A General Synthesis of Nanostructured Conductive Metal-Organic Frameworks from Insulating MOF Precursors for Supercapacitors and Chemiresistive Sensors.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) are emerging as a unique subclass of layer-stacked crystalline coordination polymers that simultaneously possess porous and conductive properties, and have broad application potential in energy and electronic devices. However, to make the best use of the intrinsic electronic properties and structural features of 2D c-MOFs, the controlled synthesis of hierarchically nanostructured 2D c-MOFs with high crystallinity and customized morphologies is essential, which remains a great challenge. Herein, we present a template strategy to synthesize a library of 2D c-MOFs with controlled morphologies and dimensions via insulating MOFs-to-c-MOFs transformations. The resultant hierarchically nanostructured 2D c-MOFs feature intrinsic electrical conductivity and higher surface areas than the reported bulk-type 2D c-MOFs, which are beneficial for improved access to active sites and enhanced mass transport. As proof-of-concept applications, the hierarchically nanostructured 2D c-MOFs exhibit a superior performance for electrical properties related applications (hollow Cu-BHT nanocubes-based supercapacitor and Cu-HHB nanoflowers-based chemiresistive gas sensor), achieving over 225 % and 250 % improvement in specific capacity and response intensity over the corresponding bulk type c-MOFs, respectively.

Blocking RAGE expression after injury reduces inflammation in mouse model of acute lung injury.

BACKGROUND: Receptor for Advanced Glycated Endproducts (RAGE) plays a major role in the inflammatory response to infectious and toxin induced acute lung injury. We tested the hypothesis that a RAGE blocking antibody when administered after the onset of injury can reduce lung inflammation compared to control antibody. METHODS: Male and female C57BL/6 (WT) mice were used. Forty-six received lipopolysaccharide (LPS) and 26 PBS by nasal instillation on day one, repeated on day three. On day 2, 36 mice receiving LPS were divided into two groups of 18, one treated with 200 µg of non-immune isotype control IgG and the second group treated with 200 µg of anti-RAGE Ab, each dose divided between IV and IP. Ten of the 46 were not treated. On day 4, before euthanasia, mice were injected with fluorescein isothiocyanate (FITC) labelled albumen. BALF and serum samples were collected as well as lung tissue for immunohistochemistry (IHC). BALF was analyzed for cell (leukocyte) counts, for FITC BALF/serum ratios indicating pulmonary vascular leak, and for cytokines/chemokines using bead based multiplex assays. Quantitative IHC was performed for MPO and RAGE. RESULTS: Ten LPS mice showed minimal inflammation by all measures indicating poor delivery of LPS and were excluded from analysis leaving n = 11 in the LPS + IgG group and n = 12 in the LPS + anti-RAGE group. BALF cell counts were low in the PBS administered mice (4.9 ± 2.1 × 105/ml) and high in the LPS injured untreated mice (109 ± 34) and in the LPS + IgG mice (91 ± 54) while in comparison, LPS + anti-RAGE ab mice counts were significantly lower (51.3 ± 18 vs. LPS + IgG, P = 0.03). The BALF/serum FITC ratios were lower for the LPS + anti-RAGE mice than for the LPS + IgG mice indicating less capillary leakiness. Quantitative IHC RAGE staining was lower in the LPS + anti-RAGE ab mice than in the LPS + IgG treated mice (P = 0.02). CONCLUSIONS: These results describe a four-day LPS protocol to sustain lung injury and allow for treatment and suggests that treatment aimed at blocking RAGE when given after onset of injury can reduce lung inflammation.

Blocking RAGE improves wound healing in diabetic pigs.

