Triflate anion chemistry for enhanced four-electron zinc-iodine aqueous batteries.

I+ hydrolysis, sluggish iodine redox kinetics and the instability of Zn anodes are the primary challenges for aqueous four-electron zinc-iodine batteries (4eZIBs). Herein, the OTf- anion chemistry in aqueous electrolyte is essential for developing advanced 4eZIBs. It is elucidated that OTf- anions establish weak hydrogen bonds (H bonds) with water to stabilize I+ species while optimizing a water-lean Zn2+ coordination structure to mitigate Zn dendrites and corrosion. Moreover, the interaction of the OTf- anions with the iodine species results in an increased equilibrium average intermolecular bond length of the iodine species, facilitating the 4e redox kinetics of iodine with improved reversibility.

Aqueous Electrolyte With Weak Hydrogen Bonds for Four-Electron Zinc-Iodine Battery Operates in a Wide Temperature Range.

In the pursuit of high-performance energy storage systems, four-electron zinc-iodine aqueous batteries (4eZIBs) with successive I-/I2/I+ redox couples are appealing for their potential to deliver high energy density and resource abundance. However, susceptibility of positive valence I+ to hydrolysis and instability of Zn plating/stripping in conventional aqueous electrolyte pose significant challenges. In response, polyethylene glycol (PEG 200) is introduced as co-solvent in 2 m ZnCl2 aqueous solution to design a wide temperature electrolyte. Through a comprehensive investigation combining spectroscopic characterizations and theoretical simulations, it is elucidated that PEG disrupts the intrinsic strong H-bonds of water by global weak PEG-H2O interaction, which strengthens the O─H covalent bond of water and intensifies the coordination with Zn2+. This synergistic effect substantially reduces water activity to restrain the I+ hydrolysis, facilitating I-/I2/I+ redox kinetics, mitigating I3 - formation and smoothening Zn deposition. The 4eZIBs in the optimized hybrid electrolyte not only deliver superior cyclability with a low fading rate of 0.0009% per cycle over 20 000 cycles and a close-to-unit coulombic efficiency but also exhibit stable performance in a wide temperature range from 40 °C to -40 °C. This study offers valuable insights into the rational design of electrolytes for 4eZIBs.

Molecule Engineering of Sugar Derivatives as Electrolyte Additives for Deep-Reversible Zn Metal Anode.

The cycling performance of zinc-ion batteries is greatly affected by dendrite formation and side reactions on zinc anode, particularly in scenarios involving high depth of discharge (DOD) and low negative/positive capacity (N/P) ratios in full cells. Herein, drawing upon principles of host-guest interaction chemistry, we investigate the impact of molecular structure of electrolyte additives, specifically the -COOH and -OH groups, on the zinc negative electrode through molecular design. Our findings reveal that molecules containing these groups exhibit strong adsorption onto zinc anode surfaces and chelate with Zn2+, forming a H2O-poor inner Helmholtz plane. This effectively suppresses side reactions and promotes dendrite-free zinc deposition of exposed (002) facets, enhancing stability and reversibility of an average coulombic efficiency of 99.89% with the introduction of Lactobionic acid (LA) additive. Under harsh conditions of 92% DOD, Zn//Zn cells exhibit stable cycling at challenging current densities of 15 mA·cm-2. Even at a low N/P ratio of 1.3, Zn//NH4V4O10 full cells with LA electrolyte exhibit high-capacity retention of 73% after 300 cycles, significantly surpassing that of the blank electrolyte. Moreover, in a conversion type Zn//Br static battery with a high areal capacity (~ 5 mAh·cm-2), LA electrolyte sustains an improved cycling stability of 700 cycles.

Comparative Metabolic Profiling of Different Colored Rice Grains Reveals the Distribution of Major Active Compounds and Key Secondary Metabolites in Green Rice.

