Hydroxychloroquine and a low antiresorptive activity bisphosphonate conjugate prevent and reverse ovariectomy-induced bone loss in mice through dual antiresorptive and anabolic effects

Osteoporosis remains incurable.The most widely used antiresorptive agents,bisphosphonates(BPs),also inhibit bone formation,while the anabolic agent,teriparatide,does not inhibit bone resorption,and thus they have limited efficacy in preventing osteoporotic fractures and cause some side effects.

Using Electrodeposition of Carboxylated Chitosan for Green Preparation of Copper Nanoclusters and Nanocomposite Films

On the basis of coordinated electrodeposition of carboxylated chitosan(CCS),we presented a green method to prepare Cu NCs and Cu NCs/CCS nanocomposite films.The method shows a range of benefits,such as the convenient and eco-friendly process,mild conditions,and simple post-treatment.The experimental results reveal that a homogeneous deposited film(Cu NCs/CCS nanocomposite film)is generated on the Cu plate(the anode)after electrodeposition,which exhibits an obvious red florescence.The results from TEM observation suggest there are nanoparticles(with the average particle size of 2.3 nm)in the deposited film.Spectral analysis results both demonstrate the existence of Cu NCs in the deposited film.Moreover,the Cu NCs/CCS film modified electrode is directly created through electrodeposition of CCS,which enables promising application in the electrochemical sensing.By means of fluorescence properties of Cu NCs,the Cu NCs/CCS film also owns the potential in fluorescence detection.Therefore,this work builds a novel method for the green synthesis of Cu NCs,meanwhile it offers a convenient and new electrodeposition strategy to prepare polysaccharide-based Cu NCs nanocomposites for uses in functional nanocomposites and bioelectronic devices.

Aminated Cyclopropylmethylphosphonates as Potent Prostate Cancer Inhibitors

Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostate cancer cell line PC-3, and showed potent inhibiting activity at low micromolar concentrations (with an IC50 of approximately 45 μM).

Synthesis,Structure and Characterization of a 3D Chiral Carboxylate and Phosphonate Metalorganic Framework Based on 1,1?-Biphenol Ligand

A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1？-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra（FTIR）, circular dichroism（CD） and thermogravimetric analyses（TGA）. Two neighboring Mn ions are linked by two carboxylate groups and one phosphate group to form a di-manganese unit [Mn2] and each [Mn2] cluster in 1 is linked by five ligands, generating a 3D network with fns topology. In addition, the photoluminescence properties of 1 and H4 L were investigated.

Hydrothermal Synthesis,Crystal Structure and Fluorescent Property of a New Zinc Carboxylate-phosphonate:[Zn_3(O_3PCH(CH_3)COO)_2(H_2O)]

A new carboxylate-phosphonate, [Zn3（O3PCH（CH3）COO）2（H2O）] 1, has been successfully synthesized by hydrothermal technique and characterized by X-ray single-crystal structure analysis, elemental analysis and infrared spectroscopy. It crystallizes in monoclinic, space group P2 1/c with a = 4.9521（5）, b = 21.953（3）, c = 13.2266（18） A, β = 100.704（2）°, V= 1412.9（3） A3, Z= 4, Mr = 516.19, Dc= 2.427 g/cm^3, F（000） = 1016,μ（MoKα） = 5.332 mm^-1 and T= 293（2） K. The final R = 0.0605 and wR = 0.1354 for 2957 observed reflections with I 〉 2σ（I）. The thermogravimetric analysis （TGA） and fluorescent measurement have been done. The structure of compound 1 is a 3D open framework with 32-atom channels.

Enabling heterogeneous catalysis to achieve carbon neutrality: Directional catalytic conversion of CO_(2) into carboxylic acids

The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.