Receptor for Advanced Glycated End-products (RAGE) is highly expressed in diabetes and impairs wound healing. We proposed that administering an antibody that blocks RAGE will hasten the healing of dorsal wounds in diabetic pigs compared with a non-immune IgG. Two purpose-bred diabetic (D) Yucatan minipigs (Sinclair, Auxvasse MO) each underwent 12 2 × 2 cm full thickness dorsal wounds: four wounds received decellularized porcine skin patches (Xylyx Bio, Bklyn NY): four anti-RAGE Ab (CR-3) infused patches, four saline infused patches and four wounds were left open. One pig received anti-RAGE Ab (CR-3) 1 mg/kg IM q 10 days and other received non-immune IgG. Wounds were measured at 2 and 4 weeks followed by euthanasia and wound harvesting. At 2 weeks few of the patches appeared to be incorporated into the wound. By 4 weeks all patches in pigs treated systemically with CR-3 were detached and the wounds almost healed. For all 24 wounds for both pigs regardless of presence of patch or type of patch, the average IgG treated pig wound size at 4 weeks was 69.2 ± 14.6% of initial size and the average CR-3 treated pig wound size was 40.9 ± 11.3% of initial size (P = 0.0002). Quantitative immunohistology showed greater staining for collagen in the CR-3 treated wounds compared with IgG treated. Staining was positive for RAGE, Mac, and IL-6 in the IgG treated wounds and negative in the CR-3 treated wounds. From these pilot experiments, we conclude that a RAGE blocking antibody given parenterally improved wound healing in a diabetic pig while patches were not effective.

Artificial Light-Harvesting System with White-Light Emission in a Bicontinuous Ionic Medium.

Artificial light-harvesting systems (ALHSs), which are closely related to Förster resonance energy transfer (FRET), are among the most attractive scientific topics during the past few decades. Specifically, binary ALHSs that are composed of a fluid donor and acceptor have a simplified composition and high number density of the donor units. However, largely due to the difficulty in obtaining a fluid donor, investigation of these systems is still quite limited, especially for the ionic systems. Herein, we report a new type of binary ALHS using an ionic naphthalimide (NPI) derivative as a donor, which shows greatly improved photoluminescence for its bicontinuous liquid structure. When blending with an acceptor such as rhodamine 6G or trans-4-[4-(dimethylamino)styryl]-methylpyridinium iodide, efficient FRET was confirmed by both experimental results and molecular dynamics simulations, with an energy transfer efficiency up to ∼90%. Tunable color, including white-light emission, was achieved by tuning the acceptor/donor ratio, opening the door for a variety of applications such as light-emitting diodes and photoluminescent inks.

Cardiomyocyte death in sepsis: Mechanisms and regulation (Review).

Sepsis­induced cardiac dysfunction is one of the most common types of organ dysfunction in sepsis; its pathogenesis is highly complex and not yet fully understood. Cardiomyocytes serve a key role in the pathophysiology of cardiac function; due to the limited ability of cardiomyocytes to regenerate, their loss contributes to decreased cardiac function. The activation of inflammatory signalling pathways affects cardiomyocyte function and modes of cardiomyocyte death in sepsis. Prevention of cardiomyocyte death is an important therapeutic strategy for sepsis­induced cardiac dysfunction. Thus, understanding the signalling pathways that activate cardiomyocyte death and cross­regulation between death modes are key to finding therapeutic targets. The present review focused on advances in understanding of sepsis­induced cardiomyocyte death pathways, including apoptosis, necroptosis, mitochondria­mediated necrosis, pyroptosis, ferroptosis and autophagy. The present review summarizes the effect of inflammatory activation on cardiomyocyte death mechanisms, the diversity of regulatory mechanisms and cross­regulation between death modes and the effect on cardiac function in sepsis to provide a theoretical basis for treatment of sepsis­induced cardiac dysfunction.

Clinico-histopathologic and single-nuclei RNA-sequencing insights into cardiac injury and microthrombi in critical COVID-19.