Pigmented rice grains are important resources for health and nutritional perspectives. Thus, a thorough dissection of the variation of nutrients and bioactive metabolites in different colored rice is of global interest. This study applied LC-MS-based widely targeted metabolite profiling and unraveled the variability of metabolites and nutraceuticals in long grain/non-glutinous black (BR), red (RR), green (GR), and white rice (WR) grains. We identified and classified 1292 metabolites, including five flavonoid compounds specific to BR. The metabolite profiles of the four rice grains showed significant variation, with 275-543 differentially accumulated metabolites identified. Flavonoid (flavone, flavonol, and anthocyanin) and cofactor biosynthesis were the most differentially regulated pathways among the four rice types. Most bioactive flavonoids, anthocyanidins (glycosylated cyanidins and peonidins), phenolic acids, and lignans had the highest relative content in BR, followed by RR. Most alkaloids, amino acids and derivatives, lipids, and vitamins (B6, B3, B1, nicotinamide, and isonicotinic acid) had higher relative contents in GR than others. Procyanidins (B1, B2, and B3) had the highest relative content in RR. In addition, we identified 25 potential discriminatory biomarkers, including fagomine, which could be used to authenticate GR. Our results show that BR and RR are important materials for medicinal use, while GR is an excellent source of nutrients (amino acids and vitamins) and bioactive alkaloids. Moreover, they provide data resources for the science-based use of different colored rice varieties in diverse industries.

Rocking-Chair Aqueous Fluoride-Ion Batteries Enabled by Hydrogen Bonding Competition.

Aqueous fluoride ion batteries (FIBs) have garnered attention for their high theoretical energy density, yet they are challenged by sluggish fluorination kinetics, active material dissolution, and electrolyte instability. Here, we present a room temperature rocking-chair aqueous FIBs featuring KOAc-KF binary salt electrolytes, enabling concurrent fluorination and defluorination reactions at both cathode and anode electrodes. Experimental and theoretical results reveal that acetate ions in the electrolyte compete with fluoride ions in hydrogen bonding formation, weakening the excessively strong solvation between H2O and F- ions. This results in the suppression of detrimental HF formation and a reduced desolvation energy of F- ions, enhancing the electrochemical reaction kinetics. The bismuth-based cathode exhibits direct conversion in the optimized electrolyte, effectively suppressing the detrimental disproportionation reactions from Bi2+ intermediates. Additionally, zinc anode undergoes a typical fluorination process, forming solid KZnF3 as the electrode product, minimizing the risks of hydrogen evolution. The proposed aqueous FIBs with the optimized electrolyte demonstrate high discharge capacity, long-term cycling stability and excellent rate capabilities.

Practical four-electron zinc-iodine aqueous batteries enabled by orbital hybridization induced adsorption-catalysis.

The successive I-/I0/I+ redox couples in the four-electron zinc-iodine aqueous battery (4eZIB) is plagued by the instability of the electrophilic I+ species, which could either be hydrolyzed or be neutralized by the I3- redox intermediates. We present an adsorption-catalysis approach that effectively suppresses the hydrolysis of ICl species and also provides an enhanced reaction kinetics to surpass the formation of triiodide ions. We elucidate that the improved stability is attributed to the pronounced orbital hybridization between the d orbitals of Fe-N4 moieties (atomic Fe supported on nitrogen doped carbon) and the p orbitals of iodine species (I2 and ICl). Such d-p orbital hybridization leads to enhanced adsorption for iodine species, increased energy barrier for proton detachment from the ICl·HOH intermediate during hydrolysis, and efficient catalysis of the iodine redox reactions with high conversion efficiency. The proposed 4eZIB demonstrates practical areal capacity (>3 mAh cm-2) with a near-unity coulombic efficiency, high energy density of 420 Wh kg-1 (based on cathode mass), and long-term stability (over 10,000 cycles). Even at -20 °C, the battery exhibits stable performance for over 1000 cycles with high iodine utilization ratio.

Unravelling rechargeable zinc-copper batteries by a chloride shuttle in a biphasic electrolyte.

