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1.
J Phys Chem Lett ; 15(41): 10341-10348, 2024 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-39373553

RESUMO

Since the proposition of the Hofmeister series, guanidinium (Gdm) salts hold a special mention in protein science owing to their contrasting effect on protein(s) depending on the counteranion(s). For example, while GdmCl is known to act as a potential protein denaturant, Gdm2SO4 offers minimal effect on protein structure. Despite the fact that theoretical studies reckon the formation of ion-pairing to be responsible for such behavior, experimental validation of this hypothesis is still in sparse. In this study, we combine electrochemical impedance spectroscopy (EIS) and THz spectroscopy to underline the effect of GdmCl and Gdm2SO4 on a model amide molecule N-methylacetamide (NMA). Molecular dynamics (MD) simulation studies predict that Gdm2SO4 forms heteroion pairing in water, which inhibits Gdm+ ions to approach NMA molecules, while in case of GdmCl, Gdm+ ions directly interact with NMA. The experimental findings on ion hydration, specifically the detailed analysis of the ion-water rattling mode, which appears in the THz frequency domain, unambiguously endorse this hypothesis. Our study establishes the fact that the propensity of ion-pairing in Gdm salts dictates their (de)stabilization effect on proteins.


Assuntos
Guanidina , Simulação de Dinâmica Molecular , Guanidina/química , Sais/química , Estabilidade Proteica , Acetamidas/química , Água/química , Íons/química , Proteínas/química , Espectroscopia Dielétrica
2.
Phys Chem Chem Phys ; 25(45): 31326-31334, 2023 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-37960951

RESUMO

While the phenomenon of excipient mediated membrane fusion has been studied widely, the inherent role of interfacial hydration involved in the process has mostly remained unaddressed. Here we report the experimental validation of the fact that PEG-induced membrane fusion is associated with the dehydration of the membrane(s). We explore the explicit hydration behavior at three different lipids (DOPC, POPC and DPPC) membranes with different aliphatic tails as they undergo fusogenic transition in the presence of PEG of average molecular weight of 4000 using THz-FTIR spectroscopy in the frequency window of 1.5-13.5 THz. Dynamic light scattering and electron microscopic measurements confirm the formation of different intermediate steps of the liposomes during the fusion process: bilayer aggregation, destabilization and finally lipid fusion. We observe that membrane hydration follows a systematic trend with the lipid specificity as the fusion process sets in.


Assuntos
Bicamadas Lipídicas , Fosfatidilcolinas , Bicamadas Lipídicas/química , Fosfatidilcolinas/química , Polietilenoglicóis/química , Lipossomos/química , Espectroscopia de Infravermelho com Transformada de Fourier
3.
Nanoscale ; 15(43): 17398-17408, 2023 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-37796034

RESUMO

Multifunctional self-powered energy harvesting devices have attracted significant attention for wearable, portable, IoT and healthcare devices. In this study, we report transition metal dichalcogenide (TMDC) ternary alloy (Mo0.5W0.5S2)-based self-powered photosensitive vertical triboelectric nanogenerator (TENG) devices, where the ternary alloy functions both as a triboelectric layer and as a photoabsorbing material. The scalable synthesis of the highly crystalline Mo0.5W0.5S2 ternary alloy can overcome the limitations of binary TMDCs (MoS2, WS2) by utilizing its superior optical characteristics, enabling this semiconductor-based TENG device to simultaneously exhibit photoelectric and triboelectric properties. Benefiting from visible light absorption, this vertical TENG device generates higher triboelectric outputs and exhibits excellent power harvesting properties under visible light illumination. The open circuit voltage and short circuit currents of the devices under illumination (410 nm, 525 µW cm-2) are enhanced by 62% and 253%, respectively, while in the darkness, a very high photoresponsivity of ∼45.5 V mW-1 (voltage mode) is exhibited, indicating the superior energy harvesting potential under ultralow illumination. Furthermore, the energy harvesting ability from regular human activities and the operation as artificial e-skin expands the multi-functionality of this TENG device, paving a pathway for simultaneous mechanical and photonic energy harvesting with self-powered sensing.