Acute cardiac injury is prevalent in critical COVID-19 and associated with increased mortality. Its etiology remains debated, as initially presumed causes - myocarditis and cardiac necrosis - have proved uncommon. To elucidate the pathophysiology of COVID-19-associated cardiac injury, we conducted a prospective study of the first 69 consecutive COVID-19 decedents at CUIMC in New York City. Of 6 acute cardiac histopathologic features, presence of microthrombi was the most commonly detected among our cohort. We tested associations of cardiac microthrombi with biomarkers of inflammation, cardiac injury, and fibrinolysis and with in-hospital antiplatelet therapy, therapeutic anticoagulation, and corticosteroid treatment, while adjusting for multiple clinical factors, including COVID-19 therapies. Higher peak erythrocyte sedimentation rate and C-reactive protein were independently associated with increased odds of microthrombi, supporting an immunothrombotic etiology. Using single-nuclei RNA-sequencing analysis on 3 patients with and 4 patients without cardiac microthrombi, we discovered an enrichment of prothrombotic/antifibrinolytic, extracellular matrix remodeling, and immune-potentiating signaling among cardiac fibroblasts in microthrombi-positive, relative to microthrombi-negative, COVID-19 hearts. Non-COVID-19, nonfailing hearts were used as reference controls. Our study identifies a specific transcriptomic signature in cardiac fibroblasts as a salient feature of microthrombi-positive COVID-19 hearts. Our findings warrant further mechanistic study as cardiac fibroblasts may represent a potential therapeutic target for COVID-19-associated cardiac microthrombi.

Molecular Pathophysiology of Cardiac Injury and Cardiac Microthrombi in Fatal COVID-19: Insights from Clinico-histopathologic and Single Nuclei RNA Sequencing Analyses.

Cardiac injury is associated with critical COVID-19, yet its etiology remains debated. To elucidate the pathogenic mechanisms of COVID-19-associated cardiac injury, we conducted a single-center prospective cohort study of 69 COVID-19 decedents. Of six cardiac histopathologic features, microthrombi was the most commonly detected (n=48, 70%). We tested associations of cardiac microthrombi with biomarkers of inflammation, cardiac injury, and fibrinolysis and with in-hospital antiplatelet therapy, therapeutic anticoagulation, and corticosteroid treatment, while adjusting for multiple clinical factors, including COVID-19 therapies. Higher peak ESR and CRP during hospitalization were independently associated with higher odds of microthrombi. Using single nuclei RNA-sequence analysis, we discovered an enrichment of pro-thrombotic/anti-fibrinolytic, extracellular matrix remodeling, and immune-potentiating signaling amongst cardiac fibroblasts in microthrombi-positive COVID-19 hearts relative to microthrombi-negative COVID-19. Non-COVID-19 non-failing hearts were used as reference controls. Our cumulative findings identify the specific transcriptomic changes in cardiac fibroblasts as salient features of COVID-19-associated cardiac microthrombi.

Novel Receptor for Advanced Glycation End Products-Blocking Antibody to Treat Diabetic Peripheral Artery Disease.