The zinc-copper redox couple exhibits several merits, which motivated us to reconstruct the rechargeable Daniell cell by combining chloride shuttle chemistry in a zinc chloride-based aqueous/organic biphasic electrolyte. An ion-selective interface was established to restrict the copper ions in the aqueous phase while ensuring chloride transfer. We demonstrated that the copper-water-chloro solvation complexes are the descriptors, which are predominant in aqueous solutions with optimized concentrations of zinc chloride; thus, copper crossover is prevented. Without this prevention, the copper ions are mostly in the hydration state and exhibit high spontaneity to be solvated in the organic phase. The zinc-copper cell delivers a highly reversible capacity of 395 mAh g-1 with nearly 100% coulombic efficiency, affording a high energy density of 380 Wh kg-1 based on the copper chloride mass. The proposed battery chemistry is expandable to other metal chlorides, which widens the cathode materials available for aqueous chloride ion batteries.

Porous Cobalt Metal-Organic Frameworks as Active Elements in Battery-Supercapacitor Hybrid Devices.

With the trigonal linker 4,4',4″-s-triazine-2,4,6-triyltribenzoic acid as a building block, porous cobalt metal-organic frameworks (named as PCN) have been successfully prepared and directly utilized as active materials in alkaline battery-type devices. For comparison, their carbon-supported hybrids (CNFs/PCN) have also been employed as battery-type electrodes. We found that the pristine PCN displayed a better performance than the CNFs/PCN composite electrode in electrochemical cells. To further investigate their electrochemical performances, alkaline battery-supercapacitor hybrid (BSH) devices with these materials as positive electrodes and activated carbon (AC) as the negative electrode were fabricated. The results indicate that the PCN//AC BSH devices delivered a maximum energy density of 16.0 Wh kg-1 at a power density of 749 W kg-1 within the voltage range of 0-1.5 V, which are much higher than those of CNFs/PCN//AC devices (12.4 Wh kg-1 at 753 W kg-1).

Boosting the performance of broccoli-like Ni-triazole frameworks through a CNTs conductive-matrix.

Different approaches for the fabrication of CNT-supported Ni-triazole composites, such as room-temperature stirring and hydrothermal treatment for a distinct reaction time has been presented. As a result, various morphologies, MMOF wrapped CNTs, CNTs entangled with an MMOF and CNTs attached on an MMOF, were synthesized and investigated through electrochemical measurements. The as-synthesized CNTs/MMOF-based hybrids, especially for the CNTs/MMOF-8H structure, show a good rate capability after 20 times increase, a superior coulombic efficiency and an excellent long-term cycling stability (more than 98% retained after 2000 cycles). This enhancement can be ascribed to the introduction of the CNT conductive additives, which promote the fast charge-transfer ability of ions and electrons. Even for the other CNTs/MMOF-based composites, the overall electrochemical performances are still superior to those of pristine MMOF electrodes.

Healthcare Utilization and Quality of Life Improvement after Ablation for Paroxysmal AF in Younger and Older Patients.

BACKGROUND: Atrial fibrillation (AF) prevalence increases significantly with age. Little is known about the effect of AF ablation on quality of life and healthcare utilization in the elderly. The objective of this study was to quantify the healthcare utilization and quality of life benefits of catheter ablation for AF, for patients ≥65 years compared to patients <65 years. METHODS: Two multicenter U.S. registry studies enrolled patients with paroxysmal AF. Baseline characteristics and acute outcomes were collected for 736 patients receiving catheter ablation with the Navistar® ThermoCool® SF Catheter (Biosense Webster, Inc., Diamond Bar, CA, USA). Healthcare utilization and quality of life outcomes were collected through 1 year postablation for 508 patients. RESULTS: The rates of acute pulmonary vein isolation were high and similar between patients ≥65 years and <65 years (97.5% vs 95.8%, P = 0.2130). Length of stay for the index procedure was similar between age groups with 82.2% of the older group and 83.2% of the younger group having one-day hospitalization. Disease-specific quality of life instrument scores improved significantly and similarly for older and younger patients at 1 year postablation, compared to baseline. AF-related hospitalizations and emergency department visits were similar or lower in older patients compared to younger patients, as reported at 1 year postablation. CONCLUSION: For older patients undergoing catheter ablation for paroxysmal AF, healthcare utilization parameters were lower or not significantly different than for younger patients, and quality of life outcomes were similarly improved. These findings support the use of catheter ablation as a treatment option in older patients with paroxysmal AF.