4.
J Phys Chem B ; 127(41): 8825-8832, 2023 10 19.
Artigo em Inglês | MEDLINE | ID: mdl-37816171

RESUMO

Insulin plays vital roles in controlling blood sugar level in the human body. However, it sometimes aggregates during the storage, and its efficacy (on the treatment of diabetes II disease) reduces significantly. So, understanding the insulin aggregation could help in long-term storage. Here we investigate the amyloid growth of human insulin protein in the presence of sugar molecules and observe that glucose and sucrose delay the insulin aggregation, the effect being systematically sugar dependent. We then investigate protein hydration during the aggregation process using terahertz spectroscopy, as the hydration plays a pioneering role in maintaining biological systems. Our study infers that the water network changes systematically with protein conformations and solvation entropy-enthalpy balance plays a decisive role in the aggregation process.


Assuntos
Insulina , Água , Humanos , Insulina/química , Termodinâmica , Água/química , Entropia , Sacarose
5.
Phys Chem Chem Phys ; 25(40): 27161-27169, 2023 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-37789695

RESUMO

The relationship between the local solvation structures and global thermodynamics, specifically in the case of amphiphilic molecules, is a complex phenomenon and is not yet fully understood. With the prior knowledge that local solvation structures can impose a significant impact on the overall solvation process, we here combine THz spectroscopic analysis with MD simulations to investigate the impact of the altered hydrophobicity and polarity of amphiphilic solute molecules on the local solvation configurations. We use two water soluble alcohols: ethanol (EtOH) and its fluorinated counterpart, 2,2,2-trifluoroethanol (TFE), as model solutes. Our study is aimed to determine the relative abundance of different hydrogen bonded conformers and to establish a correlation between the spectral signatures (as obtained from THz spectroscopic measurements) and microscopic solute-solvent interactions associated with the local solvation structures (as obtained from MD simulations). Finally, we estimate the possible energetic parameters associated with the alcohol solubilization process. We found that while both the alcohols are completely water soluble, they receive a contrasting solvation energy share in terms of entropy and enthalpy. We understand that these findings are not limited to the specific system studied here but can be broadly extrapolated to other amphiphilic aqueous solutions.

6.
J Phys Chem B ; 127(40): 8576-8585, 2023 10 12.
Artigo em Inglês | MEDLINE | ID: mdl-37769128

RESUMO

An elevated level of creatinine (CRN) is a mark of kidney ailment, and prolonged retention of such condition could lead to renal failure, associated with severe ischemia. Antioxidants are clinically known to excrete CRN from the body through urine, thereby reducing its level in blood. The molecular mechanism of such an exclusion process is still illusive. As the excretion channel is urine, solvation of the solute is expected to play a pivotal role. Here, we report a detailed time-domain and frequency-domain terahertz (THz) spectroscopic investigation to understand the solvation of CRN in the presence of two model antioxidants, mostly used to treat elevated CRN level: N-Acetyl-l-cysteine (NAC) and ascorbic acid (ASC). FTIR spectroscopy in the mid-infrared region and UV absorption spectroscopy measurements coupled with quantum chemical calculations [at the B3LYP/6-311G++(d,p) level] reveal that both NAC and ASC form HBonded complexes with CRN and rapidly undergo a barrier-less proton transfer process to form creatinium ions. THz measurements provide explicit evidence of the formation of highly solvated complexes compared with bare CRN, which eventually enables its excretion through urine. These observations could provide a foundation for designing more beneficial drugs to resolve kidney diseases..


Assuntos
Antioxidantes , Nefropatias , Humanos , Creatinina/urina , Ácido Ascórbico , Espectroscopia de Infravermelho com Transformada de Fourier , Acetilcisteína
7.
MethodsX ; 11: 102263, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37416489