Background Expression of receptor for advanced glycation end products (RAGE) plays an important role in diabetic peripheral artery disease. We proposed to show that treatment with an antibody blocking RAGE would improve hind limb perfusion and muscle viability in diabetic pig with femoral artery (FA) ligation. Methods and Results Purpose-bred diabetic Yucatan minipigs with average fasting blood sugar of 357 mg/dL on insulin to maintain a glucose range of 300 to 500 mg/dL were treated with either a humanized monoclonal anti-RAGE antibody (CR-3) or nonimmune IgG. All pigs underwent intravascular occlusion of the anterior FA. Animals underwent (201Tl) single-photon emission computed tomography/x-ray computed tomography imaging on days 1 and 28 after FA occlusion, angiogenesis imaging with [99mTc]dodecane tetra-acetic acid-polyethylene glycol-single chain vascular endothelial growth factor (scVEGF), muscle biopsies on day 7, and contrast angiogram day 28. Results showed greater increases in perfusion to the gastrocnemius from day 1 to day 28 in CR-3 compared with IgG treated pigs (P=0.0024), greater uptake of [99mTc]dodecane tetra-acetic acid-polyethylene glycol-scVEGF (scV/Tc) in the proximal gastrocnemius at day 7, confirmed by tissue staining for capillaries and vascular endothelial growth factor A, and less muscle loss and fibrosis at day 28. Contrast angiograms showed better reconstitution of the distal FA from collaterals in the CR-3 versus IgG treated diabetic pigs (P=0.01). The gastrocnemius on nonoccluded limb at necropsy had higher 201Tl uptake (percentage injected dose per gram) and reduced RAGE staining in arterioles in CR-3 treated compared with IgG treated animals (P=0.04). Conclusions A novel RAGE-blocking antibody improved hind limb perfusion and angiogenesis in diabetic pigs with FA occlusion. Contributing factors are increased collaterals and reduced vascular RAGE expression. CR-3 shows promise for clinical treatment in diabetic peripheral artery disease.

VEGF receptor targeted imaging of angiogenic response to limb ischemia in diabetic vs. non-diabetic Yucatan minipigs.

BACKGROUND: New therapies to treat diabetic peripheral artery disease (PAD) require target-specific non-invasive imaging modalities to follow efficacy. As a translational study, we performed targeted imaging of receptors for vascular endothelial growth factor (VEGF) in response to anterior femoral artery occlusion (FAO) in Yucatan minipigs and compare the normal response to response in diabetic Yucatan minipigs. METHODS: Eleven Yucatan minipigs, 6 non-diabetic (non-D) and 5 purpose bred diabetic (D) (Sinclair, Auxvasse MO), underwent intravascular total occlusion of the anterior femoral artery (FA). At days 1 and 28, pigs underwent SPECT/CT 201Tl hindlimb perfusion imaging and at day 7 were injected with [99mTc]DOTA-PEG-scVEGF (scV/Tc) tracer targeting VEGF receptor, and underwent biopsies of the hindlimb muscles for gamma counting and histology, followed by imaging. One day after the final scan, pigs underwent contrast angiography of the lower extremities. Counts from scans were converted to percentage injected activity (%IA). RESULTS: Perfusion was lower in the occluded hindlimb compared to non-occluded on day 1 in both the D and non-D pigs. At day 7, scV/Tc count ratio of counts from ROIs drawn in proximal gastrocnemius muscle for the occluded over non-occluded limb was significantly higher in non-D vs. D pigs (1.32 ± 0.06 vs. 1.04 ± 0.13, P = 0.02) reflecting higher level of angiogenesis. Perfusion increased between days 1 and 28 in the muscles in the occluded limb for the non-diabetic pigs while the diabetic pig showed no increase (+ 0.13 ± 0.08 %IA vs. - 0.13 ± 0.11, P = 0.003). The anterior FA showed poor contrast filling beyond occluder and qualitatively fewer bridging collaterals compared to non-D pigs at 28 days. CONCLUSION: VEGF receptor targeted imaging showed the effects of diabetes to suppress angiogenesis in response to occlusion of the anterior femoral artery of purpose bred diabetic Yucatan minipigs and indicates potential applicability as a marker to follow efficacy of novel therapies to improve blood flow by stimulating angiogenesis in diabetic PAD.

Self-Stabilized Giant Aggregates in Water from Room-Temperature Ionic Liquids with an Asymmetric Polar-Apolar-Polar Architecture.