[Chondrogenesis of bone marrow mesenchymal stem cells induced by transforming growth factor beta3 gene in Diannan small-ear pigs].

OBJECTIVE: To observe transforming growth factor beta3 (TGF-beta3) gene expression and the chondrogenesis of bone marrow mesenchymal stem cells (BMSCs) after TGF-beta3 gene is transfected into BMSCs of Diannan small-ear pig. METHODS: Recombinant adenovirus 5 (rAd5) was extracted as gene vector and packed into recombinant adenovirus rAd5-TGF-beta3, double enzyme digestion and PCR identification were performed. BMSCs were isolated and cultured from bone marrow of 2-month-old Diannan small-ear pigs (weighing, 12-15 kg), and the 2nd generation of BMSCs were harvested for experiments. The experiments were divided into 3 groups. BMSCs were transfected with rAd5-TGF-beta3 as experimental group and with empty vector as control group, and non-transfected BMSCs were used as blank control group. The transfection efficiency of exogenous gene was identified by flow cytometry, TGF-beta3 protein expression by immunofluorescence and Western blot. The cell morphology of experimental group was observed by inverted phase contrast microscope, and the expression of collagen type II in each group was detected by Western blot. RESULTS: The rAd5-TGF-beta3 recombinant adenovirus was successfully constructed and transfected into BMSCs. Green fluorescence was observed by immunofluorescence microscope. Flow cytometry test showed the best transfection at 72 hours (transfection efficiency of 84.86%). Immunofluorescence staining showed that the expression of TGF-beta3 protein was obvious at 72 hours; Western blot showed that there was a TGF-beta3 positive band with a relative molecular mass of 30 x 10(3), while the control group and blank control group had no positive band. Obvious chondrogenic differentiation was observed in the experimental group after transfection in vitro, while the control group and blank control group had no obvious chondrogenic differentiation. Western blot showed that there was collagen type II positive band with a relative molecular mass of 130 x 10(3) at 21 days after culture, while the control group and blank control group had no positive band. CONCLUSION: rAd5-TGF-beta3 gene can be successfully transfected into BMSCs via adenovirus vectors, and stable expression of TGF-beta3 protein can be observed, enhancing BMSCs differentiation into chondrocytes, which may provide an experimental basis for gene therapy of joint cartilage defects.

Acute safety of an open-irrigated ablation catheter with 56-hole porous tip for radiofrequency ablation of paroxysmal atrial fibrillation: analysis from 2 observational registry studies.

INTRODUCTION: This report presents safety data on the use of a new open-irrigation radiofrequency ablation (RFA) catheter with a 56-hole porous tip in 742 patients enrolled in 2 US prospective, multicenter observational registry studies representing real-world use of the catheter. METHODS: This analysis is comprised of patients who underwent RFA of drug-refractory recurrent symptomatic paroxysmal atrial fibrillation (AF). Acute adverse events (AEs) were collected and categorized by seriousness, timing, and relatedness, with 7 days of follow-up data in one study and at least 120 days of data from a 1-year follow-up in the other. Acute serious adverse events (SAEs) that were identified as potentially related to the device and/or procedure were adjudicated by an independent safety committee. RESULTS: A total of 30 patients (4.0%) in the combined studies experienced an acute SAE related to the device and/or procedure, which was similar in the subset of patients age 65 and over (4.2%). These SAEs included 1.2% cardiac tamponade/perforation, 0.7% pericarditis, 0.5% pulmonary events, and 0.8% vascular access complications. No myocardial infarction, stroke, transient ischemic attack, or atrioesophageal fistulas within 7 days postprocedure were reported. In the study with extended follow-up, 1 pulmonary vein stenosis and 1 esophageal injury were seen beyond 7 days postprocedure (0.2% each). There were no device or procedure related deaths. CONCLUSION: Results from 2 large observational studies demonstrated that a new porous tip RFA catheter was safe for the treatment of drug refractory, recurrent, symptomatic paroxysmal AF, including treatment of older patients (≥65 years).

