Amino-functionalized UiO-66-doped mixed matrix membranes with high permeation performance and fouling resistance

For the reduction of bovine serum proteins from wastewater,a novel mixed matrix membrane was prepared by functionalizing the substrate material polyaryletherketone(PAEK),followed by carboxyl groups(C-SPAEKS),and then adding amino-functionalized UiO-66-NH_(2)(Am-UiO-66-NH_(2)).Aminofunctionalization of UiO-66 was accomplished by melamine,followed by an amidation reaction to immobilize Am-UiO-66-NH_(2),which was immobilized on the surface of the membrane as well as in the pore channels,which enhanced the hydrophilicity of the membrane surface while increasing the negative potential of the membrane surface.This nanoparticle-loaded ultrafiltration membrane has good permeation performance,with a pure water flux of up to 482.3 L·m^(-2)·h^(-1) for C-SPAEKS/AmUiO-66-NH_(2) and a retention rate of up to 98.7%for bovine serum albumin(BSA)-contaminated solutions.Meanwhile,after several hydrophilic modifications,the flux recovery of BSA contaminants by this series of membranes increased from 56.2%to 80.55%of pure membranes.The results of ultra-filtration flux time tests performed at room temperature showed that the series of ultrafiltration membranes remained relatively stable over a test time of 300 min.Thus,the newly developed mixed matrix membrane showed potential for high efficiency and stability in wastewater treatment containing bovine serum proteins.

Hollow Ni Mo-based nitride heterojunction with super-hydrophilic/aerophobic surface for efficient urea-assisted hydrogen production

Hydrogen evolution reaction(HER)and urea oxidation reaction(UOR)are key reactions of the watercycling associated catalytic process/device.The design of catalysts with a super-hydrophilic/aerophobic structure and optimized electron distribution holds great promise.Here,we have designed a threedimensional(3D)hollow Ni/NiMoN hierarchical structure with arrayed-sheet surface based on a onepot hydrothermal route for efficient urea-assisted HER based on a simple hydrothermal process.The Ni/NiMoN catalyst exhibits super-hydrophilic/aerophobic properties with a small droplet contact angle of 6.07°and an underwater bubble contact angle of 155.7°,thus facilitating an escape of bubbles from the electrodes.Density functional theory calculations and X-ray photoelectron spectroscopy results indicate the optimized electronic structure at the interface of Ni and NiMoN,which can promote the adsorption/desorption of reactants and intermediates.The virtues combining with a large specific surface area endow Ni/NiMoN with efficient catalytic activity of low potentials of 25 mV for HER and 1.33 V for UOR at10 mA cm^(-2).The coupled HER and UOR system demonstrates a low cell voltage of 1.42 V at 10 mA cm^(-2),which is approximately 209 mV lower than water electrolysis.

Multifunctional AlPO_(4)reconstructed LiMn_(2)O_(4)surface for electrochemical lithium extraction from brine

LiMn_(2)O_(4)(LMO)electrochemical lithium-ion pump has gained widespread attention due to its green,high efficiency,and low energy consumption in selectively extracting lithium from brine.However,collapse of crystal structure and loss of lithium extraction capacity caused by Mn dissolution loss limits its industrialized application.Hence,a multifunctional coating was developed by depositing amorphous AlPO_(4)on the surface of LMO using sol-gel method.The characterization and electrochemical performance test provided insights into the mechanism of Li^(+)embedment and de-embedment and revealed that multifunctional AlPO_(4)can reconstruct the physical and chemical state of LMO surface to improve the interface hydrophilicity,promote the transport of Li^(+),strengthen cycle stability.Remarkably,after 20 cycles,the capacity retention rate of 0.5AP-LMO reached 93.6%with only 0.147%Mn dissolution loss.The average Li^(+)release capacity of 0.5AP-LMO//Ag system in simulated brine is 28.77 mg/(g h),which is 90.4%higher than LMO.Encouragingly,even in the more complex Zabuye real brine,0.5AP-LMO//Ag can still maintain excellent lithium extraction performance.These results indicate that the 0.5AP-LMO//Ag lithium-ion pump shows promising potential as a Li^(+)selective extraction system.

