was mediated by activation of caspase-3, PARP and inhibiting of Bcl-2, Bcl-xL and XIAP. Conclusion THHta was effective in inhibiting tumor growth both in vitro and in vivo at less toxic concentrations by inducing apoptosis which suggested it could be developed as a potential anticancer agent.

In solar applications, collectors are usually installed with a tilt angel to obtain the maximum amount of radiation. In this paper, the anisotropic model -Hay model was used to calculate the daily total radiation on the tilt face and theoretical analysis was used to get the optimum tilt angel of southern collector face in winter months. Then the diffused radiation on horizontal face was obtained by using the isolation between daily total radiation and daily diffused radiation. Computer program was written to calculate the month radiation under different tilt angel and the maximum angel corresponding to the maximum month radiation was found. At last, the two results were compared and analyzed.

In order to explore the influence law of the uneven covering layer foundation on lock chamber structure, used the large-scale finite element software called ANSYS, chosen the first hub lock chamber on Guxue Hydroelectric Power Station which was under construction as research object, constructed a lock chamber model which had thickness variations of covering layer along the dam axis direction, calculated the results of displacement and stress distribution on lock chamber, the analysis showed that; the uneven covering layer only has impact on the displacement along thickness variation and vertical direction of the lock chamber, the affecting factor of the stress distribution on lock chamber is the size of the corresponding covering layer gap under the floor; the lock chamber deformation amount meets the operational requirements, the reinforcement on the floor of number (3) lock chamber should be strengthened, to meet structural stability requirements, it only need to have the minimum reinforcement rate reinforcement for the other two lock chamber floor and all the gate piers.

A rod-packing, breathing MOF (1), with two crystalline structural intermediates (1 a and 1 b; H(2) btca = benzotriazole-5-carboxylic acid) has been investigated. An underlying net approach for analyzing possible breathing MOFs, and a set of geometric parameters that can quantitatively describe such a breathing structural feature, are suggested. The 3D luminescent MOF is a promising candidate for specific sensors with exceptional sorption capacity.

Two coordination compounds, Cu(pim) (1) and Cu2(ppt)·1.5H2O (2) (Hpim = 2-(4-pyridyl)-imidazole, H2ppt = 5-(4-pyridyl)-1H-1,2,4-triazole-3-thiol), based on ligands with a “T”-shaped structural unit were reported here. 1 presents a 2D layer network, whereas 2 shows a MOF containing a 1D tubular channel, which are constructed utilizing a similar unit to the 2D layer in 1, representing a new strategy to construct tubular frameworks. Furthermore, basic properties such as photoluminescence and gas adsorption have been investigated as well.

Please cite this paper as: Li et al. (2012) Immunogenicity and safety of a 2009 pandemic influenza A (H1N1) monovalent vaccine in Chinese infants aged 6–35 months: a randomized, double-blind, controlled phase I clinical trial. Influenza and Other Respiratory Viruses DOI: 10.1111/irv.12028. Objectives The goal of this double-blind, randomized, controlled clinical trial was to assess the safety and immunogenicity of two different doses of a monovalent split-virion 2009 pandemic influenza A/H1N1 vaccine without adjuvant in Chinese infants aged 6-35 months. Design and setting Subjects were randomly assigned to receive either a 2009 pandemic (H1N1) vaccine containing 7.5 or 15 μg haemagglutinin (HA) or a seasonal influenza vaccine. 2 doses of the H1N1 vaccines or the seasonal influenza vaccine were given 21 days apart in younger infants aged 6-23 months or older infants aged 24-35 months. Sample Serum samples were collected immediately before the first injection and before and 21 days after the second injection. Main outcome measures Primary outcomes were haemagglutinin inhibition (HI) antibody responses 21 days following each vaccination. Safety was monitoring throughout the study. Results The first vaccination of 7.5 μg and 15 μg H1N1 vaccine induced seroprotective antibody titers (HI titers ≥ 1: 40) in 42.9-57.4% of younger infants and 49.1-61.0% older infants. Immune responses after completion of the two dose schedule were comparable in both age groups with seroprotective rates of 91-98% in each vaccine and age group and GMTs of 173-263. The H1N1 vaccine elicited similar rates of local and systemic adverse reactions as the seasonal influenza vaccine. Conclusions The 2009 pandemic influenza A /H1N1 vaccine were highly immunogenic in infants aged 6-35 months, and displayed a safety and reactogenicity profile similar to the seasonal influenza vaccine. Trial registration ClinicalTrial.gov identifier: NCT01047202

The interaction of various gas molecules including H2, N2, O2 (in triplet and singlet), and H2O on the geometrical structures, energies, and electronic structures with open edges of zigzag (10, 0) ...