RESUMO

This study elaborately manifests a simplified Technique for Order Preference by Similarity to Ideal Solution (TOPSIS) multicriteria decision-making (MCDM) approach that goals to determine the disparity among the distances between the positive and negative ideal solutions. MCDM methods evaluate options based on a variety of criteria by using mathematical and analytical methodologies. This promotes a more transparent and objective decision-making process by removing human biases and subjective judgements. By considering the comparative proximity to the optimal situation, TOPSIS considers the distances between the ideal and the negative-ideal alternatives. This study has concentrated on the normalization process, the appropriate determination of the ideal and the anti-ideal solution, and the metric utilized to compute the euclidean distances from the ideal best and the ideal worst.•This study expresses the simplified TOPSIS methodology as stated by Hwang and Yoon (1981). The categorization and weight assignments of the criteria have been executed from the expert's opinion and based on existing literatures.•Integration of the TOPSIS technique with GIS has been properly performed for the production of a flood susceptibility map of a highly vulnerable region and visual interpretation of the TOPSIS algorithm.•This kind of investigation saved time by sufficiently skilled specialized personnel in this field.

8.
Nanotechnology ; 34(43)2023 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-37478833

RESUMO

In addition to the superior electrical and optoelectronic attributes, ultrathin two-dimensional transition metal dichalcogenides (TMDCs) have evoked appreciable attention for their piezoelectric properties. In this study, we report, the piezoelectric characteristics of large area, chemically exfoliated TMDCs and their heterostructures for the first time, as verified by piezoelectric force microscopy measurements. Piezoelectric output voltage response of the MoS2-WSe2heterostructure piezoelectric nanogenerator (PENG) is enhanced by ∼47.5% if compared with WSe2and ∼29% if compared to MoS2PENG, attributed to large band offset induced by heterojunction formation. This allows the scalable fabrication of self-powered energy harvesting PENGs, which can overcome the various shortcomings of complicated synthesis processes, complex fabrication steps, low yield, and poor stability. The fabricated flexible, self-powered MoS2-WSe2heterostructure nanogenerator exhibits piezoelectric output ∼46 mV under a strain of ∼0.66% yielding a power output ∼12.3 nW, which offers better performance than other two-dimensional material based piezoelectric devices and also reveals the ability of bio-mechanical energy harvesting. This cost effective approach to fabricate eco-friendly MoS2-WSe2based fatigue free, superior performance piezoelectric-nanogenerators can be utilized to evolve flexible energy harvesting devices and may also be attractive as a self-powered, smart wearable sensor devices.

9.
Heliyon ; 9(5): e16186, 2023 May.
Artigo em Inglês | MEDLINE | ID: mdl-37234665

RESUMO

Predicting landslides is becoming a crucial global challenge for sustainable development in mountainous areas. This research compares the landslide susceptibility maps (LSMs) prepared from five GIS-based data-driven bivariate statistical models, namely, (a) Frequency Ratio (FR), (b) Index of Entropy (IOE), (c) Statistical Index (SI), (d) Modified Information Value Model (MIV) and (e) Evidential Belief Function (EBF). These five models were tested in the high landslides-prone humid sub-tropical type Upper Tista basin of the Darjeeling-Sikkim Himalaya by integrating the GIS and remote sensing. The landslide inventory map consisting of 477 landslide locations was prepared, and about 70% of all landslide data was utilized for training the model, and 30% was used to validate it after training. A total of fourteen landslide triggering parameters (elevation, slope, aspect, curvature, roughness, stream power index, TWI, distance to stream, distance to road, NDVI, LULC, rainfall, modified fournier index, and lithology) were taken into consideration for preparing the LSMs. The multicollinearity statistics revealed no collinearity problem among the fourteen causative factors used in this study. Based on the FR, MIV, IOE, SI, and EBF approaches, 12.00%, 21.46%, 28.53%, 31.42%, and 14.17% areas, respectively, identified in the high and very high landslide-prone zones. The research also revealed that the IOE model has the highest training accuracy of 95.80%, followed by SI (92.60%), MIV (92.20%), FR (91.50%), and EBF (89.90%) models. Consistent with the actual distribution of landslides, the very high, high, and medium hazardous zones stretch along the Tista River and major roads. The suggested landslide susceptibility models have enough accuracy for usage in landslide mitigation and long-term land use planning in the study area. Decision-makers and local planners may utilise the study's findings. The techniques for determining landslide susceptibility can also be employed in other Himalayan regions to manage and evaluate landslide hazards.

