In-situ coating and surface partial protonation co-promoting performance of single-crystal nickel-rich cathode in all-solid-state batteries

The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.

Proton pump inhibitors and all-cause mortality risk among cancer patients

BACKGROUND Proton pump inhibitors(PPIs)are widely used,including among cancer patients,to manage gastroesophageal reflux and other gastric acid-related disorders.Recent evidence suggests associations between long-term PPI use and higher risks for various adverse health outcomes,including greater mortality.AIM To investigate the association between PPI use and all-cause mortality among cancer patients by a comprehensive analysis after adjustment for various confounders and a robust methodological approach to minimize bias.METHODS This retrospective cohort study used data from the TriNetX research network,with electronic health records from multiple healthcare organizations.The study employed a new-user,active comparator design,which compared newly treated PPI users with non-users and newly treated histamine2 receptor antagonists(H2RA)users among adult cancer patients.Newly prescribed PPIs(esomeprazole,lansoprazole,omeprazole,pantoprazole,or rabeprazole)users were compared to non-users or newly prescribed H2RAs(cimetidine,famotidine,nizatidine,or ranitidine)users.The primary outcome was all-cause mortality.Each patient in the main group was matched to a patient in the control group using 1:1 propensity score matching to reduce confounding effects.Multivariable Cox regression models were used to estimate hazard ratios(HRs)and 95% confidence interval(CI).RESULTS During the follow-up period(median 5.4±1.8 years for PPI users and 6.5±1.0 years for non-users),PPI users demonstrated a higher all-cause mortality rate than non-users after 1 year,2 years,and at the end of follow up(HRs:2.34-2.72).Compared with H2RA users,PPI users demonstrated a higher rate of all-cause mortality HR:1.51(95%CI:1.41-1.69).Similar results were observed across sensitivity analyses by excluding deaths from the first 9 months and 1-year post-exposure,confirming the robustness of these findings.In a sensitivity analysis,we analyzed all-cause mortality outcomes between former PPI users and individuals who have never used PPIs,providing insights into the long-term effects of past PPI use.In addition,at 1-year follow-up,the analysis revealed a significant difference in mortality rates between former PPI users and non-users(HR:1.84;95%CI:1.82-1.96).CONCLUSION PPI use among cancer patients was associated with a higher risk of all-cause mortality compared to non-users or H2RA users.These findings emphasize the need for cautious use of PPIs in cancer patients and suggest that alternative treatments should be considered when clinically feasible.However,further studies are needed to corroborate our findings,given the significant adverse outcomes in cancer patients.

Protonation of 5,10,15,20-Tetra(4-hydroxyphenyl)-porphyrin in SDS Micellar Solution

An amphiphilic porphyrin, 5, 10, 15, 20-tetra(4-hydroxyphenyl)-porphyrin (P) was solubilized in SDS micellar solutions. By taking advantage of protonation property of pyridine groups of amphiphilic porphyrin and the UV-Vis spectral sensitivity of Soret band and Q bands to the microenvironment of the porphyrin moiety, two-step protonation was studied in detail by means of UV-Vis spectroscopy. The free base, monocation and dication were described in detail in SDS micellar solution. The possibility of microphase transition was proposed to relate to the observation of two isosbestic points.

黄芩苷与苦参碱分子间相互作用的量子化学计算与验证

为探究苦参碱能极大增强黄芩苷在水中的溶解度的原因,采用量子计算对二者反应过程及共存状态进行分析,并使用单晶衍射和红外图谱验证计算结果.本研究表明,黄芩苷和苦参碱并非简单的以非共价作用相结合,二者存在质子转移现象,反应生成黄芩苷阴离子和苦参碱阳离子,以静电作用为主导形成共无定型物,导致水溶性极大增加.

内镜下电凝止血联合艾司奥美拉唑钠治疗消化性溃疡出血疗效观察

目的探讨内镜下电凝止血联合艾司奥美拉唑钠治疗消化性溃疡(PUD)出血的临床疗效。方法将92例PUD出血患者按照患者意愿分为两组,每组46例。对照组患者采用艾司奥美拉唑钠治疗,研究组患者采用内镜下电凝止血联合艾司奥美拉唑钠治疗,均治疗5 d。比较两组患者的临床疗效、临床症状缓解时间、治疗前后凝血功能[凝血酶原时间(PT)、纤维蛋白原(FIB)水平、凝血活酶时间(APTT)及凝血酶时间(TT)],治疗前及治疗后1个月胃酸分泌情况[基础胃酸分泌量(BAO)、最大胃酸分泌量(MAO)、高峰胃酸分泌量(PAO)]。结果研究组患者临床疗效总有效率为91.30%,对照组患者为76.09%,研究组高于对照组(P<0.05)。治疗5 d,两组患者PT、APTT及TT较治疗前缩短,FIB水平较治疗前升高,且研究组优于对照组(P<0.01)。研究组患者腹痛、腹胀、呕血或便血及嗳气症状缓解时间短于对照组(P<0.01)。治疗后1月,两组患者BAO、MAO、PAO较治疗前减少,且研究组少于对照组(P<0.05或0.01)。结论内镜下电凝止血联合艾司奥美拉唑钠治疗PUD出血患者效果良好,能发挥协同增效作用,快速改善临床症状,抑制胃酸分泌,保护胃肠黏膜,加速患者康复进程。

