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1.
Chemistry ; 30(34): e202400046, 2024 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-38619364

RESUMO

Förster resonance energy transfer (FRET) has been widely applied in fluorescence imaging, sensing and so on, while developing useful strategy of boosting FRET efficiency becomes a key issue that limits the application. Except optimizing spectral properties, promoting orientation factor (κ2) has been well discussed but rarely utilized for boosting FRET. Herein, we constructed binary nano-assembling of two thermally activated delayed fluorescence (TADF) emitters (2CzPN and DMAC-DPS) with J-type aggregate of cyanine dye (C8S4) as doping films by taking advantage of their electrostatic interactions. Time-resolved spectroscopic measurements indicated that 2CzPN/Cy-J films exhibit an order of magnitude higher kFRET than DMAC-DPS/Cy-J films. Further quantitative analysing on kFRET and kDET indicated higher orientation factor (κ2) in 2CzPN/Cy-J films play a key role for achieving fast kFRET, which was subsequently confirmed by anisotropic measurements. Corresponding DFT/TDDFT calculation revealed strong "two-point" electrostatic anchoring in 2CzPN/Cy-J films that is responsible for highly orientated transitions. We provide a new strategy for boosting FRET in nano-assemblies, which might be inspired for designing FRET-based devices of sensing, imaging and information encryption.

2.
Soft Matter ; 20(18): 3780-3786, 2024 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-38639061

RESUMO

Acylphosphatase (AcP) is an enzyme which catalyses the hydrolysis of acylphosphate. The binding with the phosphate ion (Pi) assumes significance in preserving both the stability and enzymatic activity of AcP. While previous studies using single molecule force spectroscopy explored the mechanical properties of AcP, the influence of Pi on its folding and unfolding dynamic behaviors remains unexplored. In this work, using stable magnetic tweezers, we measured and compared the force-dependent folding and unfolding rates of AcP in the Tris buffer and phosphate buffer within a force range from 2 pN to 40 pN. We found that Pi exerts no discernible effect on the folding dynamics but consistently decreases the force-dependent unfolding rate of AcP by a constant ratio across the entire force spectrum. The free energy landscapes of AcP in the absence and presence of Pi are constructed. Our results reveal that Pi selectively binds to the native state of AcP, stabilizing it and suggesting the general properties of specific ligand-receptor interactions.


Assuntos
Acilfosfatase , Dobramento de Proteína , Desdobramento de Proteína , Termodinâmica , Ligantes , Fosfatos/química , Fosfatos/metabolismo
3.
Phys Rev Lett ; 131(21): 218402, 2023 Nov 24.
Artigo em Inglês | MEDLINE | ID: mdl-38072617

RESUMO

The tenth domain of type III fibronectin (FNIII_{10}) mediates cell adhesion to the extracellular matrix. Despite its structural similarity to immunoglobulin domains, FNIII_{10} exhibits unique unfolding behaviors. We employed magnetic tweezers to investigate the unfolding and folding dynamics of FNIII_{10} under physiological forces (4-50 pN). Our results showed that FNIII_{10} follows a consistent transition pathway with an intermediate state characterized by detached A and G ß strands. We determined the folding free energies and all force-dependent transition rates of FNIII_{10} and found that both unfolding rates from the native state to the intermediate state and from the intermediate state to the unfolded state deviate from Bell's model. We constructed a quantitative free energy landscape with well-defined traps and barriers that exhibits a hierarchical symmetrical pattern. Our findings provide a comprehensive understanding of FNIII_{10} conformational dynamics and demonstrate how free energy landscape of multistate biomolecules can be precisely mapped, illuminating the relationship between thermal stability, intermediate states, and folding rates in protein folding.


