Sputtering thin films: Materials, applications, challenges and future directions.

Sputtering is an effective technique for producing ultrathin films with diverse applications. The review begins by providing an in-depth overview of the background, introducing the early development of sputtering and its principles. Consequently, progress in advancements made in recent decades highlights the renaissance of sputtering as a powerful technology for creating thin films with varied compositions, structures, and properties. For the first time, we have discussed a thorough overview of several sputtered thin film materials based on metal and metal oxide, metal nitride, alloys, carbon, and ceramic-based thin film along with their properties and their applicability in various fields. We further delve into the applications of sputter-coated thin films, specifically emphasizing their relevance in environmental sustainability, energy and electronics, and biomedical fields. We critically examine the recent advancements in developing sputter-coated catalysts for eliminating water pollutants andhydrogen generation. Additionally, the review sheds light on advantages, shortcomings, and future directions for developing sputter-coated thin films utilized in biodegradable metals and alloys with enhanced corrosion resistance and biocompatibility. This review is a comprehensive integration of recent literature, covering diverse sputtering thin film applications. We delve deeply into various material types and emphasize critical analysis of recent advancements, particularly in environmental, energy, and biomedical fields. By offering insights into both advancements and limitations, the review provides a nuanced understanding essential for practical utilization.

Modulated Ultrathin NiCo-LDH Nanosheet-Decorated Zr3+-Rich Defective NH2-UiO-66 Nanostructure for Efficient Photocatalytic Hydrogen Evolution.

Defect engineering through modification of their surface linkage is found to be an effective pathway to escalate the solar energy conversion efficiency of metal-organic frameworks (MOFs). Herein, defect engineering using controlled decarboxylation on the NH2-UiO-66 surface and integration of ultrathin NiCo-LDH nanosheets synergizes the hydrogen evolution reaction (HER) under a broad visible light regime. Diversified analytical methods including positron annihilation lifetime spectroscopy were employed to investigate the role of Zr3+-rich defects by analyzing the annihilation characteristics of positrons in NH2-UiO-66, which provides a deep insight into the effects of structural defects on the electronic properties. The progressively tuned photophysical properties of the NiCo-LDH@NH2-UiO-66-D-heterostructured nanocatalyst led to an impressive rate of HER (∼2458 µmol h-1 g-1), with an apparent quantum yield of ∼6.02%. The ultrathin NiCo-LDH nanosheet structure was found to be highly favored toward electrostatic self-assembly in the heterostructure for efficient charge separation. Coordination of Zr3+ on the surface of the NiCo-LDH nanosheet support through NH2-UiO-66 was confirmed by X-ray absorption spectroscopy and electron paramagnetic resonance spectroscopy techniques. Femtosecond transient absorption spectroscopy studies unveiled a photoexcited charge migration process from MOF to NiCo-LDH which favorably occurred on a picosecond time scale to boost the catalytic activity of the composite system. Furthermore, the experimental finding and HER activity are validated by density functional theory studies and evaluation of the free energy pathway which reveals the strong hydrogen binding over the surface and infers the anchoring effect of the ultrathin layered double hydroxide (LDH) in the vicinity of the Zr cluster with a strong host-guest interaction. This work provided a novel insight into efficient photocatalysis via defect engineering at the linker modulation in MOFs.

Controlled Ni doping on a g-C3N4/CuWO4 photocatalyst for improved hydrogen evolution.