Aminated (Cyclopropylmethyl)Phosphonates: Synthesis and Anti-Pancreatic Cancer Activity

Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyclopropyl)methyl)phosphonate and various amines in the presence of Hunig’s base. Upon biological activity screening these compounds demonstrated encouraging anti-pancreatic cancer properties at low micromolar concentrations.

Synthesis of phosphonated graphene oxide by electrochemical exfoliation to enhance the performance and durability of high-temperature proton exchange membrane fuel cells

The doping of functionalized graphene oxide(GO)in the membranes becomes a promising method for improving the performance of high-temperature proton exchange membrane fuel cells(HT-PEMFC).Phosphonated graphene oxide(PGO)with a P/O ratio of 8.5%was quickly synthesised by one-step electrochemical exfoliation based on a three-dimensiaonal(3D)printed reactor and natural graphite flakes.Compared with the GO prepared by the two-step electrochemical exfoliation method,the PGO synthesized by the one-step electrochemical exfoliation can better improve the performance of the membrane-electrode-assembly(MEA)based on the polybenzimidazole(PBI)membrane in the HTPEMFC.The doping of 1.5 wt%GO synthesised by electrochemical exfoliation with the 2-step method or reactor method in PBI increased the peak power density by 17.4%or 35.4%compared to MEA based on pure PBI membrane at 150℃,respectively.In addition,the doping of PGO in PBI improves its durability under accelerated stress test(AST).

Carboxylic bacterial cellulose fiber-based hydrogel electrolyte with imidazole-type ionic liquid for dendrite-free zinc metal batteries

Aqueous zinc metal batteries are regarded as the most promising energy storage system due to their advantages of high safety,low cost,and high theoretical capacity.However,the growth of dendrites and the occurrence of side reactions hinder the development of zinc metal batteries.Despite previous attempts to design advanced hydrogel electrolytes,achieving high mechanical performance and ionic conductivity of hydrogel electrolytes has remained challenging.In this work,a hydrogel electrolyte with an ionic crosslinked network is prepared by carboxylic bacterial cellulose fiber and imidazole-type ionic liquid,following by a covalent network of polyacrylamide.The hydrogel electrolyte possesses a superior ionic conductivity of 43.76 mS cm^(−1),leading to a Zn^(2+)migration number of 0.45,and high mechanical performance with an elastic modulus of 3.48 GPa and an elongation at breaking of 38.36%.More importantly,under the anion-coordination effect of the carboxyl group in bacterial cellulose and[BF4]−in imidazole-type ionic liquid,the solvation sheath of hydrated Zn^(2+)ions and the nucleation overpotential of Zn plating are regulated.The results of cycled testing show that the growth of zinc dendrites is effectively inhibited and the generation of irreversible by-products is reduced.With the carboxylic bacterial cellulose-based hydrogel electrolyte,the Zn||Zn symmetric batteries offer good cyclability as well as Zn||Ti batteries.

AAV mediated carboxyl terminus of Hsp70 interacting protein overexpression mitigates the cognitive and pathological phenotypes of APP/PS1 mice

The E3 ubiquitin ligase,carboxyl terminus of heat shock protein 70(Hsp70)interacting protein(CHIP),also functions as a co-chaperone and plays a crucial role in the protein quality control system.In this study,we aimed to investigate the neuroprotective effect of overexpressed CHIP on Alzheimer’s disease.We used an adeno-associated virus vector that can cross the blood-brain barrier to mediate CHIP overexpression in APP/PS1 mouse brain.CHIP overexpression significantly ameliorated the performance of APP/PS1 mice in the Morris water maze and nest building tests,reduced amyloid-βplaques,and decreased the expression of both amyloid-βand phosphorylated tau.CHIP also alleviated the concentration of microglia and astrocytes around plaques.In APP/PS1 mice of a younger age,CHIP overexpression promoted an increase in ADAM10 expression and inhibitedβ-site APP cleaving enzyme 1,insulin degrading enzyme,and neprilysin expression.Levels of HSP70 and HSP40,which have functional relevance to CHIP,were also increased.Single nuclei transcriptome sequencing in the hippocampus of CHIP overexpressed mice showed that the lysosomal pathway and oligodendrocyte-related biological processes were up-regulated,which may also reflect a potential mechanism for the neuroprotective effect of CHIP.Our research shows that CHIP effectively reduces the behavior and pathological manifestations of APP/PS1 mice.Indeed,overexpression of CHIP could be a beneficial approach for the treatment of Alzheimer’s disease.