[CONSTRUCTION AND IDENTIFICATION OF ADENOVIRUS VECTOR EXPRESSING BONE MORPHOGENETIC PROTEIN 2 AND TRANSFORMING GROWTH FACTOR ß3 GENES AND THEIR EXPRESSION IN BONE MARROW MESENCHYMAL STEM CELLS OF DIANNAN SMALL-EAR PIGS].

OBJECTIVE: To construct and identify the recombinant adenovirus vector expressing bone morphogenetic protein 2 (BMP-2) and transforming growth factor ß3 (TGF-ß3) genes, to observe the expressions of BMP-2 and TGF-ß3 after transfected into bone marrow mesenchymal stem cells (BMSCs) of the Diannan small-ear pigs. METHODS: BMP-2 cDNA and TGF-ß3 cDNA were amplified by PCR, and were subcloned into the pEC3.1 (+) plasmid to obtain pEC-GIE 3.1-BMP-2 and pEC-GIE3.1-TGF-ß3 plasmid respectively. They were subcloned into pGSadeno vector by homologous recombination reaction and HEK293 cells were transfected after linearization to obtain Ad-BMP-2 and Ad-TGF-ß3. The BMSCs were isolated from the bone marrow of Diannan small-ear pig and cultured. The 3rd passage BMSCs were transfered with Ad-BMP-2 (group A), Ad-TGF-ß3 (group B), Ad-BMP-2+ Ad-TGF-ß3 (group C), and untransfected cells served as a control (group D). The expressions of BMP-2 and TGF-ß3 genes and proteins were detected by PCR, immunofluorescence, and Western blot. The chondrogenic differentiation of BMSCs was evaluated by immunohistochemical of collagen type II. RESULTS: The Ad-BMP-2 and Ad-TGF-ß3 were constructed successfully and confirmed by PCR and sequencing. The expression clones of Ad-BMP-2 and Ad-TGF-ß3 were packaged into maturated adenovirus successfully, the titer was 5.6 x 10(8) and 1.6 x 10(8) pfu/mL respectively. The PCR results showed a light band at 310 bp in group A and at 114 bp in group B, and both 310 bp and 114 bp bands in group C, but no band in group D. The image of immunofluorescence showed that there were red fluorescence and green fluorescence expressions in the cytoplasm of BMSCs at 72 hours after transfection in groups A and B, respectively; in group C, both red and green fluorescence expressions were detected, and no red or green fluorescence was detected in group D. The results of Western blot showed that there was a light band at 18 x 10(3) in group A and at 50 x 10(3) in group B; both 18 x 10(3) and 50 x 10(3) bands were detected in group C; but no band was detected in group D. The cells were positive for collagen type II in groups A, B, and C; group C acquired strong collagen type II staining when compared with group A and group B; in group D, the cells were negative for collagen type II staining. CONCLUSION: The recombinant adenovirus vector expressing BMP-2 and TGF-ß3 are constructed successfully. The BMP-2 and TGF-ß3 genes could be expressed effectively in BMSCs of Diannan small-ear pig after transfection, which could afford modified seeding cells for cartilage tissue engineering.

[Effectiveness of computer-assisted preoperative planning system in anterior cruciate ligament reconstruction].

OBJECTIVE: To evaluate the feasibility and effectiveness of computer-assisted preoperative planning system-ACL Detector in anterior cruciate ligament (ACL) reconstruction. METHODS: Between March 2009 and January 2012, 80 patients with ACL rupture received arthroscopic ACL single-bundle reconstruction with autologous hamstring tendon transplantation. Before operation, the preoperative planning was done by computer-assisted preoperative planning system-ACL Detector (trial group, n=40) or by conventional method (control group, n=40). There was no significant difference in gender, age, disease duration, injury cause, preoperative Lysholm score, and preoperative International Knee Documentation Committee (IKDC) score between 2 groups (P > 0.05). After operation, the effectiveness was evaluated by Lachman test, pivot shift test, Lysholm score, and IKDC score; the digital three-dimensinal model of knee was reconstructed, and the impingement rate of ACL graft was measured. RESULTS: All incisions healed by first intention, and no complication was found. The patients were followed up 18-25 months (mean, 20 months) in trial group and 18-24 months (mean, 21 months) in control group. The Lysholm score and IKDC score were significantly increased at 18 months after operation when compared with preoperative scores (P < 0.05), but no significant difference was found between 2 groups (P > 0.05). The results of Lachman test and pivot shift test at 18 months after operation were significantly better than those before operation in 2 groups (P < 0.05), but no significant difference between 2 groups after operation (P > 0.05). MRI showed that impingement was observed in 1 case of trial group (2.50%) and in 8 cases of control group (20.00%), showing significant difference (chi2=4.51, P=0.03). CONCLUSION: The computer-assisted preoperative planning system-ACL Detector could be successfully applied to ACL reconstruction. It has the same improvement in knee functional score as conventional surgery, but it is better than conventional surgery in reducing the impingement incidence.