10.
Langmuir ; 39(13): 4601-4610, 2023 04 04.
Artigo em Inglês | MEDLINE | ID: mdl-36952287

RESUMO

Proteins, in the presence of trivalent cations, exhibit intriguing phase behavior which is contrasting compared to mono- and divalent cations. At room temperature (RT), trivalent cations induce microscopic liquid-liquid phase separation (LLPS) in which a protein-rich phase coexists with a dilute phase. The critical solution temperature related phenomena in these complex fluids are well studied; however, such studies have mostly been restricted below the denaturation temperature (TM) of the protein(s) involved. Here, we probe the phase behavior of bovine serum albumin (BSA) incubated at 70 °C (>TM) in the presence of Na+, Mg2+, La3+, Y3+, and Ho3+ ions. BSA in the presence of mono- and bivalent ions forms an intense gel phase at 70 °C; however, the trivalent salts offer remarkable thermal resistivity and retain the fluid LLPS phase. We determine the microscopic phase behavior using differential interference contrast optical microscopy, which shows that the LLPS droplet structures in the M3+ ion-containing protein solutions prevail upon heating, whereas Mg2+ forms composed cross-linking gelation upon thermal incubation. We probe the interior environment of the protein aggregates by ps-resolved fluorescence anisotropy measurements using 8-anilino-1-naphthalenesulfonic acid (ANS) as an extrinsic fluorophore. It reveals that while the LLPS phase retains the rotational time constants upon heating, in the case of gelation, the immediate environment of ANS gets significantly perturbed. We investigate the explicit protein hydration at RT as well as at T > TM using the ATR THz-FTIR (1.5-22.5 THz) spectroscopy technique and found that hydration shows strong ion specificity and correlates the phase transition behavior.


Assuntos
Soroalbumina Bovina , Fenômenos Químicos , Temperatura , Cátions/química , Transição de Fase , Soroalbumina Bovina/química
11.
Langmuir ; 39(7): 2850-2858, 2023 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-36758211

RESUMO

Polymer/surfactant composites are used in industry as an excipient for water-insoluble solutes. Such enhanced dissolution ability of composite media is related to the spontaneous formation of pre-micellar polymer surfactant aggregates (PS) at a magnitude of order lower than the surfactant critical micelle concentration in water. Combining electrochemical and spectroscopic studies, we investigate the microscopic interfacial structure (i.e., interface electrostatics and surface polarity) of PS formed in composite media. We establish that in a composite system, a mere change in the polymer concentration at a fixed surfactant concentration makes possible to regulate the counter-ion binding ability, surface potential, surface charge density, packing and surface polarity of the PS interface. Our study shows that the higher dissolution of water-insoluble nonionic solutes in composite media is driven by the depressing of surface charge density and polarity of the PS interface. A similar modulation of the PS interface acts as a barrier for the passive relocation of water-soluble charged solutes into the PS pseudo-phase. The time-resolved fluorescence anisotropy study allows us to underline the effect of surface charge modulation on the dynamical aspects of solutes at the PS interface.

12.
Environ Sci Pollut Res Int ; 30(6): 16036-16067, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36180798

RESUMO

In the Sub-Himalayan foothills region of eastern India, floods are considered the most powerful annually occurring natural disaster, which cause severe losses to the socio-economic life of the inhabitants. Therefore, the present study integrated geographic information system (GIS) and three comprehensive and systematic multicriteria decision-making (MCDM) techniques such as Technique for Order Preference by Similarity to Ideal Solution (TOPSIS), Vise Kriterijumska Optimizacijaik Ompromisno Resenje (VIKOR), and Evaluation Based on Distance from Average Solution (EDAS) in Koch Bihar district for comparative assessment of the flood-susceptible zones. The multi-dimensional 21 indicators were considered, and multicollinearity statistics were employed to erase the issues regarding highly correlated parameters (i.e., MFI and long-term annual rainfall). Results of MCDM models depicted that the riparian areas and riverine "chars" (islands) are the most susceptible sectors, accounting for around 40% of the total area. The microlevel assessment revealed that flooding was most susceptible in the Tufanganj-I, Tufanganj-II, and Mathabhanga-I blocks, while Haldibari, Sitalkuchi, and Sitai blocks were less susceptible. Spearman's rank (rs) tests among the three MCDM models revealed that TOPSIS-EDAS persisted in a high correlation (rs = 0.714) in contrast to the relationships between VIKOR-EDAS (rs = 0.651) and TOPSIS-VIKOR (rs = 0.639). The model's efficiency was statistically judged by applying the receiver operating characteristic-area under the curve (ROC-AUC), mean absolute error (MAE), mean square error (MSE), and root mean square error (RMSE) techniques to recognize the better-suited models for mapping the flood susceptibility. The performance of all techniques is found good enough (ROC-AUC = > 0.700 and MAE, MSE and RMSE = < 0.300). However, TOPSIS and VIKOR have manifested an excellent outcome and are highly recommended for identifying flood susceptibility in such active flood-prone areas. Thus, this kind of study addresses the role of GIS in the construction of the flood susceptibility of the region and the performance of the respective models in a very lucid manner.