Assuntos
Fibronectinas , Dobramento de Proteína , Fibronectinas/metabolismo , Fenômenos Mecânicos
4.
Appl Opt ; 62(27): 7163-7168, 2023 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-37855571

RESUMO

Transparent nanopaper (T-paper) can be applied in the field of electromagnetic shielding materials, antistatic materials, composite conductive materials, electric pool materials, super capacitors, and thermal management systems. However, this kind of T-paper has not been employed in ultrafast photonics yet. For the first time, to our knowledge, transparent electrical nanopaper is used in fiber lasers, different from the conventional pulsed fiber laser, which operates in the Q-switched regime under low pump power and then in the mode-locked regime under high pump power. Mode-locking is achieved first with a pulse duration of 550 fs under low pump power (166 mW). When further increasing the pump power up to 198 mW, the proposed fiber laser can be converted from a mode-locked to Q-switched state, which is a result of the two-photon absorption effect. The proposed fiber laser based on T-paper can be potentially applied in optical tomography, metrology, spectroscopy, micro-machining technology, and biomedical diagnostics.

5.
Sensors (Basel) ; 22(20)2022 Oct 13.
Artigo em Inglês | MEDLINE | ID: mdl-36298135

RESUMO

In recent years, vital signals monitoring in sports and health have been considered the research focus in the field of wearable sensing technologies. Typical signals include bioelectrical signals, biophysical signals, and biochemical signals, which have applications in the fields of athletic training, medical diagnosis and prevention, and rehabilitation. In particular, since the COVID-19 pandemic, there has been a dramatic increase in real-time interest in personal health. This has created an urgent need for flexible, wearable, portable, and real-time monitoring sensors to remotely monitor these signals in response to health management. To this end, the paper reviews recent advances in flexible wearable sensors for monitoring vital signals in sports and health. More precisely, emerging wearable devices and systems for health and exercise-related vital signals (e.g., ECG, EEG, EMG, inertia, body movements, heart rate, blood, sweat, and interstitial fluid) are reviewed first. Then, the paper creatively presents multidimensional and multimodal wearable sensors and systems. The paper also summarizes the current challenges and limitations and future directions of wearable sensors for vital typical signal detection. Through the review, the paper finds that these signals can be effectively monitored and used for health management (e.g., disease prediction) thanks to advanced manufacturing, flexible electronics, IoT, and artificial intelligence algorithms; however, wearable sensors and systems with multidimensional and multimodal are more compliant.


Assuntos
COVID-19 , Esportes , Dispositivos Eletrônicos Vestíveis , Humanos , Inteligência Artificial , Pandemias , COVID-19/diagnóstico , Monitorização Fisiológica/métodos
6.
Molecules ; 27(10)2022 May 19.
Artigo em Inglês | MEDLINE | ID: mdl-35630739

RESUMO

The execution of specific processing protocols endows Wuyi rock tea with distinctive qualities produced through signature metabolic processes. In this work, tea leaves were collected before and after each of three processing stages for both targeted and untargeted metabolomic analysis. Metabolic profiles of processing stages through each processing stage of rotation, pan-firing and roasting were studied. Overall, 614 metabolites were significantly altered, predominantly through nitrogen- enriching (N) pathways. Roasting led to the enrichment of 342 N metabolites, including 34 lipids, 17 organic acids, 32 alkaloids and 25 amino acids, as well as secondary derivatives beneficial for tea quality. This distinctive shift towards enrichment of N metabolites strongly supports concluding that this directed accumulation of N metabolites is how each of the three processing stages endows Wuyi rock tea with singular quality.


Assuntos
Metabolômica , Nitrogênio , Aminoácidos/metabolismo , Metaboloma , Metabolômica/métodos , Chá/química
7.
Fa Yi Xue Za Zhi ; 38(5): 579-583, 2022 Oct 25.
Artigo em Inglês, Zh | MEDLINE | ID: mdl-36727172