Unexpected, dramatic improvement in atrioventricular conduction during pacemaker implantation for apparent complete heart block.

We describe the case of a 29-year-old man with complete heart block after aortic and mitral valve surgery for bacterial endocarditis. Prior to pacemaker implantation, the patient had sinus bradycardia with third degree atrioventricular (AV) block. During testing of the atrial lead, the patient manifested intact AV conduction with a constant PR interval, which was robust up to 120 beats/min. This case represents a dramatic example of unexpected, improved AV conduction, perhaps a result of loss of Phase IV block.

Use of health care resources and cost of care for adults with constipation.

BACKGROUND & AIMS: Constipation is a multisymptom disorder that frequently compromises quality of life and leads patients to seek medical advice. To evaluate the clinical and fiscal effects of constipation, we assessed health care resource use by patients with constipation enrolled in a large state Medicaid program. METHODS: We identified 105,130 patients older than age 18 who saw a physician at least once for constipation and were enrolled in the California Medicaid program (Medi-Cal). We then studied health care resource use and costs (reimbursed by Medi-Cal) in 76,854 patients without supplementary insurance. The 15-month analysis period encompassed 3 months before and 12 months after the first visit. The prevalence of comorbid conditions was assessed in the sample of 105,130 patients. RESULTS: During the study period, 106,555 physician visits were for constipation; the total associated cost was $3,016,017 ($39/patient). The total cost for gastrointestinal procedures and laboratory testing was $14,052,503 ($183/patient). There were 41,723 over-the-counter and 1665 prescription drug purchases; the total cost was $388,780 ($5/patient). Approximately 0.6% of patients (n = 479) were admitted to the hospital for constipation; the total cost was $1,433,708 ($2993/admission). The total direct health care costs for patients with constipation in the Medi-Cal system for the 15-month period was $18,891,008 ($246/patient). Within 12 months of the first physician visit for constipation, 5657 of 105,130 patients had hemorrhoids and 2288 had intestinal impaction or obstruction. CONCLUSIONS: Adults seeking treatment for constipation account for significant health care resource use and often have comorbid conditions. The clinical and fiscal burden of constipation in US adults cannot be disregarded or trivialized.

Molecular cloning of nonsecreted endothelial cell-derived lipase isoforms.

To expand our knowledge of factors involved in lipid metabolism in the blood vessel wall, we have cloned unique molecular isoforms of endothelial cell-derived lipase (EDL) (HGMW-approved symbol/LIPG). One isoform encoded a truncated protein (EDL2a) lacking the first 80 amino acid residues of the previously characterized EDL1a isoform, including the signal peptide. A similar second clone (EDL2b) was identified that lacked not only the first 80 amino acids, but also a 74-amino-acid region that encodes a portion of the lid domain. RT-PCR analysis confirmed expression of EDL2a/2b isoforms in several human tissues and cultured cells, including endothelial cells. Western blot and immunofluorescence studies using stable transfectants revealed that EDL2a and EDL2b were localized in the cytosol, while, EDL1a was secreted into the culture medium. Cell extracts of EDL2a/2b transfectants did not have triglyceride or phospholipase activity. Thus endothelial cells express three EDL isoforms, two of which remain intracellular and do not function as lipases.