The development of a low-cost, environment-friendly and suitable semiconductor-based heterogeneous photocatalyst poses a great challenge towards extremely competent and substantial hydrogen evolution. A series of environment-friendly and proficient S-scheme Ni-doped CuWO4 nanocrystals supported on g-C3N4 nanocomposites (Ni-CuWO4/g-C3N4) were constructed to ameliorate the photocatalytic efficacy of pure g-C3N4 and Ni-CuWO4 and their activity in H2 generation through photocatalytic water splitting was evaluated. The Ni-CuWO4 nanoparticles were synthesized through doping of Ni2+ on wolframite CuWO4 crystals via the chemical precipitation method. An elevated hydrogen generation rate of 1980 µmol h-1 g-1 was accomplished over the 0.2Ni-CuWO4/g-C3N4 (0.2NCWCN) nanocomposite with an apparent quantum yield (AQY) of 6.49% upon visible light illumination (λ ≥ 420 nm), which is evidently 7.1 and 17.2 fold higher than those produced from pristine g-C3N4 and Ni-CuWO4. The substantial enhancement in the photocatalytic behaviour is primarily because of the large surface area, limited band gap energy of the semiconductor composite and magnified light harvesting capability towards visible light through the inclusion of g-C3N4, thus diminishing the reassembly rate of photoinduced excitons. Further, density functional theory (DFT) calculations were performed to investigate the structural, electronic and optical properties of the composite. Theoretical results confirmed that the Ni-CuWO4/g-C3N4 composite is a potential candidate for visible-light-driven photocatalysts and corroborated with the experimental findings. This research provides a meaningful and appealing perspective on developing cost-effective and very proficient two-dimensional (2D) g-C3N4-based materials for photocatalytic H2 production to accelerate the separation and transmission process of radiative charge carriers.

Recent advances in solution assisted synthesis of transition metal chalcogenides for photo-electrocatalytic hydrogen evolution.

Hydrogen evolution from water splitting is considered to be an important renewable clean energy source and alternative to fossil fuels for future energy sustainability. Photocatalytic and electrocatalytic water splitting is considered to be an effective method for the sustainable production of clean energy, H2. This perspective especially emphasizes research advances in the solution-assisted synthesis of transition metal chalcogenides for both photo and electrocatalytic hydrogen evolution applications. Transition metal chalcogenides (CdS, MoS2, WS2, TiS2, TaS2, ReS2, MoSe2, and WSe2) have received intensified research interest over the past two decades on account of their unique properties and great potential across a wide range of applications. The photocatalytic activity of transition metal chalcogenides can further be improved by elemental doping, heterojunction formation with noble metals (Au, Pt, etc.), non-chalcogenides (MoS2, In2S3, NiS1-X), morphological tuning, through various solution-assisted synthesis processes, including liquid-phase exfoliation, heat-up, hot-injection methods, hydrothermal/solvothermal routes and template-mediated synthesis processes. In this review we will discuss recent developments in transition metal chalcogenides (TMCs), the role of TMCs for hydrogen production and various strategies for surface functionalization to increase their activity, different synthesis methods, and prospects of TMCs for hydrogen evolution. We have included a brief discussion on the effect of surface hydrogen binding energy and Gibbs free energy change for HER in electrocatalytic hydrogen evolution.

Anisotropic phenanthroline-based ruthenium polymers grafted on a titanium metal-organic framework for efficient photocatalytic hydrogen evolution.

Conjugated polymers and titanium-based metal-organic framework (Ti-MOF) photocatalysts have demonstrated promising features for visible-light-driven hydrogen production. We report herein a strategy of anisotropic phenanthroline-based ruthenium polymers (PPDARs) over Ti-MOF, a tunable platform for efficient visible-light-driven photocatalytic hydrogen evolution reaction (HER). Several analytical methods including X-ray absorption spectroscopy (XAS) revealed the judicious integration of the surface-active polymer over the Ti-MOF reinforcing the catalytic activity over the broad chemical space. PPDAR-4 polyacrylate achitecture led to a substantial increase in the H2 evolution rate of 2438 µmolg-1h-1 (AQY: 5.33%) compared to pristine Ti-MOF (238 µmol g-1 h-1). The separation of photogenerated charge carriers at the PPDAR-4/Ti-MOF interface was confirmed by the optical and electrochemical investigations. The experimental, as well as theoretical data, revealed their physical and chemical properties which are positively correlated with the H2 generation rate. This offers a new avenue in creating polymer-based MOF robust photocatalysts for sustainable energy.