Amine-functionalized metal organic framework@graphene oxide as filler in PAEK-containing carboxyl group membrane for ultrafiltration with ultra-high permeability and strong fouling resistance

Achieving high fouling resistance and permeability using membrane separation technology in water treatment processes remains a challenge.In this work,a novel mixed-matrix membrane(MMM)(poly(arylene ether ketone)[PAEK]-containing carboxyl groups[PAEK-COOH]/UiO-66-NH_(2)@graphene oxide[GO])with superb fouling resistance and high permeability was prepared by the nonsolvent-induced phase separation method,by in-situ growth of UiO-66-NH_(2) on the GO layer,and by preparing hydrophilic PAEK-COOH.On the basis of the structure and performance analysis of the MMM,the maximum water flux reached 591.25 L·m^(-2)·h^(-1) for PAEK-COOH/UiO-66-NH_(2)@GO,whereas the retention rate for bovine serum albumin increased from 85.40%to 94.87%.As the loading gradually increased,the hydrophilicity of the MMMs increased,significantly enhancing their fouling resistance.The strongest anti-fouling ability observed was 94.74%,which was 2.02 times greater than that of the pure membrane.At the same time,the MMMs contained internal amide and hydrogen bonds during the preparation process,forming a cross-linked structure,which further enhanced the mechanical strength and chemical stability.In summary,the MMMs with high retention rate,strong permeability,and anti-fouling ability were successfully prepared.

一个新的三维超分子配位聚合物[Ni(pyridine-2-carboxylate)2]n·2nH2O的水热合成及晶体结构

采用水热法合成了一个新的金属-有机配位聚合物[Ni(pyridine-2-carboxylate)2]n.2nH2O,对其进行元素分析、红外光谱和X射线单晶衍射测定.结构分析表明:该晶体属于三斜晶系,P-1空间群,晶胞参数a=5.1284(6)nm,b=7.6346(9)nm,c=9.2295(11)nm,α=74.902(2)°,β=84.347(2)°,γ=71.442(2)°,V=330.70(7)nm3,化学式为C12H12NiN2O6,Mr=338.95,Dc=1.702g/cm3,μ(Mo,Kα)=1.497mm-1,F(000)=174,Z=1,R=0.0333,wR=0.0384((I>2σ(I)).并且该配合物通过O—H…O和C—H…O氢键形成了三维超分子网状结构.

Enantioselective synthesis of chiral phosphonylated 2,3-dihydrofurans by copper catalyzed asymmetric formal [3+2] cycloaddition of propargylic esters with β-keto phosphonates

Copper catalyzed asymmetric formal [3＋2] cycloaddition of propargylic esters toβ‐keto phospho‐nates for the synthesis of chiral phosphonylated 2,3‐dihydrofurans was developed. By using a bulky and structurally rigid tridentate ketimine P,N,N ligand, a series of optically active phosphonylated 2,3‐dihydrofurans were prepared in high yield and up to 92%ee.