Structural effects induced by dialysis-based purification of carbon nanomaterials

Dialysis plays a crucial role in the purification of nanomaterials but its impact on the structural properties of carbon nanomaterials was never investigated.Herein,a carbon-based nanomaterial generated electrochemically in potassium phosphate buffer,was characterized before and after dialysis against pure water.It is shown that dialysis affects the size of the carbon domains,structural organization,surface functionalization,oxidation degree of carbon,and grade of amorphicity.Accordingly,dialysis drives the nanomaterial organization from discrete roundish carbon domains,with sizes ranging from 70 to 160 nm,towards linear stacking structures of small nanoparticles(<15 nm).In parallel,alcohol and ether(epoxide)surface groups evolve into more oxidized carbon groups(e.g.,ketone and ester groups).Investigation of the as-prepared nanomaterial by electron paramagnetic resonance(EPR)revealed a resonance signal consistent with carbon-oxygen centred radicals.Additionally,this study brings to light the selective affinity of the carbon nanomaterial under study to capture Na^(+)ions,a property greatly enhanced by the dialysis process,and its high ability to trap oxygen,particularly before dialysis.These findings open new perspectives for the application of carbon-based nanomaterials and raise awareness of the importance of structural changes that can occur during the purification of carbon-based nanomaterials.

Interfacial modification using the cross-linkable tannic acid for highly-efficient perovskite solar cells with excellent stability

Although the performance of perovskite solar cells(PSCs)has been dramatically increased in recent years,stability is still the main obstacle preventing the PSCs from being commercial.PSC device instability can be caused by a variety of reasons,including ions diffusion,surface and grain boundary defects,etc.In this work,the cross-linkable tannic acid(TA)is introduced to modify perovskite film through post-treatment method.The numerous organic functional groups(–OH and C=O)in TA can interact with the uncoordinated Pb^(2+)and I^(-)ions in perovskite,thus passivating defects and inhibiting ions diffusion.In addition,the formed TA network can absorb a small amount of the residual moisture inside the device to protect the perovskite layer.Furthermore,TA modification regulates the energy level of perovskite,and reduces interfacial charge recombination.Ultimately,following TA treatment,the device efficiency is increased significantly from 21.31%to 23.11%,with a decreased hysteresis effect.Notably,the treated device shows excellent air,thermal,and operational stability.In light of this,the readily available,inexpensive TA has the potential to operate as a multipurpose interfacial modifier to increase device efficiency while also enhancing device stability.

Reconcile the contradictory wettability requirements for the reduction and oxidation half-reactions in overall CO_(2) photoreduction via alternately hydrophobic surfaces

The overall photocatalytic CO_(2) reduction reaction(OPCRR)that can directly convert CO_(2) and H_(2)O into fuels represents a promising renewable energy conversion technology.As a typical redox reaction,the OPCRR involves two half-reactions:the CO_(2) reduction half-reaction(CRHR)and the water oxidation half-reaction(WOHR).Generally,both half-reactions can be promoted by adjusting the wettability of catalysts.However,there is a contradiction in wettability requirements for the two half-reactions.Specifically,CRHR prefers a hydrophobic surface that can accumulate more CO_(2) molecules on the active sites,ensuring the appropriate ratio of gas-phase(CO_(2))to liquid-phase(H_(2)O)reactants.Conversely,the WOHR prefers a hydrophilic surface that can promote the departure of the gaseous product(O_(2))from the catalyst surface,preventing isolation between active sites and the reactant(H_(2)O).Here,we successfully reconciled the contradictory wettability requirements for the CRHR and WOHR by creating an alternately hydrophobic catalyst.This was achieved through a selectively hydrophobic modification method and a charge-transfer-control strategy.Consequently,the collaboratively promoted CRHR and WOHR led to a significantly enhanced OPCRR with a solar-to-fuel conversion efficiency of 0.186%.Notably,in ethanol production,the catalyst exhibited a 10.64-fold increase in generation rate(271.44μmol g^(-1)h~(-1))and a 4-fold increase in selectivity(55.77%)compared to the benchmark catalyst.This innovative approach holds great potential for application in universal overall reactions involving gas participation.

Pervaporation performance and characterization of hydrophilic ZSM-5 zeolite membranes for high inorganic acid and inorganic salts

The hydrophilic ZSM-5 zeolite membranes are applied to separate the inorganic acid solutions and inorganic acid/inorganic salt mixtures by pervaporation,and the membrane presents good stability,dehydration,and desalination performance.Influences of inorganic acid type(H_(2)SO_(4),H_(3)PO_(4),HNO_(3),and HCl),H_(2)SO_(4)concentration(1-6 mol·L^(-1)),test temperature(60-90℃)and inorganic acid/inorganic salt type(2 mol·L^(-1)H_(2)SO_(4)and sulfate,2 mol·L^(-1)H3PO4 and phosphate)on the pervaporation performance are investigated in this work.Either for concentrating 3%(mass)H_(2)SO_(4)solution or consecutive dehydrating 20%(mass)H_(2)SO_(4)solution,the hydrophilic ZSM-5 zeolite membrane has a good dehydration performance and stability.Even though the H_(2)SO_(4)concentration and test temperature are increased to 6 M and 90℃,only H_(2)O molecules could pass through the membrane and pH value of the permeation is kept neutral.Besides,the membrane has good dehydration and desalination performance for H_(2)SO_(4)/sulfates and H_(3)PO_(4)/phosphate mixtures,and the rejection of natrium salt,molysite,and magnesium is almost 100%.