Hot injection-induced synthesis of ZnCdS-rGO/MoS2 heterostructures for efficient hydrogen production and CO2 photoreduction.

A highly efficient hybrid ZnCdS-rGO/MoS2 heterostructure is successfully synthesized through a hot injection method and control loading of rGO/MoS2. The synergism provides an unprecedently high H2-generation rate of 193.4 mmol H2 g-1 h-1 from water under full arc solar radiation and MeOH production (5.26 mmol g-1 h-1, AQY of 14.6% at λ = 420 ± 20 nm) from CO2 reduction.

A2B- and A3-Type Boron(III)Subchlorins Derived from meso-Diethoxycarbonyltripyrrane: Synthesis and Photophysical Exploration.

The first direct fabrication of A2B- and A3-type B(III)subchlorins from meso-ethoxycarbonyl-substituted tripyrrane has been realized by condensation with appropriate acid chlorides (benzoyl chloride, butyryl chloride, and ethyl chlorooxoacetate). The aliphatic acid chloride-based annulation reaction is new to subporphyrinoid chemistry. The phenyl (6a)- or n-propyl (6b)-substituted derivatives could be oxidized to the corresponding B(III)subporphyrins upon refluxing with DDQ, whereas the triethoxycarbonyl moiety (6c) was found to be resistant to oxidation and exhibits the most red-shifted absorption (587 nm) and emission (604 nm). The study indicates that absorption and emission behaviors of the B(III)subchlorin can be tuned by the introduction of electron-rich or electron-deficient substituents at the meso-position. B(III)subchlorins 6a and 6c generate singlet oxygen efficiently (44 and 40%, respectively) and, thus, may find application as potential photosensitizers in photodynamic therapy (PDT).

Structural Stability and Conformational Dynamics of Cytochrome c in Hydrated Deep Eutectic Solvents.

Many deep eutectic solvents (DESs) are currently being explored as environment-friendly media for biorelated applications. As an understanding of the effect of these solvents on the structure of biomolecules is crucial for these applications, we study how two DESs comprising trimethylglycine (TMG) and ethylene glycol (EG) or glycerol (GL) influence the structural stability and conformational dynamics of cytochrome c (Cytc) using single-molecule-based fluorescence correlation spectroscopy (FCS) technique and several other ensemble-based biophysical methods. The FCS studies on A488-labeled Cytc enable an estimation of the size (20.5 ± 1.5 Å) of the protein and capture its conformational dynamics (54 ± 2 µs) in aqueous buffered solution. It is observed that both size and conformational dynamics of the protein are influenced in the presence of the DESs, but this effect is more pronounced in the case of TMG-EG. The ensemble measurements on both labeled and wild-type Cytc reveal that the protein structure is unfolded completely by TMG-EG, whereas the structure is slightly altered by TMG-GL. The results suggest that the behavior of Cytc in hydrated DESs is determined by the strength of interactions between the DES constituents as well as that between the constituents and the water molecules present in the system.

Sensing and modulation of amyloid fibrils by photo-switchable organic dots.

Abnormal aggregation of amyloidogenic proteins (like Aß 42, amylin, α-synuclein, insulin) and the deposition of these aggregates is believed to be associated with several diseases known as amyloidosis. The pathway of aggregation involves three distinct phases: the oligomeric, elongation and plateau phases. Among them, the oligomeric phase of Aß 42 and α-synuclein involves the generation of transient oligomeric species suspected to cause several neurological disorders, including Alzheimer's and Parkinson's diseases. Over the past few years, scientists have devoted much more effort to devising new fluorescent molecular probes to estimate the mechanisms of formation, and have gained vital information about possible therapeutic routes for amyloidosis. However, such fluorescent probes face serious limitations because of self-quenching at high concentrations of the probe; therefore, they are inappropriate for quantitative analysis and bio-imaging experiments. Hence, smart biocompatible fluorescent probes are indispensable, as they not only overcome the drawbacks of conventional fluorescent probes, but also have the potential ability to fight amyloidosis through modulation of the pathways involved. In this work, for the first time we introduce a series of promising photo-switchable aggregation-induced emission (AIE) dots (DPAPMI, CPMI) and aggregation caused quenching (ACQ) dots (DMAPMI) which can detect amyloid fibrils in terms of switching and enhancing their fluorescence emission. Interestingly, the organic dots enhance the aggregation rate of insulin by speeding up the microscopic processes, specifically secondary nucleation (with rate constant k2) and the elongation process (with rate constant k+). Moreover, the comparison of kinetics studies with ThT suggests that our organic dots can sense pre-fibrillar aggregates of insulin during the aggregation process, which may be beneficial for the early detection of amyloid fibrils. In summary, our study indicates that these organic dots can be used for the imaging and early stage detection of amyloid fibril formation and the modulation of amyloid formation pathways.