The Determination of the Protonation Constants of A New Macrocyclic Dinucleating Ligand, BDBPH

The protonation constants of a new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, BDBPH, were determined by potentiometric measurement at 25.0 degreesC and mu = 0.100 mol.L-1 (KCl). The species distributions of the deprotonated and protonated compounds in the pH range from 2 to 12 aqueous solutions were also described.

Understanding De-protonation Induced Formation of Spinel Phase in Li-rich Layered Oxides for Improved Rate Performance

Constructing layered-spinel composites is important to improve the rate performance of lithium-rich layered oxides.However,up to now,the effect of microstructure of composites on the rate performance has not been well investigated.In this study,a series of samples were prepared by a simple protonation and de-protonation for the pristine layered material(LiMnNiCoO)obtained by sol-gel method.The characterizations of XRD,Raman and oxidation-reduction potentials of charge-discharge curves demonstrated that these samples after de-protonation are layered-spinel composites.When these composites were tested as a cathode of lithium-ion batteries,the sample treated with 0.1 M of nitric acid exhibited higher discharge capacities at each current density than that of other composites.The outstanding rate performance is attributed to the high concentration of conduction electron resulting from the low average valence state(44.2%of Ni)as confirmed by its high conductivity(1.124×10??mat39800Hz)and ambient temperature magnetic susceptibility(8.40×10emu/Oe?mol).This work has a guiding significance for the synthesis of high rate performance of lithium battery cathode materials.

早期认知功能损害患者脑组织谷氨酸代谢浓度变化的氢质子磁共振波谱相关研究

目的:探讨早期认知功能损害患者的脑组织谷氨酸代谢浓度变化及氢质子磁共振波谱(1 H-MRS)特征。方法:回顾性分析2018年8月至2022年8月间136例早期认知损害患者(观察组)和100名健康志愿者(对照组)的1 H-MRS扫描数据。比较两组及观察组内不同认知障碍程度患者的NAA/Cr、mI/Cr、Glx/Cr比值。结果:观察组NAA/Cr显著低于对照组,而mI/Cr、Glx/Cr显著高于对照组。ROC分析显示,NAA/Cr、mI/Cr、Glx/Cr均可用于诊断早期认知损害。在观察组内,随着认知障碍加剧,NAA/Cr降低,而mI/Cr、Glx/Cr升高。1 H-MRS结果显示,NAA/Cr与认知障碍程度负相关,mI/Cr、Glx/Cr负相关。结论:基于以上发现,NAA/Cr、mI/Cr、Glx/Cr的变化不仅可用于早期认知损害的诊断,还与认知障碍程度密切相关,为临床治疗提供参考。因此,具有较高的临床应用价值和推广意义。

质子交换膜水电解制氢阳极铱基催化剂的研究进展

氢能作为一种清洁、高效、可再生的能源,在我国能源绿色低碳转型过程中具有重要的战略地位。质子交换膜水电解(PEMWE)制氢技术因其工作电流密度大、能量效率高以及动态响应快等优势,被认为是一种极具发展前景的制绿氢技术。然而,受限于该系统核心组件之一阳极铱基催化剂的资源稀缺性和高昂成本,PEMWE在产业界仍难以得到大规模应用。针对这一问题,研究者们致力于探索兼具经济性和高效的铱基催化剂,实现PEMWE大规模应用时面临的降本增效问题。本文介绍了PEMWE制氢的基本原理、系统构成和相应功能,从金属型、氧化物型及负载型3个角度详细综述了铱基催化剂在PEMWE制氢阳极析氧反应中的应用现状,重点讨论形貌调控、结构设计和载体选择对催化性能的影响,并提出未来应致力于开发低铱载量且高活性和稳定性的催化剂。

Protonation effect on catalytic water oxidation activity of a mononuclear Ru catalyst containing a free pyridine unit

Two efficient single-site Ru water oxidation catalysts [Ru（bda）（pic）（Ln）] （bda=2,2＇-bipyridine- 6,6＇-dicarboxylic acid, pic=picoline, Ll=4,5-bipyridine-2,7-di-tett-butyl-9,9-dimethylxanthene, L2=4- pyridine-5-phenyl-2,7-di-tert-butyl-9,9-dimethylxanthene） were only synthesized containing different xanthene ligands at the axial site. These complexes have been thoroughly characterized by spectroscopic （UV-vis, NMR） and electrochemical （CV and DIV） techniques. Kinetic analysis proved that the mechanism of water oxidation comprises the water nucleophilic attack process on high-valence ruthenium species. It is found that the catalyst I displayed higher activity than catalyst 2 on water oxidation, caused by the protonation of the axial ligand LI with a free pyridine.