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.

Statins decrease the risk of hepatocellular carcinoma in metabolic dysfunction-associated steatotic liver disease:A systematic review and meta-analysis

BACKGROUND Metabolic dysfunction-associated steatotic liver disease(MASLD)is a leading cause of chronic liver disease with a significant risk of developing hepatocellular carcinoma(HCC).Recent clinical evidence indicates the potential benefits of statins in cancer chemoprevention and therapeutics.However,it is still unclear if these drugs can lower the specific risk of HCC among patients with MASLD.AIM To investigate the impact of statin use on the risk of HCC development in patients with MASLD.METHODS A systematic review and meta-analysis of all the studies was performed that measured the effect of statin use on HCC occurrence in patients with MASLD.The difference in HCC risk between statin users and non-users was calculated among MASLD patients.We also evaluated the risk difference between lipophilic versus hydrophilic statins and the effect of cumulative dose on HCC risk reduction.RESULTS A total of four studies consisting of 291684 patients were included.MASLD patients on statin therapy had a 60%lower pooled risk of developing HCC compared to the non-statin group[relative risk(RR)=0.40,95%CI:0.31-0.53,I2=16.5%].Patients taking lipophilic statins had a reduced risk of HCC(RR=0.42,95%CI:0.28-0.64),whereas those on hydrophilic statins had not shown the risk reduction(RR=0.57,95%CI:0.27-1.20).The higher(>600)cumulative defined daily doses(cDDD)had a 70%reduced risk of HCC(RR=0.30,95%CI:0.21-0.43).There was a 29%(RR=0.71,95%CI:0.55-0.91)and 43%(RR=0.57,95%CI:0.40-0.82)decreased risk in patients receiving 300-599 cDDD and 30-299 cDDD,respectively.CONCLUSION Statin use lowers the risk of HCC in patients with MASLD.The higher cDDD and lipophilicity of statins correlate with the HCC risk reduction.

An electron beam irradiation-assisted coating method for the regulation of hydrophilicity and hydrophobicity

Developing a stable,reliable,and industrially compatible method to control hydrophobicity is crucial for separation,transportation,and the generation of special surfaces.An e-HMS-PDMS silica gel nanoparticle coating was prepared using a two-step electron beam irradiation(EBI)process,consisting of(i)grafting of two organic groups onto thiol-functionalized hollow mesoporous silica(HMS-SH)with 10 MeV EBI and(ii)curing of polydimethylsiloxane(PDMS)onto silicone rubber using the HMS hybrid materials prepared in step i as an additive with 200 keV EBI.The tuneable grafting of functional groups and the surface properties of the silica,which was embedded in the PDMS layer,allowed us to precisely control the hydrophilicity of the PDMS layer by means of altering the grafting gradient of the silica and the loading ratio of the monomers.A diverse range of vinyl-structured monomers can be used in this method,and the selection of suitable monomers is vital in determining the physical properties of the coating layer.The hydrophilicity of the coating can be linearly controlled within a specific range(50°to 155°)by using suitable monomers,allowing for the design of surfaces with specific hydrophilic and hydrophobic requirements.

Hydrophilic and photocatalytic activities of Nd-doped titanium dioxide thin films

The Nd-doped TiO2 thin films with higher hydrophilic and photocatalytic activities were prepared on glass slides by an acid-catalyzed sol？gel method. The effects of Nd doping on crystalline phase, surface composition and optical property were investigated by means of techniques such as X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, Fourier transform infrared spectroscopy （FT-IR）, optical contact angle tester and UV-Vis spectroscopy. The results show that Nd doping obviously influences the hydrophilic and photocatalytic activities of TiO2thin films. Nd doping could cause the TiO2 lattice distortion, inhibit phase transition from anatase to rutile, cause red shift of the absorption spectrum edge, produce hydroxyl radicals （·OH）, and accelerate surface hydroxylation, which result in a significant improvement in the hydrophilicity and photoreactivity of Nd-doped TiO2 thin films. When the content of Nd is 0.1% （mass fraction）, TiO2 thin films achieve the smallest grain size （about 15 nm）, and the hydrophilic and photocatalytic activities of TiO2 thin film reach the maximum, the contact angle is only 8.1°, and 92% of methylene blue is finally degraded. Moreover, the modification mechanism of Nd doping was also discussed.

