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1.
J Am Chem Soc ; 146(3): 2219-2226, 2024 01 24.
Artigo em Inglês | MEDLINE | ID: mdl-38207218

RESUMO

Marine organisms produce biological materials through the complex self-assembly of protein condensates in seawater, but our understanding of the mechanisms of microstructure evolution and maturation remains incomplete. Here, we show that critical processing attributes of mussel holdfast proteins can be captured by the design of an amphiphilic, fluorescent polymer (PECHIA) consisting of a polyepichlorohydrin backbone grafted with 1-imidazolium acetonitrile. Aqueous solutions of PECHIA were extruded into seawater, wherein the charge repulsion of PECHIA is screened by high salinity, facilitating interfacial condensation via enhanced "cation-dipole" interactions. Diffusion of seawater into the PECHIA solution caused droplets to form immiscibly within the PECHIA phase (i.e., inverse coacervation). Simultaneously, weakly alkaline seawater catalyzes nitrile cyclization and time-dependent solidification of the PECHIA phase, leading to hierarchically porous membranes analogous to porous architectures in mussel plaques. In contrast to conventional polymer processing technologies, processing of this biomimetic polymer required neither organic solvents nor heating and enabled the template-free production of hollow spheres and fibers over a wide range of salinities.


Assuntos
Bivalves , Proteínas , Animais , Proteínas/química , Água do Mar , Água , Bivalves/química , Polímeros
2.
Angew Chem Int Ed Engl ; 62(48): e202312795, 2023 Nov 27.
Artigo em Inglês | MEDLINE | ID: mdl-37796136

RESUMO

Efficient Mg2+ /Li+ separation is crucial to combating the lithium shortage worldwide, yet current nanofiltration membranes suffer from low efficacy and/or poor scalability, because desirable properties of membranes are entangled and there is a trade-off. This work reports a "tagged-modification" approach to tackle the challenge. A mixture of 3-bromo-trimethylpropan-1-aminium bromide (E1 ) and 3-aminopropyltrimethylazanium (E2 ) was designed to modify polyethylenimine - trimesoyl chloride (PEI-TMC) membranes. E1 and E2 reacted with the PEI and TMC, respectively, and thus, the membrane properties (hydrophilicity, pore sizes, charge) were untangled and intensified simultaneously. The permeance (34.3 L m-2 h-1 bar-1 ) and Mg2+ /Li+ selectivity (23.2) of the modified membranes are about 4 times and 2 times higher than the pristine membrane, and they remain stable in a 30-days test. The permeance is the highest among all analogous nanofiltration membranes. The tagged-modification method enables the preparation of large-area membranes and modules that produce high-purity lithium carbonate (Li2 CO3 ) from simulated brine.

3.
Adv Mater ; 36(9): e2309406, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-37907065

RESUMO

Polyester nanofiltration membranes highlight beneficial chlorine resistance, but their loose structures and negative charge result in poor cations retention precluding advanced use in cations separation. This work designs a new monomer (TET) containing "hydroxyl-ammonium" entities that confer dense structures and positive charge to polyester nanofiltration membranes. The TET monomer undergoes efficient interfacial polymerization with the trimesoyl chloride (TMC) monomer, and the resultant TET-TMC membranes feature one of the lowest molecular weight cut-offs (389 Da) and the highest zeta potential (4 mv, pH: 7) among all polyester nanofiltration membranes. The MgCl2 rejection of the TET-TMC membrane is 95.5%, significantly higher than state-of-the-art polyester nanofiltration membranes (<50%). The Li+ /Mg2+ separation performance of TET-TMC membrane is on par with cutting-edge polyamide membranes, while additionally, the membrane is stable against NaClO though polyamide membranes readily degrade. Thus the TET-TMC is the first polyester nanofiltration membrane for efficient cations separation.