RESUMO

OBJECTIVES: To study the cooling reaction kinetic characteristics of the temperature difference between cadaver temperature and ambient temperature (hereinafter referred to as "cadaver temperature difference") according to the reaction kinetics method. METHODS: Thirty rabbits were randomly divided into 5 groups with 6 rabbits in each group. The rabbits were injected with 10% potassium chloride solution intravenously. After death, the rabbits were placed at 5 ℃, 10 ℃, 15 ℃, 20 ℃ and 25 ℃ environment condition, respectively, and the rectal temperature was measured every minute for 20 hours. The measured cadaver temperature was subtracted from ambient temperature, and the cadaver temperature difference data was calculated using the reaction kinetics formula. The linear regression equation was fitted for analysis, and the experimental results were applied to the temperature difference data of human body after death for verification. RESULTS: Under different environmental conditions, the linear coefficient determination of temperature difference -ln(C/C0) in rabbits was 0.99, showing a good linear relationship with time t. The application of human body temperature data after death was consistent with the results of animal experiments. CONCLUSIONS: Under stable conditions, the temperature difference cooling process after death in rabbits is a first-order kinetic response. The method can also be used to study the temperature difference in human body after death.


Assuntos
Temperatura Corporal , Animais , Humanos , Coelhos , Temperatura , Cinética , Cadáver
8.
Plant Biotechnol J ; 19(4): 814-829, 2021 04.
Artigo em Inglês | MEDLINE | ID: mdl-33159401

RESUMO

Lodging reduces grain yield in cereal crops. Understanding the genetic basis of lodging resistance (LR) benefits LR breeding. In the study, 524 accessions from a rice germplasm collection and 193 recombinant inbred lines were phenotyped for 17 LR-related traits. Height and culm strength (the magnitude of applied force necessary to break the culm) were two major factors affecting LR. We conducted genome-wide association study (GWAS) and identified 127 LR-associated loci. Significant phenotypic correlations between culm-strength traits and yield-related traits were observed. To reveal the genetic relationship between them, we conducted GWAS of culm-strength traits with adding yield-related trait as a covariate and detected 63 loci linking culm strength and yield. As a proof, a near-isogenic line for an association locus on chromosome 7 showed enhanced LR and yield. Strikingly, 58 additional loci were identified in the covariate-added GWAS. Several LR-associated loci had undergone divergent selection. Linkage analysis supported the GWAS results. We propose that introgression of alleles beneficial for both culm strength and panicle weight without negative effects on panicle number or pyramiding high-yielding alleles and lodging-resistant alleles without effects on yield can be employed for the post-Green-Revolution breeding.


Assuntos
Oryza , Alelos , Estudo de Associação Genômica Ampla , Oryza/genética , Fenótipo , Melhoramento Vegetal , Locos de Características Quantitativas/genética
9.
Plant Physiol ; 184(3): 1317-1332, 2020 11.
Artigo em Inglês | MEDLINE | ID: mdl-32948668

RESUMO

Protein phosphatase1 (PP1) plays important roles in eukaryotes, including in plant hormone responses, and functions as a holoenzyme that consists of catalytic and regulatory subunits. Animal genomes encode ∼200 PP1-interacting proteins; by contrast, only a few have been reported in plants. In this study, PP1 Regulatory Subunit3 (PP1R3), a protein that interacts with PP1 in Arabidopsis (Arabidopsis thaliana), was characterized by mass spectrometry. PP1R3 was widely expressed in various plant tissues and PP1R3 colocalized with Type One Protein Phosphatases (TOPPs) in the nucleus and cytoplasm. The pp1r3 mutants were hypersensitive to abscisic acid (ABA), similar to the dominant-negative mutant topp4-1 or the loss-of-function multiple mutants topp1 topp4-3, topp8 topp9, topp6/7/9, topp1/2/4-3/6/7/9, and topp1/4-3/5/6/7/8/9 (topp-7m). About two-thirds of differentially expressed genes in topp-7m showed the same gene expression changes as in pp1r3-2 In response to ABA, the phenotypes of pp1r3 topp1 topp4-3 and pp1r3 topp4-1 were consistent with those of pp1r3, while pp1r3 abi1-1 showed an additive effect of the pp1r3 and abi1-1 (mutation in Abscisic Acid Insensitive1 [ABI1]) single mutants. Moreover, pp1r3 could partially recover the ABA response-related phenotype, gene expression, and plant morphology of topp4-1 PP1R3 inhibited TOPP enzyme activity and facilitated the nuclear localization of TOPP4. By contrast, ABA treatment increased the amounts of TOPP1 and TOPP4 in the cytoplasm. Importantly, nuclear localization of TOPP4 partially restored the ABA-hypersensitive phenotype of topp4-1 Overall, our results suggest that the PP1R3:TOPP holoenzyme functions in parallel with ABI1 in the nucleus to regulate ABA signaling.