A novel electrochemical strategy was proposed for detection of 2,4-Dichlorophenol (2,4-DCP) at fabricated carbon fiber microelectrode (CFME). The resultant CFME was characterized using scan electron microscopy (SEM) and cyclic voltammetry (CV). Upon addition of surfactant TritonX-100 in analytical system, the electrochemical signal of 2,4-DCP was obviously increased. Under the optimized conditions, the resulted CFME showed wide linear range for 2,4-DCP from 3.0×10-8to 1.8×10-6M with the detection limit of 1.0×10-8M (S/N = 3). The proposed method is simple, low-cost and convenient and will be a promising alternative for CFME fabrication.

A detailed theoretical study of the potential energy surface of poorly understood ion-molecule reaction of NH(2)(-) and O(2) (a(1)Δ(g)) is explored at the density functional theory B3LYP/6-311++G(d,p), ab initio of QCISD/6-311++G(d,p) and CCSD(T)/6-311++G(3df, 2pd) (single-point) theoretical levels for the first time. It is shown that there are six total possible products from P(1) to P(6) on the singlet potential energy surface. Among these, the charge-transfer product P(1) (NH(2) + O(2)(-)) is the most favorable product with predominant abundances, whereas P(4) (NO(-) + H(2)O) and P(2) (HNO + OH(-)) may be the second and third feasible products followed by the almost neglectable P(3) (NO(2)(-) + H(2)), while P(5) (c-NO(2)(-) + H(2)) and P(6) (ONO(-) + H(2)) will not be observed due to their either high barriers or being secondary products. The present theoretical study points out that besides P(1) (NH(2) + O(2)(-)) and P(2) (HNO + OH(-)), P(4) (NO(-) + H(2)O) should be also observed, which is different from the previous experiment study by Anthony Midey et al. in 2008. In addition, almost all of the reaction pathways to products are exothermic and the reaction rate should be very fast since the reaction barriers are very low except for P(5) (c-NO(2)(-) + H(2)) which is in agreement with the measured total reaction rate constant k = 9.0 × 10(-10) cm(3)s(-1) at 300 K in the experiment study. It is expected that the present theoretical study may be helpful for the understanding of the reaction mechanism related to NHX(-), NX(2)(-), PHX(-), and PX(2)(-) (X = H, F, and Cl).

By systematically varying the geometric length and electronic properties of the second ligating ligands of halogen (Cl(-), Br(-), and I(-)) and pseudohalogen (CN(-), SCN(-), and N(3)(-)) anions, we synthesized 11 isomeric/isostructural copper(I) complexes: [Cu(2)(L3-3)I](n) (1), [Cu(2)(L4-4)Br](n) (2-Br), [Cu(2)(L4-4)Cl](n) (2-Cl), [Cu(2)(L3-4)(CN)](n) (3), [Cu(2)(L3-3)(CN)](n) (4), [Cu(3)(L4-4)(CN)(2)](n) (5), {[Cu(2)(L4-4)Br](2)·CuBr}(n) (6-Br), {[Cu(2)(L4-4)Cl](2)·CuCl}(n) (6-Cl), [Cu(2)(L4-4)(SCN)](n) (7α-SCN), [Cu(2)(L4-4)(SCN)](n) (7β-SCN), and [Cu(2)(L4-4)(N(3))](n) (7α-N(3)). These structures are based on a series of isomeric pyridylpyrazole ligands, namely, 3,5-bis(3-pyridyl)-1H-pyrazole (HL3-3), 3-(3-pyridyl)-5-(4-pyridyl)-1H-pyrazole (HL3-4), and 3,5-bis(4-pyridyl)-1H-pyrazole (HL4-4), and their structural features range from 1-D (1), 2-D (2), and 3-D noninterpenetration (3), to 3-D 2-fold interpenetration (4 and 5), to 3-D self-catenation (6 and 7), exhibiting a trend from simple to complex with dimension expansion and an interpenetrating degree increase. The five most complex structures (6 and 7) with self-catenated networks are based on 2-fold interpenetrated networks linked via appropriate second ligating spacers (Cl(-), Br(-), SCN(-), and N(3)(-)), representing a strategy to construct self-catenated coordination polymers through cross-linking interpenetrated frameworks. Moreover, these complexes exhibit strong photoluminescence, which is mainly ascribed to Cu(I)-related charge transfers (MLCT, MC, and MMLCT) regulated by the electronic properties of halogen or pseudohalogen. The topological evolution and luminescence variation presented in this work open an avenue to understanding the luminescence origin and the structure-property relationship of luminescent coordination polymers.