4.
Nat Commun ; 14(1): 5483, 2023 Sep 07.
Artigo em Inglês | MEDLINE | ID: mdl-37673942

RESUMO

Current polyamide lithium extraction nanofiltration membranes are susceptible to chlorine degradation and/or low permeance, two problems that are hard to reconcile. Here we simultaneously circumvented these problems by designing a quaternized-spiro piperazine monomer and translating its beneficial properties into large-area membranes (1 × 2 m2) via interfacial polymerization with trimesoyl chloride. The quaternary ammonium and spiral conformation of the monomer confer more positive charge and free volume to the membrane, leading to one of the highest permeance (~22 L m-2 h-1 bar-1) compared to the state-of-the-art Mg2+/Li+ nanofiltration membranes. Meanwhile, membrane structures are chlorine resistant as the amine-acyl bonding contains no sensitive N-H group. Thus the high performance of membrane is stable versus 400-h immersion in sodium hypochlorite, while control membranes degraded readily. Molecular simulations show that the high permeance and chlorine resistance, which were reproducible at the membrane module level, arise from the spiral conformation and secondary amine structures of the monomer.

5.
Front Public Health ; 10: 1014470, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36268004

RESUMO

Background: The reinfection rate of SARS-CoV-2 Omicron variant is high; thus, exploring the risk factors for reinfection is important for the effective control of the epidemic. This study aimed to explore the effects of psychological and sleep factors on re-positivity with Omicron. Methods: Through a prospective cohort study, 933 adult patients diagnosed with Omicron BA.2.2 infection and testing negative after treatment were included for screening and follow-up. We collected data on patients' demographic characteristics, SARS-CoV-2 Omicron vaccination status, anxiety, depression, and sleep status. Patients underwent nucleic acid testing for SARS-CoV-2 Omicron for 30 days. Regression and Kaplan-Meier analyses were used to determine the risk factors for re-positivity of Omicron. Results: Ultimately, 683 patients were included in the analysis. Logistic regression analysis showed that older age (P = 0.006) and depressive status (P = 0.006) were two independent risk factors for Omicron re-positivity. The odds ratios of re-positivity in patients aged ≥60 years and with a Patient Health Questionnaire-9 (PHQ-9) score ≥5 was 1.82 (95% confidence interval:1.18-2.78) and 2.22 (1.27-3.85), respectively. In addition, the time from infection to recovery was significantly longer in patients aged ≥60 years (17.2 ± 4.5 vs. 16.0 ± 4.4, P = 0.003) and in patients with PHQ-9≥5 (17.5 ± 4.2vs. 16.2 ± 4.5, P = 0.026). Kaplan-Meier analysis showed that there was a significantly higher primary re-positivity rate in patients aged ≥60 years (P = 0.004) and PHQ-9 ≥ 5 (P = 0.007). Conclusion: This study demonstrated that age of ≥60 years and depressive status were two independent risk factors for re-positivity with Omicron and that these factors could prolong the time from infection to recovery. Thus, it is necessary to pay particular attention to older adults and patients in a depressive state.


Assuntos
COVID-19 , Ácidos Nucleicos , Humanos , Idoso , SARS-CoV-2 , Reinfecção , Estudos Prospectivos , COVID-19/epidemiologia , Fatores de Risco
6.
Adv Mater ; 32(23): e2001383, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32350974

RESUMO

Water transport rate in network membranes is inversely correlated to thickness, thus superior permeance is achievable with ultrathin membranes prepared by complicated methods circumventing nanofilm weakness and defects. Conferring ultrahigh permeance to easily prepared thicker membranes remains challenging. Here, a tetrakis(hydroxymethyl) phosphonium chloride (THPC) monomer is discovered that enables straightforward modification of polyamide composite membranes. Water permeance of the modified membrane is ≈6 times improved, give rising to permeability (permeance × thickness) one magnitude higher than state-of-the-art polymer nanofiltration membranes. Meanwhile, the membrane exhibits good rejection (RNa2SO4 = 98%) and antibacterial properties under crossflow conditions. THPC modification not only improves membrane hydrophilicity, but also creates additional angstrom-scale channels in polyamide membranes for unimpeded transport of water. This unique mechanism provides a paradigm shift in facile preparation of ultrapermeable membranes with unreduced thickness for clean water and desalination.


Assuntos
Antibacterianos/química , Antibacterianos/farmacologia , Membranas Artificiais , Nylons/química , Nylons/farmacologia , Compostos Organofosforados/química , Permeabilidade , Água/química
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