Complete Solvation Dynamics of Coumarin 153 in Tetraalkylammonium Bromide-Based Deep Eutectic Solvents.

Deep eutectic solvents (DESs) are novel environment-friendly media for a variety of applications. In order to obtain insight into the structure and dynamics of some less-explored DESs comprising ethylene glycol and tetraalkylammonium bromide salts with variable alkyl chain length, we have captured complete dynamics occurring in these solvents in a timescale of few femtoseconds to several nanoseconds by monitoring the time-dependent fluorescence Stokes shift of coumarin 153 employing a combination of time-correlated single-photon counting and fluorescence upconversion techniques. The solvent response function constructed from the measured data reveals a sub-picosecond component (∼0.8 ps, 20-35%) in addition to a slow component (180-475 ps) with a distribution of relaxation time. The slow time component is found to be strongly dependent on the viscosity of the medium, indicating that it arises from the diffusive motions of the solvent constituents into and out of the solvation shell, whereas the ultrafast time component, which is nearly independent of the solvent viscosity, arises from fast local motions of the constituents in the immediate vicinity of the solute molecule.

Insights into the Folding Pathway of a c-MYC-Promoter-Based i-Motif DNA in Crowded Environments at the Single-Molecule Level.

Cytosine-rich DNA sequences fold into secondary structures called i-Motifs, which are usually stable at acidic pH. However, molecular crowding agents, such as poly(ethylene glycol) (PEG), are known to facilitate the formation of these structures even at neutral pH. As crowding mimics the intracellular environment and not much is known about the folding pathway of i-Motifs in such constrained media, we have probed, in detail, the conformational changes of a 22-mer c-MYC-promoter-based C-rich sequence (Py22) in the presence of PEG, employing Förster resonance energy transfer and fluorescence lifetime measurements at the single-molecule level. We find that the folding process is not a simple two-state transition between a random coil and a folded i-Motif structure. Rather, it involves a partially folded conformation as an intermediate in which the bases are not as efficiently stacked as in the completely folded i-Motif form. The relative population of each species is governed by the size and concentration of PEG, and 30% (w/w) PEG6000 is the optimum condition for the folding of Py22. Under this condition, ∼80% of Py22 exists in the fully folded i-Motif form and ∼20% of it is in the partially folded state.

Liquid Structure and Dynamics of Tetraalkylammonium Bromide-Based Deep Eutectic Solvents: Effect of Cation Chain Length.

Deep eutectic solvents (DESs) have emerged in recent years as environmentally sustainable media across several fields. However, knowledge of liquid structure, dynamics, and solute-solvent interactions in many DESs that is essential for exploiting their potential is still lacking. In this work, we make an attempt to obtain some insight into these aspects of a set of less-explored DESs comprising tetraalkylammonium bromide salts and ethylene glycol (EG) by monitoring the fluorescence response of some carefully chosen dipolar (C153 and 4-AP) and nonpolar (9-PA) solutes in these media. Specifically, we have studied the translational and rotational diffusion dynamics of these molecular systems using single-molecule-based fluorescence correlation spectroscopy technique and ensemble-based time-resolved fluorescence anisotropy measurements. These results point to spatial and dynamic heterogeneity of these DESs, which becomes prominent in systems comprising cations with a longer alkyl chain length. This study reveals that diffusion dynamics of the probe molecules is determined not only by the solvent bulk viscosity but also dependent on their microenvironments and solute-solvent interactions experienced in these media.