Assuntos
Ácido Abscísico/metabolismo , Arabidopsis/genética , Arabidopsis/metabolismo , Fosfoproteínas Fosfatases/genética , Fosfoproteínas Fosfatases/metabolismo , Estresse Fisiológico/genética , Estresse Fisiológico/fisiologia , Regulação da Expressão Gênica de Plantas , Genes de Plantas , Variação Genética , Genótipo , Nicotiana/genética , Nicotiana/metabolismo
10.
Crit Rev Biotechnol ; 41(6): 953-968, 2021 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-34015998

RESUMO

Alginate, a kind of linear acidic polysaccharide, consists of α-L-guluronate (G) and ß-D-mannuronate (M). Both alginate and its degradation products (alginate oligosaccharides) possess abundant biological activities such as antioxidant activity, antitumor activity, and antimicrobial activity. Therefore, alginate and alginate oligosaccharides have great value in food, pharmaceutical, and agricultural fields. Alginate lyase can degrade alginate into alginate oligosaccharides via the ß-elimination reaction. It plays an important role in marine carbon recycling and the deep utilization of brown algae. Elucidating the structural features of alginate lyase can improve our knowledge of its catalytic mechanisms. With the development of structural analysis techniques, increasing numbers of alginate lyases have been characterized at the structural level. Hence, it is essential and helpful to summarize and discuss the up-to-date findings. In this review, we have summarized progress on the structural features and the catalytic mechanisms of alginate lyases. Furthermore, the molecular modification strategies and the applications of alginate lyases have also been discussed. This comprehensive information should be helpful to expand the applications of alginate lyases.


Assuntos
Alginatos , Polissacarídeo-Liases , Oligossacarídeos , Polissacarídeo-Liases/metabolismo , Especificidade por Substrato
11.
Appl Opt ; 60(34): 10548-10554, 2021 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-35200915

RESUMO

A fiber-optic vector magnetic field sensor based on a large-core-offset Mach-Zehnder interferometer (MZI) infiltrated by magnetic fluid (MF) is proposed and demonstrated in this paper. By large-core-offset fusion splicing of a short single-mode fiber (SMF) between a lead-in SMF and a coupling multi-mode fiber, the MZI with a sub-millimeter length is formed, which is then sealed in an MF-infiltrated glass capillary. Through the MF's refractive index modulation by external magnetic field, the phase of the light passing through the MZI is altered. As a result, the transmission spectrum can be monitored for the magnetic field measurement. Furthermore, from the axial-asymmetry of the large-core-offset MZI structure, the proposed sensor possesses vectorial magnetic-field-sensing ability. Experiments show that the MF-infiltrated large-core-offset MZI vector magnetic-field sensor can achieve a high wavelength sensitivity of 96.68 pm/Oe in a magnetic field range of 50-130 Oe.

12.
Phys Rev Lett ; 125(19): 198101, 2020 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-33216575

RESUMO

Atomic force microscopy experiments found that GB1, a typical two-state model protein used for study of folding and unfolding dynamics, can sustain forces of more than 100 pN, but its response to low forces still remains unclear. Using ultrastable magnetic tweezers, we discovered that GB1 has an unexpected nonmonotonic force-dependent unfolding rate at 5-160 pN, from which a free energy landscape with two main barriers and a hidden intermediate state was constructed. A model combining two separate models by Dudko et al. with two pathways between the native state and this intermediate state is proposed to rebuild the unfolding dynamics over the full experimental force range. One candidate of this transient intermediate state is the theoretically proposed molten globule state with a loosely collapsed conformation, which might exist universally in the folding and unfolding processes of two-state proteins.