Candida infections have become an increasingly significant problem, mainly because of the widespread nature of Candida and drug resistance. There is an urgent need to develop new classes of drugs for the treatment of opportunistic Candida infections, especially in medically complex patients. Previous studies have confirmed that 2-amino-nonyl-6-methoxyl-tetralin muriate (10b) possesses powerful antifungal activity in vitro against Candia albicans. To clarify the underlying action mechanism, an oligonucleotide microarray study was performed in C. albicans SC5314 without and with 10b treatment. The analytical results showed that energy metabolism-related genes, including glycolysis-related genes (PFK1, CDC19 and HXK2), fermentation-related genes (PDC11, ALD5 and ADH1) and respiratory electron transport chain-related genes (CBP3, COR1 and QCR8), were downregulated significantly. Functional analysis revealed that 10b treatment increased the generation of endogenous reactive oxygen species, and decreased mitochondrial membrane potential, ubiquinone–cytochrome c reductase (complex III) activity and intracellular ATP levels in C. albicans SC5314. Also, addition of the antioxidant ascorbic acid reduced the antifungal activity of 10b significantly. These results suggest that mitochondrial aerobic respiration shift and endogenous reactive oxygen species augmentation might contribute to the antifungal activity of 10b against C. albicans. This information may prove to be useful for the development of new strategies to treat Candida infections.

One flexible star-shaped bridging molecule tris-(4-cyanophenyl)amine (TCPA) is synthesized from tris-(4-iodophenyl)amine by treatment with CuCN in hexamethylphosphorotriamide (HMPA) as a catalyst in high yield. Anion-template-controlled reactions of TCPA and silver salts give a series of coordination polymers (CPs) with various topological patterns. The complex [Ag(TCPA)(ClO4)]n·nC6H6 (1) forms an undulating 4.82 network, which displays unusual net entanglement. Two 4.82 nets interweave each other to give rise to 2-fold interpenetrating basic layers, which link together via double μ-Operchlorate bridging interactions. The complex [Ag(TCPA)(CF3SO3)]n·2nC6H6 (2) forms noninterpenetrating (6,3) nets. The solid state structure of [Ag3(TCPA)(CF3CO2)3]n·nCH2Cl2 (3) also is a (6,3) honeycomb network, differently, including a sphere-type Ag4(CF3CO2)62− cluster-anion in the host frameworks, which is a rare example of the host cationic network containing a guest cluster-anion. The complexes [Ag(TCPA)(BF4)·0.5H2O]n·...

A first example of 1D coordination polymer [MnTHPP·H2O·(DMF)2 (1)] with right-handed helicity and opticity was successfully assembled. Crystal analyses indicate that the right-handed helical assembly is based on coordination bonds from peripheral to center, associating with the saddle distortion of the molecular planes. In its crystal architecture, MnTHPP [manganese (III) ion coordinated by 5,10,15,20-tetra(4-hydroxyphenyl) porphyrin] molecules were ligated each other via the axial coordination between –PhO− → MnIII (peripheral to center model, from the peripherally deprotonated hydroxyphenyl to the central metal of the neighbor molecule) to construct the right-handed helices, and the helices are sustained by plentiful hydrogen bonding. Meanwhile DMF molecules are entrapped within the voids among the helices. This is a rare example of the multiporphyrin arrays with right-handed helices bearing opticity.