Surface modification of NiTi alloy by sol-gel derived porous TiO_(2)film

Titania films with nano-sized pores were prepared on the NaOH？HCl pretreated NiTi alloy substrate by sol？gel method.A crack-free film is obtained for the sample with a dense inner layer and a porous outside layer（sample TC1＋1）.The X-ray diffraction shows that the titania films are composed of anatase,and a little Ni4Ti3 phase in the heat treated substrate is also detected.The X-ray photoelectron spectroscopy results indicate that the titania film completely covered the NiTi substrate for sample TC1＋1.The sample TC1＋1 is hydrophilic with a contact angle about 20°,and UV illumination treatment for 15 min further decreases the contact angle to（9.2±3.2）°.The potentiodynamic polarization test in 0.9% NaCl solution reveals a better corrosion resistance of sample TC1＋1 than the polished NiTi sample.

豫北地区嗜水气单胞菌灭活疫苗的制备及免疫效果的研究

目的:选取毒力因子多、毒性强的嗜水气单胞菌株(Aeromonas hydrophil)制成灭活疫苗,研究疫苗的免疫保护效果。方法:采用甲醛灭活制备疫苗,对银鲫进行腹腔注射,设立免疫组和对照组,然后进行血清抗体效价检测、病理切片分析和攻毒保护试验。结果:银鲫在经注射免疫后,各免疫时间均有抗体产生,抗体效价在第6周检测时达到高峰,而对照组在整个试验过程中均没有检测到抗体;病理切片也表明,该疫苗能够对鲫鱼靶器官产生很好的保护作用;攻毒保护试验中,免疫组的免疫保护率达100%,且免疫保护期长达6个月以上。结论:嗜水气单胞菌灭活疫苗对银鲫有显著的免疫保护效应,可作为预防细菌性败血症感染的疫苗。

Sol-gel preparation, corrosion resistance and hydrophilicity of Ta-containing TiO_2 films on Ti6Al4V alloy

Ta-containing TiO2 films with Ta contents of 5%, 20%, 33% （mole fraction） were sol-gel coated on the surface roughened Ti6AI4V alloy by dip coating method for biomedical applications. The Ta-TiO2 films on 1.5 mol/L NaOH-HCI pretreated substrate are adherent, but there are cracks for the sample with 33% Ta. X-ray photoelectron spectroscopy results show that Ti and Ta exist as TiP2 and Ta205 in the film, and A1 element is not detectable. X-ray diffraction and Raman scattering analyses reveal that the addition of Ta decreases crystallization of the films. Potentiodynamic polarization test in a Ca-free Hank＇s balanced solution demonstrates that the coating samples markedly improve the corrosion resistance compared with the polished sample. The addition of Ta impedes UV light-induced hydrophilic conversion of the coating samples. The sample with 20% Ta has enough film integrity and hydrophilic conversion rate, and is expected to possess good biological properties.

Ag Deposition Forms and Uniformity on Porous Silicon by Electrochemical Method

The electrochemical deposition technique was applied to achieve porous silicon （PS） surface passivated with Ag deposition for improving the properties of PS photoluminescence. The relation of Ag depositing forms to current density and the effect of PS hydrophilic surface on deposition uniformity were investigated. The experimental results indicated that there were two critical current densities （maximum and minimum） in which Ag was absent and electroplated on PS surface correspondingly, and the range of current density for deposition of Ag on porous silicon was from 50 μA/cm^2 to 400 μA/cm^2. The process of changing PS surface from hydrophobic into hydrophilic had positive effect on Ag deposition uniformity. Under the same experimental conditions, PS hydrophobic surface presented uneven Ag deposition.However, hydrophilic surface treated with SC-1 solution was even. Finally, the effect of PS surface passivation with Ag even deposition on photoluminescence intensity and stabilization of PS was studied. It was discovered that Ag passivation inhibited the degradation of PL intensity effectively. In addition, excessive Ag deposition had a quenching effect on room-temperature visible photoluminescence of PS.