Assuntos
Proteínas de Bactérias/química , Modelos Químicos , Cinética , Magnetismo , Microscopia de Força Atômica , Domínios Proteicos , Dobramento de Proteína , Termodinâmica
13.
PLoS Genet ; 13(7): e1006889, 2017 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-28686596

RESUMO

A variety of adverse conditions including drought stress severely affect rice production. Root system plays a critical role in drought avoidance, which is one of the major mechanisms of drought resistance. In this study, we adopted genome-wide association study (GWAS) to dissect the genetic basis controlling various root traits by using a natural population consisting of 529 representative rice accessions. A total of 413 suggestive associations, containing 143 significant associations, were identified for 21 root traits, such as maximum root length, root volume, and root dry weight under normal and drought stress conditions at the maturation stage. More than 80 percent of the suggestive loci were located in the region of reported QTLs for root traits, while about 20 percent of suggestive loci were novel loci detected in this study. Besides, 11 reported root-related genes, including DRO1, WOX11, and OsPID, were found to co-locate with the association loci. We further proved that the association results can facilitate the efficient identification of causal genes for root traits by the two case studies of Nal1 and OsJAZ1. These loci and their candidate causal genes provide an important basis for the genetic improvement of root traits and drought resistance.


Assuntos
Oryza/genética , Raízes de Plantas/genética , Locos de Características Quantitativas/genética , Mapeamento Cromossômico , Cromossomos de Plantas/genética , Secas , Regulação da Expressão Gênica de Plantas , Genoma de Planta , Estudo de Associação Genômica Ampla , Oryza/crescimento & desenvolvimento , Raízes de Plantas/crescimento & desenvolvimento
14.
Opt Express ; 27(14): 19887-19895, 2019 Jul 08.
Artigo em Inglês | MEDLINE | ID: mdl-31503743

RESUMO

A non-contact all-fiber optic acceleration measurement system has been proposed in this work. Using a fiber delay line in the fiber-optic path, the difference between two Doppler shifted frequencies of a laser beam corresponding to two different velocities of a moving object with a fixed time delay was measured and used for acceleration extraction. By performing acceleration measurements for a piezoelectric ceramic oscillator driven by an open-loop piezo controller at different voltages, a measurement error of better than -3.766% and nonlinearity degree of 0.314% were achieved.

15.
J Exp Bot ; 70(2): 545-561, 2019 01 07.
Artigo em Inglês | MEDLINE | ID: mdl-30380099

RESUMO

Manual phenotyping of rice tillers is time consuming and labor intensive, and lags behind the rapid development of rice functional genomics. Thus, automated, non-destructive methods of phenotyping rice tiller traits at a high spatial resolution and high throughput for large-scale assessment of rice accessions are urgently needed. In this study, we developed a high-throughput micro-CT-RGB imaging system to non-destructively extract 739 traits from 234 rice accessions at nine time points. We could explain 30% of the grain yield variance from two tiller traits assessed in the early growth stages. A total of 402 significantly associated loci were identified by genome-wide association study, and dynamic and static genetic components were found across the nine time points. A major locus associated with tiller angle was detected at time point 9, which contained a major gene, TAC1. Significant variants associated with tiller angle were enriched in the 3'-untranslated region of TAC1. Three haplotypes for the gene were found, and rice accessions containing haplotype H3 displayed much smaller tiller angles. Further, we found two loci containing associations with both vigor-related traits identified by high-throughput micro-CT-RGB imaging and yield. The superior alleles would be beneficial for breeding for high yield and dense planting.