Assuntos
Inundações , Sistemas de Informação Geográfica , Índia , Área Sob a Curva
13.
Phys Chem Chem Phys ; 24(38): 23661-23668, 2022 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-36148614

RESUMO

Multivalent (specifically trivalent) metal ions are known to induce microscopic phase separation (commonly termed as liquid-liquid phase separation (LLPS)) in negatively charged globular proteins even at ambient temperatures, the process being mostly driven by protein charge neutralization followed by aggregation. Recent simulation studies have revealed that such self-aggregation of proteins is entropy driven; however, it is associated with a solvation effect, which could as well be different from the usual notion of hydrophobic hydration. In this contribution we have experimentally probed the explicit change in hydration associated with ion-induced LLPS formation of a globular protein bovine serum albumin (BSA) at ambient temperature using FIR-THz FTIR spectroscopy (50-750 cm-1; 1.5-22.5 THz). We have used ions of different charges: Na+, K+, Ca2+, Mg2+, La3+, Y3+, Ho3+ and Al3+. We found that all the trivalent ions induce LLPS; the formation of large aggregates has been evidenced from dynamic light scattering (DLS) measurements, but without perturbing the protein structure as confirmed from circular dichroism (CD) measurements. From the frequency dependent absorption coefficient (α(ν)) measurements in the THz frequency domain we estimate the various stretching/vibrational modes of water and we found that ions, forming LLPS, produce definite perturbation in the overall hydration, the extent of which is ion specific, invoking the definite role of hydrophilic (electrostatic) hydration of ions in the observed LLPS process.


Assuntos
Líquidos Iônicos , Soroalbumina Bovina , Cátions/química , Interações Hidrofóbicas e Hidrofílicas , Soroalbumina Bovina/química , Eletricidade Estática , Água/química
14.
Phys Chem Chem Phys ; 24(34): 20381-20389, 2022 Aug 31.
Artigo em Inglês | MEDLINE | ID: mdl-35983752

RESUMO

Cholesterol is known to modify the phase behavior of model lipid membranes as it makes phospholipid bilayers more structured. Simulation results have shown that the addition of cholesterol allows more bulk-like water to protrude into phospholipid interfaces. However, such claims have not yet been verified experimentally. We have investigated the alteration in the hydrogen bond network structure of water at the surface of two model phospholipids DOPC and DOPG as cholesterol is added into these using ATR-FTIR spectroscopy in the FIR-THz region. Our measurements and analysis led us to probe the collective H-bond network explicitly at the lipid surface. A detailed principal component analysis of the measured data concludes that the water-water H-bond vibration dynamics gets slower at the lipid surface as compared to bulk water, the effect being more prominent in the case of the charged phospholipid, DOPG. However, as cholesterol is added and more bulk-like water protrudes into the liposome interface, the H-bond vibration gets weaker and correspondingly the dynamics gets accelerated.