Conjugate addition‐enantioselective protonation to forge tertiary stereocentresαto azaarenes via cooperative hydrogen atom transfer and chiral hydrogen‐bonding catalysis

Cooperative hydrogen atom transfer and chiral hydrogen‐bonding catalysis as a new platform for the asymmetric synthesis of azaarene derivatives is reported.By using a tetrabutylammonium decatungstate as the photocatalyst and a chiral phosphoric acid as the hydrogen‐bonding catalyst,transformations of a variety of commercially available hydrocarbons and silanes with diverseα‐branched 2‐vinylazaarenes could efficiently experience a tandem radical conjugate addition and enantioselective protonation process,providing a convenient and fully atom economical approach to access a range of valuable enantioenrichedα‐tertiary azaarenes in high yields with good to excellent enantioselectivities(up to 93%ee).Through the direct use of tert‐butyl methylcarbamate as the feedstock,this method enables a highly practical and concise synthesis of the enantiomerically pure medicinal molecule pheniramine(Avil).

Synthesis,Characterization and Protonation Study of Novel Poly(thioether imide)s based on Aromatic Heterocyclic Diimide

Novel poly（thioether imide）s were synthesized by 2,5-dimercapto-l,3,4-thiadiazole, and aromatic heterocyclic chlorodiimids through nucleophilic!substitution reaction as alkali catalysts were presented. The poly（thioether imide）s exhibited good thermal property. The glass transition temperatures of polymers were around 373 ℃, and 10% weight loss temperatures were in the range of 450-500 ℃ in nitrogen/air atmosphere. Meanwhile, the chloroform dilute solutions of these polYmers could show strong UV-vis absorption peaks at about 289 nm. After being protonated by inorganic acids （HC1）, the new shoulder absorption peaks were observed at 350 nm. The PL absorption bands of polymer solutions were in the region of 350-550 nm, which showed the green-yellow fluorescence.

Protonation and Dehydrogenation During the Multiphoton Ionization of the Cluster:C_4H_5N(H_2O)_n

Multiphoton ionization (MPI) of the hydrogen-bonded clusters C4H5N-(H2O)(m) was studied with a time of flight (TOF) mass spectrometer at 355 nm. Series of the pyrrole-water cluster ions were observed, including unprotonated cluster ions [C4H5N-(H2O)(n)](+), protonated cluster ions [C4H5N-(H2O)(n)H](+) and dehydrogenated cluster ions [C4H4N-(H2O)(n)](+). Both the experimental and ab initio calculated results agree with that the dehydrogenation has more probabilities to occur while the value of n is raised.

Sites of Protonation and Unimolecular Fragmentation of Protonated N-Hydroxyphthalimide in the Gas Phase

The low energy collisioninduced dissociation, linked scan techniques and isotopic labeling experiment were used to investigate the unimolecular fragmentation of protonated N-hydroxyphthalimide under electron impact and chemical ionization conditions. It was found that this compound shows an unusual reactivity towards protonation. Two possible sites of protonation have been proposed to explain the corresponding fragmentation processes, one is that the protonation takes place on the oxygen atom of hydroxyl group, resulting in the loss of water and the other is the formation of an intermediary protonbound complex in the fragmentation process, giving rise to the fragment ions of m/z 133 and m/z 135. The results show both cases are coexistence in the fragmentations of protonated N-hydroxyphthalimide, and the unimolecular fragmentation pathways are available.

Protonation Effect on One- and Two-photon Absorption Property of a Newly Synthesized Octupolar Chromophore

The protonation effects on one- and two-photon absorption properties of an octupolar molecule TA with 1,3,5-triazine core and pyrrole electron-donating end-groups have been studied at hybrid density functional theory level. A computational scheme is developed to simulate a proton attached to an atom. The numerical results show that large changes in both one- and two-photon absorption properties are observed when the compound is transformed from neutral to threefold protonated states. When the compound is protonated, more charge transfer states appear and the absorption band has a red-shift. Furthermore, the two-photon absorption cross-section is largely enhanced. The theoretical calculations demonstrate the protonation effect on promoting the intramolecular charge transfer strength. The results present qualitative agreement with the experimental observations. A two-photon absorption switch with the compound TA based on the protonation effect is proposed.