Assuntos
Oryza/crescimento & desenvolvimento , Oryza/genética , Biomassa , Secas , Grão Comestível/crescimento & desenvolvimento , Genoma de Planta , Estudo de Associação Genômica Ampla , Microtomografia por Raio-X
16.
Plant Cell ; 28(9): 2161-2177, 2016 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-27468891

RESUMO

Plants have evolved complicated protective mechanisms to survive adverse conditions. Previously, we reported that the transcription factor OsbZIP46 regulates abscisic acid (ABA) signaling-mediated drought tolerance in rice (Oryza sativa) by modulating stress-related genes. An intrinsic D domain represses OsbZIP46 activity, but the detailed mechanism for the repression of OsbZIP46 activation remains unknown. Here, we report an OsbZIP46-interacting protein, MODD (Mediator of OsbZIP46 deactivation and degradation), which is homologous to the Arabidopsis thaliana ABSCISIC ACID-INSENSITIVE5 binding protein AFP. MODD was induced by ABA and drought stress, but the induction was much slower than that of OsbZIP46 In contrast to OsbZIP46, MODD negatively regulates ABA signaling and drought tolerance, and inhibits the expression of OsbZIP46 target genes. We found that MODD negatively regulates OsbZIP46 activity and stability. MODD represses OsbZIP46 activity via interaction with the OsTPR3-HDA702 corepressor complex and downregulation of the histone acetylation level at OsbZIP46 target genes. MODD promotes OsbZIP46 degradation via interaction with the U-box type ubiquitin E3 ligase OsPUB70. Interestingly, the D domain is required for both deactivation and degradation of OsbZIP46 via its interaction with MODD. These findings show that plants fine-tune their drought responses by elaborate regulatory mechanisms, including the coordination of activity and stability of key transcription factors.

17.
PLoS Genet ; 12(11): e1006412, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27814357

RESUMO

Tiller angle is one of the most important components of the ideal plant architecture that can greatly enhance rice grain yield. Understanding the genetic basis of tiller angle and mining favorable alleles will be helpful for breeding new plant-type varieties. Here, we performed genome-wide association studies (GWAS) to identify genes controlling tiller angle using 529 diverse accessions of Oryza sativa including 295 indica and 156 japonica accessions in two environments. We identified 7 common quantitative trait loci (QTLs), including the previously reported major gene Tiller Angle Control 1 (TAC1), in the two environments, 10 and 13 unique QTLs in Hainan and Wuhan, respectively. More QTLs were identified in indica than in japonica, and three major QTLs (qTA3, qTA1b/DWARF2 (D2) and qTA9c/TAC1) were fixed in japonica but segregating in indica, which explained the wider variation observed in indica compared with that in japonica. No common QTLs were identified between the indica and japonica subpopulations. Mutant analysis for the candidate gene of qTA3 on chromosome 3 indicated a novel gene, Tiller Angle Control 3 (TAC3), encoding a conserved hypothetical protein controlling tiller angle. TAC3 is preferentially expressed in the tiller base. The ebisu dwarf (d2) mutant exhibited a decreased tiller angle, in addition to its previously described abnormal phenotype. A nucleotide diversity analysis revealed that TAC3, D2 and TAC1 have been subjected to selection during japonica domestication. A haplotype analysis identified favorable alleles of TAC3, D2 and TAC1, which may be used for breeding plants with an ideal architecture. In conclusion, there is a diverse genetic basis for tiller angle between the two subpopulations, and it is the novel gene TAC3 together with TAC1, D2, and other newly identified genes in this study that controls tiller angle in rice cultivars.