Interactions between a Bioflavonoid and c-MYC Promoter G-Quadruplex DNA: Ensemble and Single-Molecule Investigations.

Small molecules capable of stabilizing the G-quadruplex structure of the nuclease hypersensitivity element III1 (NHE III1) are useful in controlling the overexpression of the c-MYC oncogene. In this study, we have probed the interactions of a 22-mer c-MYC promoter quadruplex-forming sequence (Pu22) with a bioflavonoid 3,4',5,7-tetrahydroxyflavone, commonly known as kaempferol (KF). Ensemble fluorescence resonance energy transfer experiments on labeled Pu22 indicate that KF decreases the affinity of the former toward its complimentary strand, suggesting the stabilization of the quadruplex structure of Pu22. Considering that binding dynamics plays an important role in supramolecular interactions, there is hardly any information on this aspect for quadruplex-flavonoid systems; we have studied the kinetics of KF-Pu22 complexation and decomplexation processes on the single-molecule level by employing fluorescence correlation spectroscopy technique. The binding dynamics is characterized by a fast relaxation time of 10-50 µs. This leads to a high association rate constant ( k+) of ∼109 M-1 s-1, which is close to the pure diffusion controlled limit. However, it is the low dissociation rate constant ( k-) of ∼104 s-1 that is mainly responsible for the stability of the KF-Pu22 complex. Molecular docking study shows that KF binds near the 3'-end of Pu22 by forming several H-bonds with the bases. These findings suggest that KF is a potential binder of the c-MYC promoter quadruplex DNA and can be useful in anticancer therapies.

Two-dimensional lanthanide coordination polymer nanosheets for detection of FOX-7.

Despite the recent surge of interest in two-dimensional (2D) inorganic nanosheets derived from photoactive coordination polymers of lanthanide ions having interesting optical properties, research in this area is still in its infancy. Luminescent lanthanide ions, Eu(iii) or/and Tb(iii), as well as a bis-terpyridine ligand (L), were used in this study as the building blocks for the synthesis of the archetypical layered structure of coordination polymers (CPs) (L·Eu/L·Tb). 2D-nanosheets were obtained through exfoliation of the layered precursor of CPs in a suitable solvent system following a sonication-assisted strategy. These nanosheets exhibit lateral sizes on the micrometer scale (0.3-1 µm) and an ultrathin thickness of 2-6.5 nm. 1,1-Diamino-2,2-dinitroethene or FOX-7 is an insensitive high explosive; in a binder mixture, it exhibits a slightly superior detonation velocity of 8870 m s-1 in comparison to RDX. The insensitive nature of FOX-7 makes it a key component for the development of low vulnerable high explosive compositions for further application in weaponry. The growing demand for FOX-7, for use as a suitable replacement of conventional explosives, is of serious concern to human security. Achieving rapid and efficient detection of this unexplored explosive is a challenging task. In the present study, the developed luminescent nanosheets were used for the first time for micromolar level detection of FOX-7 both in solution and in the solid state. A visually distinct color change of the nanosheets from red (L·Eu) and green (L·Tb) to colorless was witnessed upon UV light irradiation during the detection process. Notably, the solid-state detection technique could be exploited for developing a commercial spray kit for quick onsite screening of this important explosive.

How do the hydrocarbon chain length and hydroxyl group position influence the solute dynamics in alcohol-based deep eutectic solvents?