Influence of Polycarboxylate Superplasticizer on Rheological Behavior in Cement Paste

Molecular structures of polycarboxylate（PCE） superplasticizer significantly affect the rheological properties of cement paste. Consequently, we employed self-synthesized PCE copolymers with different carboxylic densities to investigate their influence on the rheological behavior of cement paste. Three typical rheological models were applied to analyze the rheological properties, including Power-law model, Bingham model as well as Herschel-Buikley model. In addition, the thixotropical performances of cement paste in the presence of PCE with different carboxylic densities were investigated. The results show that the carboxylic density of PCE greatly influences the dispersing performance of PCE superplasticizers. As carboxylic density increases, the dispersing capability of PCE improves, and P（PEG1-AA6） possesses the strongest dispersing capability, the initial fluidity and 1 h fluidity of cement paste are both the highest, and cement paste has the lowest viscosity and the smallest hysteresis loop.

Simultaneous quantification of prodrug oseltamivir and its metabolite oseltamivir carboxylate in human plasma by LC-MS/MS to support a bioequivalence study

A simple, precise and rapid liquid chromatography-tandem mass spectrometry （LC-MS/MS） method has been developed and validated for the simultaneous determination of oseltamivir and oseltamivir carboxylate, a neuraminidase inhibitor, using their deuterated analogs as internal standards （ISs）. The method involved solid phase extraction of the analytes and ISs from 200 μL human plasma with no reconstitution and drying steps. The chromatographic separation was achieved on a Symmetry C18 （100 mm × 4.6 mm, 5 μm） column using 10 mM ammonium formate and acetonitrile （30：70, v/v） as the mobile phase in a run time of 2.0 min. Quantitation of analytes and ISs were done by multiple reaction monitoring on a triple quadrupole mass spectrometer in the positive ionization mode. The linearity of the method was established in the concentration range of 0.5-200 ng/mL and 2.0-800 ng/mL for oseltamivir and oseltamivir carboxylate respectively. The mean extraction recovery for oseltamivir （94.4%） and oseltamivir carboxylate （92.7%） from spiked plasma samples was consistent and reproducible. The application of this method was demonstratedby a bioequivalence study in 42 healthy Indian subjects with 75 mg oseltamivir phosphate capsules. The assay reproducibility was established by reanalysis of 151 incurred subject samples.

Highly efficient production of 2,5-dihydroxymethylfuran from biomass-derived 5-hydroxymethylfurfural over an amorphous and mesoporous zirconium phosphonate catalyst

The development of high-efficiency and low-cost catalysts is very crucial for the MeerweinPonndorf-Verley (MPV) reduction of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF). In this work, an amorphous and mesoporous zirconium phosphonate catalyst (Zr-DTMP), which is a zirconium-containing organic-inorganic nanohybrid, was successfully designed and synthesized by the simple assembly of zirconium tetrachloride (ZrCl4) and diethylene triaminepenta(methylene phosphonic acid)(DTMP). Satisfactorily, when Zr-DTMP was employed for the MPV reduction of HMF in the presence of 2-butanol (secBuOH), DHMF yield could be achieved as 96.5% in 3 h under a relatively mild reaction temperature of 140℃. Systematic investigations indicated that this high catalytic activity should be mainly due to the cooperative role of enhancive Lewis acid site (Zr4+) and Lewis base site (O2-) in activating the carbonyl group of HMF and dissociating the hydroxyl group of secBuOH, respectively. Additionally, Zr-DTMP showed excellent catalytic stability, when it was successively used 5 recycles, its surface characteristics and textural properties still remained almost unchanged, and so, the catalytic activity was not obviously affected. More interestingly, Zr-DTMP could also be applied for the selective reduction of other biomass-derived carbonyl compounds, such as 5-methylfurfural (MF), furfural (FF), levulinic acid (LA), ethyl levulinate (EL) and cyclohexanone (CHN), into the corresponding products with high yields, which is beneficial to the effective synthesis of various valuable bio-based chemicals.