Assuntos
Proteínas de Transporte/genética , Variação Genética , Oryza/genética , Proteínas de Plantas/genética , Locos de Características Quantitativas/genética , Alelos , Cruzamento , Mapeamento Cromossômico , Grão Comestível/genética , Grão Comestível/crescimento & desenvolvimento , Estudo de Associação Genômica Ampla , Haplótipos , Oryza/crescimento & desenvolvimento , Fenótipo
18.
Sensors (Basel) ; 19(7)2019 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-30959736

RESUMO

A white light non-scanning correlation interrogation system was proposed and built to interrogate absolute length of the air cavity of fiber-optic compound Fabry⁻Perot pressure sensors for the extraction of pressure value. By carefully choosing thickness range and tilt angle of the optical wedge used for cavity length matching, correlation interferometric signal of the basal cavity can be naturally filtered out. Based on peak positioning by Fourier transform, bandpass filtering in frequency domain, inverse Fourier transform back to time domain, envelope fitting and zero fringe finding through a gravity center method, cavity length can be determined with an accuracy of 0.04%. The system was used for the interrogation of a fiber-optic compound Fabry⁻Perot pressure sensor under different pressures. For a pressure range of 0.1~2.9 Mpa, the linear relationship between the air cavity length and the gas pressure imposed was successfully extracted.

19.
Langmuir ; 34(25): 7428-7435, 2018 06 26.
Artigo em Inglês | MEDLINE | ID: mdl-29870265

RESUMO

Hexadecyltrimethylammonium bromide (CTAB) was utilized to template the growth of mesoporous silica particles via ammonia-catalyzed hydrolysis and condensation of tetraethoxysilane (TEOS) in the reaction solutions with varied volume fractions of ethanol ( fR). The use of 9,10-bis(phenylethynyl) anthracene (BPEA) as a fluorescence probe unraveled a clear difference in interior structure between the CTAB micelles confined at different fR. At fR of 0.3, the confined CTAB micelles consisting of regularly and densely packed alkane chains, which created crystalline interiors, in which the doped BPEA molecules were effectively isolated in the monomeric form and well protected against aggressive attack from the surrounding environment. At fR of 0.4 or 0.5, the confined CTAB micelles consisting of less regularly but densely packed alkane chains created glassy interiors, which enabled reversible aggregation of the doped BPEA in response to the surrounding environmental change, for instance, the ethanol content in the particle dispersion. At fR of 0.6 or 0.7, the confined CTAB micelles consisting of loosely packed alkane chains created amorphous interiors, which offered sufficiently large free spaces to facilitate the material exchange with the surrounding environment, as evidenced by noticeable intake of the Pyronin Y molecules present in the particle dispersion. The revealed phase modulation of the interiors of surfactant micelles, confined in the pores of mesoporous particles, from crystalline to glassy and amorphous structures, which were scarcely reported in literature, will inspire rational design of mesoporous silica particles with desired technical performance according to the purposes of the practical application.

20.
Langmuir ; 33(23): 5879-5890, 2017 06 13.
Artigo em Inglês | MEDLINE | ID: mdl-28514596

RESUMO

In this work, we investigated the kinetic balance between ammonia-catalyzed hydrolysis of tetraethyl orthosilicate (TEOS) and subsequent condensation over the growth of silica particles in the Stöber method. Our results reveal that, at the initial stage, the reaction is dictated by TEOS hydrolysis to form silanol monomers, which is denoted as pathway I and is responsible for nucleation and growth of small silica particles via condensation of neighboring silanol monomers and siloxane network clusters derived thereafter. Afterward, the reaction is dictated by condensation of newly formed silanol monomers onto the earlier formed silica particles, which is denoted as pathway II and is responsible for the enlargement in size of silica particles. When TEOS hydrolysis is significantly promoted, either at high ammonia concentration (≥0.95 M) or at low ammonia concentration in the presence of LiOH as secondary catalyst, temporal separation of pathways I and II makes the Stöber method reminiscent of in situ seeded growth. This knowledge advance enables us not only to reconcile the most prevailing aggregation-only and monomer-addition models in literature into one consistent framework to interpret the Stöber process but also to grow monodisperse silica particles with sizes in the range 15-230 nm simply but precisely regulated by the ammonia concentration with the aid of LiOH.

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