We report the assembly of four imidazolium bromides, each of which bears a naphthyl on one side of the imidazolium cation and a branched alkyl chain on the other. This design creates a new type of amphiphilic ionic liquid with an apolar-polar-apolar structure and a low melting point (mp, <-20 °C), which has not been achieved by reported counterparts bearing linear alkyl chains. In solvent-free states, microphase segregation occurs where polar and apolar domains arrange bicontinuously as proved by molecular dynamics (MD) simulations. When dispersed in water, self-stabilized giant aggregates formed with ultrahigh colloidal stability (up to years). MD simulations provide clues of discrete bicontinuous phases within the giant aggregates. These newly discovered self-assemblies provide a heterogeneous reservoir that can accommodate guest molecules including the highly apolar fullerene C60, paving the way for a wide range of potential applications.

Cubic Liquid Crystals of Polyoxometalate-Based Ionic Liquids.

Thermotropic ionic liquid crystals of polyoxometalate (POM)-based ionic liquids (POM-based ILs), which are formed by a POM, K7PW11O39, and cationic surfactants, tetra-n-alkylammonium bromide ((CnH2n+1)4N+Br-, n = 6 and 7), are first proposed. As a model system, the cubic phase structure of a POM-based IL, {(C7H15)4N+}7PW11O39, was determined to form in a wide range of temperatures, exhibiting good thermostability, excellent mechanical strength, and high viscosity. Furthermore, the lyotropic ionic liquid crystals formed by {(C7H15)4N+}7PW11O39 in solvents such as chloroform or toluene still maintained a cubic structure. These cubic ionic liquid crystals (CILCs) were used as anticorrosion coatings both in acidic and neutral environments. The electrochemical measurements of Cu and Fe surfaces coated by CILCs showed an excellent ability of anticorrosion, indicating that the metals can be perfectly protected by the CILC coatings with high resistance and low capacitance. We assume that the CILCs may serve as barriers to stop oxygen diffusing to metals and interrupt the electron tunnels between the metal surfaces and the electrolyte solutions. Such environmentally friendly CILCs of POMs-based ILs are convenient for coating and removal, being vital to versatile industrial and academic applications.

Magnetic and Biocompatible Fullerenol/Fe(III) Microcapsules with Antioxidant Activities.

Fullerene C60 (refers to C60 hereafter) has a unique three-dimensional architecture and intriguing physicochemical properties. It has great potential applications in materials chemistry and life science. However, a big obstacle for the widespread application of C60 lies in the limited strategies to make supramolecular structures with diverse morphologies and functions. Herein, we report a strategy to prepare C60-based, magnetic microcapsules which can be used as external antioxidants to effectively attenuate oxidative stress. The microcapsules are composed of fullerenol, a highly water-soluble C60 multiadduct, and iron ions (Fe3+) released from a rusty nail. They can be easily obtained through coordination between the hydrophilic functional groups in fullerenol and Fe3+ with polystyrene microspheres as templates. The fullerenol/Fe3+ microcapsules have good colloidal stability both in water and serum. Their biocompatibility has been confirmed by in vitro tests on HEK293 and Hela cells. Electron spin resonance measurements indicate that the fullerenol/Fe3+ microcapsules can effectively scavenge hydroxyl radicals (OH·-) produced by H2O2, which greatly improves the living environment of the cells. The fullerenol/Fe3+ microcapsules exhibit ferromagnetic properties and can respond to the external magnetic field, enabling magnetic manipulation, and/or separation in practical applications.

Fullerene-Directed Synthesis of Flowerlike Cu3(PO4)2 Crystals for Efficient Photocatalytic Degradation of Dyes.