Study of Sustained Release Phenylpropanolamine Hydrochloride Hydrophilic Matrix Tablets Containing Hydroxypropylmethylcellulose K100M and Carbopol 971P

选用HPMC K100M和卡波普971P为骨架材料，粉末直接压片法制备骨架片，考察释放度，反相高效液相色谱法检测盐酸苯丙醇胺（PPA·HCl）的浓度。释药曲线均符合Higuchi方程（R＞0．98，P＜0．01）。运用正交设计法，以美国市场的PPA·HCl缓释片Acutrim^R为对照，相似因子f2值为指标，筛选获得了最优处方。其工艺重现性合格。研制片在0．1mol·L^-1 HCl,H2O(pH6.5)，磷酸盐缓冲液（PBS）pH5.0,6.8和7.4的介质中，以及在0.1mol·L^-1HCl中释放2h，转移至PBS6．8中释放10h，相对于对照品的f2值为63－74，表明在各介质中两制剂的释药曲线相似。释药影响因素的考察结果表明：在本实验考察的范围内，骨架片在水中的释药速率与HPMC K100M和卡波普971P的用量呈负相关。HPMC K100M和卡波普971P的比例（保持聚合物总用量相同），硬脂酸镁量和骨架片硬度对释药速率无显著性影响。

Controlled Synthesis of PCL/PVP Copolymer by RAFT Method and Its HydrophUic Block-Dependent MiceUar Behaviors

A range of poly（ε-caprolactone）/poly（N-vinyl-2-pyrrolidone） amphiphilic block copolymers with well-defined hydrophilic chain length were synthesized by the living/controlled reversible addition fragmentation chain transfer polymerization method. The composition and struc- ture of the targeted resultants were characterized with 1H NMR, 13C NMR, FT-IR spec- troscopy and gel permeation chromatography. The various block copolymers were success- fully employed to fabricate the spherical micelle with core-shell morphological structure. The poly（N-vinyl-2-pyrrolidone） block-dependent characteristics of the copolymeric micelles were investigated by fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. The solubilization of the hydrophobic ibuprofen as a model drug in the micelle solution was also explored. It was found that the drug loading contents are related to the micellar morphology structure determined by hydrophilic chain length in the copolymer.

Improvement of hydrophilicity of porous PVDF membranes with LiCl additives

Porous polyvinylidene fluoride（PVDF）membranes blended with LiCl are prepared through the phase inversion method to obtain a good support layer for air dehumidification.The hydrophilicity of the resulting membrane is evaluated by water contact angle measurements and vapor adsorption tests.The moisture permeation performance of the membrane is measured by permeation tests in terms of total mass transfer coefficients and moisture permeability rates.It is found that water contact angles and water vapor adsorption capacities increase with the increasing LiCl content in the casting solution.As the LiCl content increases,the total mass transfer coefficient increases slightly at a low LiCl content（below 2.5%）and then improves greatly at a high LiCl content（above 2.5%）,whereas the moisture permeation rate increases.The results demonstrate that LiCl can remarkably improve the hydrophilicity of PVDF membranes,and then greatly enhance moisture permeation performance.

Bovine Serum Albumin (BSA) Microspheres Containing Methotrexate (MTX) I.Pharmaceutical Aspects

Microspheres Ⅰ,Ⅱ and Ⅲ were produced by emulsion technique.Microsphere I was solidified by glutaraldehyde crosslinking,microsphere Ⅱ was solidified by glutaraldehyde crosslinking and further treated with glycine solution and microsphere Illwas solidified by heating denaturation only.The results showed that the microsphere diameter produced by cross[inking was bigger than that prepared by heating.The microsphere Ⅱ had higher hydrophilicity than Microsphere I had.The methotrexate (MTX) contents in microspheres Ⅰ and Ⅱ were 2.73±0.053%,2.87±0.119% respectively. microsphere Ⅲ was only blank microspheres with MTX adsorbed on their surfaces.In vitro release studies,microspheres I and I have maintained sustained release of MTX till the next day,it was found that the drug releases from microspheres Ⅰ and Ⅱ were governed by Higuchi diffusion law.

Study on Liposomes of Mimetic Red Cell

Liposomes were prepared by adding hydrophilic agents PEG PE, rigidity agent SM in the bilayer membrane for mimetic red cell membrane. In PBS or serum, release of calcein content from liposomes dramatically decreased, which demonstrated increasing membrane stability by adding PEG PE or SM. The ratio b/R of the remains of liposomes in blood to that in RES was used as a parameter of biodistribution in vivo. At 2 h after iv injection, b/R of modified liposomes was enhanced 6.5～13.1 fold. Their clearance half life from blood circulation was delayed 1.6～5.8 fold. The modification of liposome membrane by PEG PE or SM is the favorable condition for drug liposomes to target the non RES.