Effect of Surface Protonation on Device Performance and Dye Stability of Dye-sensitized Ti02 Solar Cell

A flat thin TiO2 film was employed as the photo-electrode of a dye sensitized solar cell （DSSC）, on which only a geometrical mono-layer of dye was attached. The effect of sur- face protonation by HCI chemical treatment on the performance of DSSCs was studied. The results showed that the short-circuit current Jsc increased significantly upon the HCI treatment, while the open-circuit voltage Voc decreased slightly. Compared to the untreated DSSC, the Jsc and energy conversion efficiency was increased by 31% and 25%, respectively, for the 1 mol/L HCI treated cell. TiO2 surface protonation improved electronic coupling between the chemisorbed dye and the TiO2 surface, resulting in an enhanced electron in- jection. The decreased open-circuit voltage after TiO2 surface protonation was mainly due to the TiO2 conduction band edge downshift and was partially caused by increased electron recombination with the electrolyte. In situ Raman degradation study showed that the dye stability was improved after the TiO2 surface protonation. The increased dye stability was contributed by the increased electron injection and electron back reaction with the electrolyte under the open-circuit condition.

Direct Observation of Transient Species Generated from Protonation and Deprotonation of the Lowest Triplet of p-Nitrophenylphenol

Photo-induced proton coupled electron transfer(PCET)is essential in the biological,photosynthesis,catalysis and solar energy conversion processes.Recently,p-nitrophenylphenol(HO-Bp-NO2)has been used as a model compound to study the photo-induced PCET mechanism by using ultrafast spectroscopy.In transient absorption spectra both singlet and triplet states were observed to exhibit PCET behavior upon laser excitation of HO-Bp-NO2.When we focused on the PCET in the triplet state,a new sharp band attracted us.This band was recorded upon excitation of HO-Bp-NO2 in aprotic polar solvents,and has not been observed for p-nitrobiphenyl which is without hydroxyl substitution.In order to find out what the new band represents,acidic solutions were used as an additional proton donor considering the acidity of HO-Bp-NO2.With the help of results in strong(~10^-1 mol/L)and weak(~10^-4 mol/L)acidic solutions,the new band is identified as open shell singlet O-Bp-NO2H,which is generated through protonation of nitro O in 3HO-Bp-NO2 followed by deprotonation of hydroxyl.Kinetics analysis indicates that the formation of radical·OBp-NO2 competes with O-Bp-NO2H in the way of concerted electron-proton transfer and/or proton followed electron transfers and is responsible for the low yield of O-Bp-NO2H.The results in the present work will make it clear how the3HO-Bp-NO2 deactivates in aprotic polar solvents and provide a solid benchmark for the deeply studying the PCET mechanism in triplets of analogous aromatic nitro compounds.

Modeling of the Chemico-Physical Process of Protonation of Molecules Entailing Some Quantum Chemical Descriptors

Relying upon the basic tenets of scientific modeling, an ansatz for the evaluation of proton affinity of mole-cules are evolved in terms of a four component model. The components of the model chosen are global de-scriptors like ionization energies, global softness, electronegativity and electrophilicity index. These akin quantum mechanical descriptors of atoms and molecules are linked with the charge rearrangement and polarization that occur during the physico-chemical process of protonation of molecules. The suggested ansatz is invoked to compute the protonation energy of as many as 43 compounds of diverse physico-chemical nature viz, hydrocarbons, alcohols, carbonyls, carboxylic acids, esters, aliphatic amines and aromatic amines. A detailed comparative study of theoretically evaluated protonation energies of the above mentioned molecules vis-à-vis their corresponding experimental counterparts reveals that there is a close agreement between the theory and experiment. Thus the results strongly suggest that the proposed modeling and the ansatz for computing PA, the proton affinity, of molecules for studying the physico-chemical process of protonation may be valid proposition.

Protonation Sites in Benzimidazolyl-Chalcones Molecules: An ab Initio and DFT Investigation

In this work, we have focused our investigations on the protonation sites predilection in the benzimidazolyl- chalcones (BZC) derivatives. Particularly, we are interested in the study of geometrical and energetical parameters. BZC are well known for their particularly nematicidal activity. Ten (10) BZC derivatives coded BZC-1 to BZC-10, with various larvicidal concentrations, have been selected for this work. They all are different one from another by the phenyl ring which is substituted by electron modulators such as alkyl, hydroxyl, alkoxy, aminoalkyl, halogen and nitro or replaced by the furan. Quantum chemical methods, namely HF/6-311 + G(d,p) and MPW1PW91/6- 311 + G(d,p) theory levels have been used to determine the geometrical and energetical parameters by the protonation on each heteroatom of the BZC derivative. An accuracy results with relatively less time consuming has been obtained using Hartree-Fock (HF) and Density Functional Theory methods (DFT/MPW1PW91). The calculations results allow identifying the sp2 nitrogen as the preferential site of protonation in BZC derivative compounds.