Biomineralization is a typical methodology developed by nature to produce calcium-based materials. A method mimicking this process has nowadays become popular for the preparation of artificial organic-inorganic hybrids. Here, Cu3(PO4)2 crystals with a flowerlike morphology have been prepared using water-soluble derivatives of fullerene C60 as templates. In a typical system, flowerlike crystals of Cu3(PO4)2 (denoted FLCs-Cu) were obtained by simply dropping an aqueous solution of CuSO4 into phosphate-buffered saline (PBS) containing a highly water-soluble multiadduct of C60 (fullerenol). The best condition for the preparation of FLCs-Cu appeared at 0.20 mg·mL-1 fullerenol and 0.10 mol·L-1 PBS. During the formation of FLCs-Cu, fullerenol acts as a template and its content in FLCs-Cu is trace (less than 5% by atom) as confirmed by scanning electron microscopy mapping and thermogravimetric analysis. This feature makes fullerenol reusable, and the FLCs-Cu can be prepared repeatedly using the same fullerenol aqueous solution at least 10 times without a noticeable change in the morphology. The N2 adsorption/desorption isotherm showed that the doping of fullerenol increased the specific surface area of the Cu3(PO4)2 crystal. When fullerenol was replaced by C60 monoadducts that are cofunctionalized with a pyrrolidine cation and oligo(poly(ethylene oxide)) chains, FLCs-Cu can form as well, indicating that the strategy of using water-soluble C60 derivative as a template to get FLCs-Cu is universal. As a typical example of practical applications, the photocatalytic activity of the FLCs-Cu was investigated toward the degradation of dyes including rhodamine B and rhodamine 6G. In both cases, efficient photodegradation has been confirmed.

Photoluminescent sensing vesicle platform self-assembled by polyoxometalate and ionic-liquid-type imidazolium gemini surfactants for the detection of Cr3+ and MnO4- ions.

In this paper, in order to successfully achieve a fluorescent polyoxometalate (POM) probe with high luminescence, aggregation enhanced emission of POM is achieved by a self-assembly strategy. In detail, Eu-polyoxometalate (Na9[EuW10O36]·32H2O (EuW10)) and ionic-liquid-type imidazolium gemini surfactants ([C14-n-C14im]Br2, n = 2, 4, 6) constructed a vesicle with aggregation enhanced emission phenomenon. With the introduction of [C14-n-C14im]Br2, the luminescence intensity increased sharply and compared the effect of the different space length of [C14-n-C14im]Br2, the introduction of [C14-2-C14im]Br2 had the best luminescence effect and the strongest luminescence of EuW10/[C14-2-C14im]Br2 was 32 times that of pure EuW10. Thus, a sensitive selective off-luminescence chemical sensor EuW10/[C14-2-C14im]Br2 was developed for the label-free detection of Cr3+ and MnO4- in aqueous solution with lower detection limits of 0.926 µM and 1.70 µM, respectively. Collision between the fluorophore and Cr3+ or MnO4- caused dynamic quenching. Luminescence quenching of Cr3+ was attributed to Förster resonance energy transfer (FRET) while luminescence quenching of MnO4- was attributed to UV-vis competitive absorption. Our strategy for combining polyoxometalates with surfactants to construct aggregation enhanced emission systems is expected to provide new ways to develop simple, economical, fast and sensitive sensors in environmental applications such as metal ion detection.

Aggregation-Induced Emission of EuIII Complexes Balanced with Bulky and Amphiphilic Imidazolium Cations in Ethanol/Water Binary Mixtures.

A series of EuIII complexes with thenoyltrifluoroacetone (tta) as the ligands were synthesized, which are balanced with imidazolium cations bearing naphthyl and branched alkyl chains. The complex with the longest alkyl chain (1Eu(tta)4 ) shows aggregation behavior in ethanol and water mixtures. It exists as individuals at low water percentages (VH2O ), and form particles with solid interiors at VH2O ≥50 % the sizes of which decrease with the increase of VH2O . At VH2O =90 %, vesicles were observed. The aggregation of 1Eu(tta)4 in ethanol and water binary mixtures induced changes of the photoluminescence (PL) properties where an abrupt increase in PL intensity, quantum yield, and lifetime were noticed above VH2O =50 %. This PL enhancement can be explained by the encapsulation of 1Eu(tta)4 inside the aggregates, preventing it from quenching by the active hydroxyls of water molecules. Contrary to the aggregation-induced emission (AIE) of the Eu complex, the naphthyl group in the imidazolium cation exhibited an aggregation-caused quenching (ACQ) effect. When the length of the alkyl chain in the imidazolium cation is reduced, no PL enhancement can be observed owing to the difficulty in forming the aggregates.