SYNTHESIS, CHARACTERIZATION AND RING-OPENING POLYMERIZATION OF CYCLIC (ARYLENE PHOSPHONATE) OLIGOMERS

A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yield of cyclic (arylene phosphonate) oligomers is over 85% by using hexadecyltrimethylammoniun bromide as phase transfer catalyst (PTC) at 0 'C . The structures of the cyclic oligomers were confirmed by a combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and IR analysis. These cyclic oligomers undergo facile ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator to give linear polyphosphonate. Free-radical ring-opening polymerization of cyclic(arylene phosphonate) oligomers containing sulfur linkages was also performed in the melt using 2,2'-dithiobis(benzothiazole) (DTB) as the initiator at 270 °C and the resulting polymer had a Mw, of 8 × 103 with a molecular weight distribution of 4. Ring-opening copolymerization of these cyclic oligomers with cyclic carbonate oligomers was also achieved. The average molecular weight of the resulting copolymer is higher than the corresponding homopolymer and the thermal stability of the copolymer is better than the corresponding homopolymer.

Dispersion of Co-poly Carboxylate Superplasticizer Containing Poiyether Side Chain

Free radical co-polymerization was employed to synthesize co-poly carboxylate (PC) su-perplasticizers with different amount of carboxyl and methyl polyethylene glycol (MPEG) side chain. Dispersion ability and retention of PC were compared with one another. The results show that increase of side chain is advantageous to dispersion, but it decreases when amount of MPEG is beyond a certain value which is different with the proportion of carboxyl. If the amount of carboxyl increases, the influence of side chain in copolymer on dispersion diminishes. Polyether side chain is advantageous to retention. And the author explained the mechanism of PC using the theory of steric repulsive force.

Phosphonated USY,a promising catalyst for the development of environmentally benign biodiesel(methyl acetate) process

The present study focuses on the evaluation of the potential applicability of Ultra Stable Y（USY） and phosphonated USY（1 wt%-4 wt%phosphorous loading） as heterogeneous catalysts for biodiesel（methyl acetate） production.The synthesized catalysts were characterized by powder X-ray diffraction（XRD）,Brunaer-Emmett-Teller（BET） surface area,total acidity by temperature-programmed desorption of ammonia（TPD-NH3） and Fourier Transform Infrared（FTIR） spectra.The performances of catalysts were evaluated for the transesterification of butyl acetate with methanol（a model reaction in biodiesel production）.In view to obtain a maximum yield of methyl acetate,the optimization of process parameters such as reactant molar ratio,catalyst loading,reaction temperature and reaction time was performed.All the phosphonated USY catalysts showed higher catalytic activity than the parent USY,which can be attributed to the increase of total acidity due to phosphonation.2 wt% P/USY（2% phosphorous loaded on USY） exhibited 92% methyl acetate yield with 100% selectivity,which was proved to be a potential catalyst for biodiesel production.The invented catalyst was found to be stable and reusable for five catalytic cycles,demonstrating that it might be a environmentally benign catalytic process.

Phosphonate-derived nitrogen-doped cobalt phosphate/carbon nanotube hybrids as highly active oxygen reduction reaction electrocatalysts

The exploration of cost-effective non-noble-metal electrocatalysts is highly imperative to replace the state-of-the-art platinum-based catalysts for oxygen reduction reaction(ORR). Here, we prepared cobalt phosphonate-derived N-doped cobalt phosphate/carbon nanotube hybrids(Co Pi C-N/CNTs) by hydrothermal treatment of N-containing cobalt phosphonate and oxidized carbon nanotubes(o-CNT) followed by high-temperature calcination under nitrogen atmosphere. The resultant Co Pi C-N/CNT exhibits a superior electrocatalytic performance for the ORR in alkaline media, which is equal to the commercial Pt/C catalyst in the aspect of half-wave potential, onset potential and diffuse limiting current density. Furthermore, the excellent tolerance to methanol and strong durability outperform those of commercial Pt/C. It is found that cobalt phosphonate-derived N-doped cobalt phosphate and the in-situ formed graphitic carbons play key roles on the activity enhancement. Besides, introducing a suitable amount of CNTs enhances the electronic conductivity and further contributes to the improved ORR performance.