Assuntos
Colesterol , Fosfolipídeos , Colesterol/química , Ligação de Hidrogênio , Bicamadas Lipídicas/química , Fosfolipídeos/química , Espectroscopia de Infravermelho com Transformada de Fourier , Água/química
15.
Chemphyschem ; 23(19): e202200337, 2022 10 06.
Artigo em Inglês | MEDLINE | ID: mdl-35775165

RESUMO

Vesicles contain two aqueous regions: inner core and outer-to-bulk. It has remained an open question whether hydration behaviour in the inner core differs from the outer-to-bulk region, mostly owning to the inability of the conventional spectroscopic techniques to deconvolute the contribution from these two regions. We, using THz-FTIR spectroscopy (1.5-13.5 THz) experimentally probe the inner hydration of three differently charged surfactant/cholesterol vesicles composed of SDS, CTAB and Brij 30. Both dynamic light scattering (DLS) and atomic force microscopy (AFM) measurements affirm the transition from micelles to vesicles as cholesterol is added into surfactant solutions. FTIR measurements show that hydration behaviour changes significantly as micelles are converted into vesicles, the change been exclusively caused due to the formation of an inner core. Our measurements on the hydrogen bond stretch and librational motion of the inner hydration show distinct features compared to the overall hydration, which in turn is found to be surfactant type and cholesterol concentration dependent.


Assuntos
Micelas , Tensoativos , Cetrimônio , Colesterol/química , Polidocanol , Análise Espectral , Tensoativos/química
16.
Biophys Chem ; 288: 106842, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-35696897

RESUMO

We have used five different hydrophobic L-amino acids (Gly, Ala, Val, Leu, Ile) as molecular crowders to investigate their role on the enzymatic activity of lysozyme towards Micrococcus lysodeikticus (M. lys.)cell as substrate. We found that except Ile, all other amino acids show a bell like profile of catalytic efficiency (kcat/Km) with their increasing concentration whereas for Ile, the value is gradually increasing. The trend of activation energy (Ea) is also well correlated with the catalytic efficiency of lysozyme. At low concentration of amino acids, soft interaction predominates whereas at higher concentration range, excluded volume, viscosity, hydrophobicity combinedly decrease the activity of lysozyme.


Assuntos
Muramidase , Fragmentos de Peptídeos , Sequência de Aminoácidos , Aminoácidos , Interações Hidrofóbicas e Hidrofílicas , Tripsina
17.
Langmuir ; 38(10): 3105-3112, 2022 03 15.
Artigo em Inglês | MEDLINE | ID: mdl-35245073

RESUMO

Both electrostatic and hydrophobic interactions play pivotal roles in ligand-surfactant binding interaction, especially for ionic surfactants. While much studies have been reported in the micellar region, less attention has been paid on such interactions at a low (premicellar) surfactant concentration. We here study the interaction between the cationic dye rhodamine 6G (R6G) with surfactants of different charge types: anionic SDS, cationic CTAB, and nonionic Tx 100 using absorption and emission spectroscopy. We identify that R6G forms dimeric aggregates at a premicellar concentration of SDS. Formation of aggregates is also confirmed from classical simulation measurements. CTAB and Tx 100 do not form any such aggregate, presumably owing to unfavorable electrostatic interactions. For a molecular-level understanding, we perform two-photon absorption (TPA) spectroscopy for the same systems. TPA allows us to calculate the two-photon absorption cross section and subsequently the change in the dipole moment (Δµ) between ground and excited states of the dye. We calculate the Δµ and observe that it passes through a maximum at a surfactant concentration half of the critical micelle concentration of SDS. This observation imparts support to earlier quantum mechanical calculation, which infers deviation from the parallel orientation of the dye during surfactant-induced aggregation. We extended our measurements and varied the carbon chain length of the anionic surfactant, and we found that all of them exhibit a maximum in Δµ, while their relative magnitude is dependent on the surfactant carbon chain length.