Imaging VEGF Receptors and αvß3 Integrins in a Mouse Hindlimb Ischemia Model of Peripheral Arterial Disease.

PURPOSE: To compare targeted imaging of vascular endothelial growth factor (VEGF) receptors vs. αvß3 integrins in a mouse hindlimb ischemia model of peripheral artery disease. PROCEDURES: Male wild-type (WT) C57BL/6 mice (8- to 10-week old) (n = 24) underwent left femoral artery ligation. The right leg served as control. Five days later, mice were injected with either VEGF receptor targeting [99mTc]DOTA-PEG-scVEGF ([99mTc]scV) (n = 8) or with αvß3-targeting tracer [99mTc]HYNIC-cycloRGD ([99mTc]RGD) (n = 8) and underwent single photon emission computed tomography (SPECT) x-ray computed tomography imaging. To assess non-specific [99mTc]scV uptake, six additional mice received a mixture of [99mTc]scV and 30-fold excess of targeting protein, scVEGF. Tracer uptake as %ID was measured using volumetric regions encompassing the hindlimb muscles and as %ID/g from harvested limb muscles. Double and triple immunofluorescent analysis on tissue sections established localization of αvß3, VEGFR-1, VEGFR-2, as well as certain cell lineage markers. RESULTS: Tracer uptake, as %ID/g, was higher in ligated limbs of mice injected with [99mTc]scV compared to ligated hindlimbs in mice injected with [99mTc]RGD (p = 0.02). The ratio of tracer uptake for ligated/control hindlimb was borderline higher for [99mTc]scV than for [99mTc]RGD (p = 0.06). Immunofluorescent analysis showed higher prevalence of VEGFR-1, VEGFR-2, and αvß3, in damaged vs. undamaged hindlimb tissue, but with little co-localization of these markers. Double immunofluorescent staining showed partial co-localization of VEGFR-1, VEGFR-2, and αvß3, with endothelial cell marker FVIII, but not with CD31. Immunostaining for VEGFR-1 and VEGFR-2 additionally co-localized with lineage markers for endothelial progenitor cell and monocytes/macrophages, with a more diverse pattern of co-localization for VEGFR-2. CONCLUSION: In a mouse hindlimb ischemia model of peripheral artery disease, [99mTc]scV SPECT tracer-targeting VEGF receptors showed a more robust signal than [99mTc]RGD tracer-targeting αvß3. Immunofluorescent analysis suggests that uptake of [99mTc]scV and [99mTc]RGD in damaged tissue is due to non-overlapping cell populations and reflects different dynamic processes and that enhanced uptake of [99mTc]scV may be due to the presence of VEGF receptors on additional cell types.

Versatile Self-Assembly and Biosensing Applications of DNA and Carbon Quantum Dots Coordinated Cerium Ions.

Self-assembly exploits noncovalent interactions to offer a facile and effective method for the construction of soft materials with multifunctionalities and diversity. In this work, fluorescence carbon quantum dots coordinated by Ce3+ ions (CQDCe) have been synthesized and exploited as building blocks to generate a series of hierarchical structures through the ionic self-assembly of CQDCe and biomolecules, namely DNA, myoglobin (Mb), and hyaluronic acid (HA). In particular, vesicles can be constructed by the simple mixing of oppositely charged CQDCe and DNA in water. The formation of unusual vesicles can be explained by the self-assembly of CQDCe with a rearranged structure and the rigid DNA biomolecular scaffolds. This facile noncovalent self-assembly method has inspired the innovative use of virgin DNA as a building block to construct vesicles rather than resorting to a sophisticated synthesis. The self-assembly of CQDCe-biopolymers was accompanied by aggregation-induced photoluminescence (PL) quenching. The biosensing platform was designed to detect polypeptides and deoxyribonuclease I through competitive binding of CQDCe and enzymatic hydrolysis of the DNA backbone, respectively. We believe that the integrative self-assembly of CQDCe and DNA will enrich the theoretical study of vesicle formation by DNA molecules and extend the application of fluorescence carbon quantum dots in the biological field.