Assuntos
Surfactantes Pulmonares , Tensoativos , Carbono , Cátions , Cetrimônio , Excipientes , Micelas , Simulação de Dinâmica Molecular , Tensoativos/química
18.
ACS Appl Mater Interfaces ; 14(4): 5775-5784, 2022 Feb 02.
Artigo em Inglês | MEDLINE | ID: mdl-35068147

RESUMO

Recent progress in the synthesis of highly stable, eco-friendly, cost-effective transition-metal dichalcogenide (TMDC) quantum dots (QDs) with their broadband absorption spectra and wavelength selectivity features have led to their increasing use in broadband photodetectors. With the solution-based processing, we demonstrate a superlarge (∼0.75 mm2), ultraviolet-visible (UV-vis) broadband (365-633 nm) phototransistor made of WS2 QDs-decorated chemical vapor deposited (CVD) graphene as the active channel with extraordinary stability and durability under ambient conditions (without any degradation of photocurrent until 4 months after fabrication). Here, colloidal zero-dimensional (0D) WS2 QDs are used as the photoabsorbing material, and graphene acts as the conducting channel. A high photoresponsivity (3.1 × 102 A/W), moderately high detectivity (∼8.9 × 108 Jones), and low noise equivalent power (∼9.7 × 10-11 W/Hz0.5) are obtained at a low bias voltage (Vds = 1 V) at an illumination of 365 nm with optical power as low as ∼0.8 µW/cm2, which can be further tuned by modulating the gate bias. While comparing the photocurrent between two different morphologies of WS2 [QDs and two-dimensional (2D) nanosheets], a significant enhancement of photocurrent is observed in the case of QD-based devices. Ab initio density functional theory (DFT)-based calculations further support our observation, revealing the role of quantum confinement in enhanced photoresponse. Our work reveals a strategy toward developing a scalable, cost-effective, high-performance hybrid mixed-dimensional (2D-0D) photodetector with graphene-WS2 QDs for next-generation optoelectronic applications.

19.
J Phys Chem Lett ; 13(3): 931-938, 2022 Jan 27.
Artigo em Inglês | MEDLINE | ID: mdl-35050625

RESUMO

While the liquid-liquid phase separation (LLPS) process in proteins has been studied in great detail, it has not been widely explored how the associated protein hydration changes during the process and how crucial its role is in the process itself. In this contribution, we experimentally explore the alteration of lysozyme hydration during its LLPS process using attenuated total reflection (ATR)-FTIR spectroscopy in the THz frequency region (1.5-21 THz). Additionally, we explore the role of excipients (l-arginine, sucrose, bovine albumin (BSA), and ubiquitin (Ubi)) in regulating the process and found that, while sucrose stabilizes the LLPS, BSA inhibits it. The effect of Arg in the LLPS is subtle, and that of Ubi is concentration dependent. We made a detailed analysis of the hydration profile of Lys in the presence of these excipients and observe that a change in hydration in terms of H-bond making/breaking is a definite signature regulating the process.


Assuntos
Excipientes
20.
Nanoscale ; 13(37): 15819-15829, 2021 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-34528991

RESUMO

Benefiting from the advantages of low cost, light weight and mechanical flexibility, piezoelectric nanogenerators have the potential for application in renewable energy harvesting from various unexplored sources. Here, we report the demonstration of the record efficiency of flexible piezoelectric nanogenerators (PENG) using composites of polyvinylidene fluoride (PVDF) and chemically exfoliated tungsten disulfide (WS2) nanosheets, which are found to be strongly photosensitive, making them attractive for self-powered optical devices. The presence of two-dimensional (2D) WS2 nanosheets in the PVDF matrix plays a dual role in enhancing the nucleation of the electroactive ß-phase as well as inducing strong photosensitivity in the nanocomposite. The PVDF-WS2 composed flexible device is able to produce an enormously high output voltage of ∼116 V (for an impact of 105 kPa) and a piezoelectric energy conversion efficiency of ∼25.6%, which is the highest among the reported values for PVDF-2D material based self-poled piezoelectric nanogenerators. This self-poled piezo-phototronic device exhibits strain-dependent photocurrent at zero bias and exhibits a responsivity of 6.98 × 10-3 A W-1 at 0.75% strain under the illumination of 410 nm. The fabricated PENG is also able to harvest energy from routine human activities (finger tapping, writing on paper, mouse clicking, etc.) and movement of human body parts. These results open up a new horizon in piezo-phototronic materials through the realization of photosensitive multifunctional PENGs, which can be scaled up for fabricating compact, high performance, portable and self-powered wearable electronic devices for smart sensor applications.

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