Improving the Power Conversion Efficiency of Carbon Quantum Dot-Sensitized Solar Cells by Growing the Dots on a TiO2 Photoanode In Situ.

Dye-sensitized solar cells (DSSCs) are highly promising since they can potentially solve global energy issues. The development of new photosensitizers is the key to fully realizing perspectives proposed to DSSCs. Being cheap and nontoxic, carbon quantum dots (CQDs) have emerged as attractive candidates for this purpose. However, current methodologies to build up CQD-sensitized solar cells (CQDSCs) result in an imperfect apparatus with extremely low power conversion efficiencies (PCEs). Herein, we present a simple strategy of growing carbon quantum dots (CQDs) onto TiO2 surfaces in situ. The CQDs/TiO2 hybridized photoanode was then used to construct solar cell with an improved PCE of 0.87%, which is higher than all of the reported CQDSCs adopting the simple post-adsorption method. This result indicates that an in situ growing strategy has great advantages in terms of optimizing the performance of CQDSCs. In addition, we have also found that the mechanisms dominating the performance of CQDSCs are different from those behind the solar cells using inorganic semiconductor quantum dots (ISQDs) as the photosensitizers, which re-confirms the conclusion that the characteristics of CQDs differ from those of ISQDs.

Photoluminescent Honeycomb Structures from Polyoxometalates and an Imidazolium-Based Ionic Liquid Bearing a π-Conjugated Moiety and a Branched Aliphatic Chain.

Honeycomb-structured films represent an intriguing class of two-dimensional porous materials. Specifically, polyoxometalate (POM) macroanions can be introduced into these films by complexing with oppositely charged, double-tailed surfactants. Here highly-ordered honeycomb structures are reported that can be constructed by the complexes between POMs and a room temperature ionic liquid (IL1) having an imidazolium moiety in the middle and a naphthyl unit and a branched aliphatic chain at the ends. The complexes can be produced through phase transfer between an aqueous solution of POMs (typically {Mo72 Fe30 }) and a CS2 (or chloroform) solution of IL1. Based on the intrinsic properties of {Mo72 Fe30 } and the functional groups of the IL1, the honeycomb structures show multiple functions with bright photoluminescence and rich electrochemical properties. This work shows that by simply engineering the organic ligands involved in the POM-based inorganic-organic complexes, supramolecular structures with improved properties and wide applications can be obtained.

Naphthalene-Functionalized, Photoluminescent Room Temperature Ionic Liquids Bearing Small Counterions.

Obtaining π-conjugated room temperature ionic liquids (RTILs) is difficult because of the relatively strong π-π interaction among the π-moieties. Existing strategies by using bulky counterions greatly hindered further property optimization and potential applications of these intriguing functional fluids through simple ion exchange. Herein, four naphthalene-functionalized, π-conjugated RTILs with small counterions (Br(-) ) have been facilely synthesized with high yields. Our strategy is to attach branched alkyl chains to the cationic backbone of the target compounds (2 a-d), which effectively tune inter- and intramolecular interactions. Compounds 2 a-d have satisfactory thermal stability (up to 300 °C) and low melting points (<-19 °C). Rheological measurements revealed the fluid character of 2 a-d, whose viscosity decrease with the increase of the alkyl chain length and temperature. The presence of the π-conjugated naphthalene moiety imparts 2 a-d photoluminescent properties in bulk solutions. Moreover, the absence of strong π-π stacking among the naphthalene units in solvent-free states enables them to be used as a new generation of photoluminescent inks.