Deep eutectic solvents (DESs) have received considerable attention in recent years as new sustainable green media and some of their interesting properties have stimulated investigations on the microscopic solution structure, solute-solvent interactions and solute/solvation dynamics in these media. Even though the alcohol-based DESs, due to their low viscosity, serve as useful media in various applications, little is known about the structure and dynamics of these solvents. In order to obtain insight into the microscopic structure and interactions operating in these media, we have studied the rotational and translational diffusion dynamics of some carefully chosen molecular systems (both dipolar and nonpolar) using time-resolved fluorescence anisotropy and fluorescence correlation spectroscopy techniques in a series of choline chloride/alcohol based DESs differing in hydrocarbon chain length and positioning of the hydroxyl group on the hydrogen bond donor. The results reveal an increase of both spatial and dynamic heterogeneity upon an increase in chain length of one of the components of these solvents. No significant variation of heterogeneity, however, could be observed with the change in the hydroxyl group position. The analysis of the experimental results indicates that solute-solvent hydrogen-bonding interaction plays a dominant role in determining both rotational and translational diffusion dynamics of AP in these DESs.

Solute Rotation and Translation Dynamics in an Ionic Deep Eutectic Solvent Based on Choline Chloride.

Deep eutectic solvents (DESs) are an emerging class of environment-friendly media useful in a variety of applications. However, the microscopic structure of these liquids is quite unclear, and issues like whether spatial and dynamic heterogeneity is a generic feature of the ionic DESs and whether the solute molecules experience similar environment and interactions with the medium irrespective of their charge are still open. In this work, we have attempted to address some of these issues for ethaline, a less viscous and ionic DES consisting of a mixture of 1:2 mole ratio of choline chloride and ethylene glycol by monitoring the fluorescence response of a number of carefully chosen neutral and charged probe molecules in ensemble and single molecule conditions. Specifically, we have examined the liquid state structure of ethaline by studying the rotational and translational diffusion dynamics of the solutes measured by monitoring the time dependence of fluorescence anisotropy in ensemble condition and fluorescence correlation signal of extremely dilute samples diffusing through confocal volume. These studies clearly reveal dynamic heterogeneity of the medium, though no spatial heterogeneity is observable through excitation wavelength dependent fluorescence measurements. The insights obtained from this study will be helpful in understanding the nature of solute-solvent interactions in this type of complex media.

Roles of the methyl and methylene groups of mercapto acids in the photoluminescence efficiency and carrier trapping dynamics of CdTe QDs.

Surface protection using an appropriate ligand is essential for controlling the size, stability and luminescence properties of the quantum dots (QDs). Though 3-mercaptopropanoic acid (3-MPA) is regarded as the most suitable protecting ligand among the mercapto acids for water soluble CdTe QDs, one receives a different picture from recent studies, which report a much higher luminescence efficiency of 3-mercaptobutyric acid (3-MBA) capped QDs compared with those capped by 3-MPA and attribute the observation to the influence of the side methyl group of mercapto acids. Herein we report the luminescence properties and carrier trapping dynamics of four different, but structurally related mercapto acid capped CdTe QDs prepared using a different method. The results show that these QDs are much more fluorescent than those prepared directly in an aqueous environment and surprisingly, no enhanced luminescence for the QDs capped by mercapto acids containing a side methyl group is observed. Ultrafast pump-probe measurements confirm these results in addition to providing insight into the carrier trapping dynamics of these systems. It is shown that our findings, which appear to be in conflict with the recent literature, can be rationalized and the exact role of the side methyl group of the mercapto acids can be understood by careful analysis of the results taking into consideration the difference in the methods of preparation of the QDs in the two cases.

Effect of fuzzy partitioning in Crohn's disease classification: a neuro-fuzzy-based approach.

Crohn's disease (CD) diagnosis is a tremendously serious health problem due to its ultimately effect on the gastrointestinal tract that leads to the need of complex medical assistance. In this study, the backpropagation neural network fuzzy classifier and a neuro-fuzzy model are combined for diagnosing the CD. Factor analysis is used for data dimension reduction. The effect on the system performance has been investigated when using fuzzy partitioning and dimension reduction. Additionally, further comparison is done between the different levels of the fuzzy partition to reach the optimal performance accuracy level. The performance evaluation of the proposed system is estimated using the classification accuracy and other metrics. The experimental results revealed that the classification with level-8 partitioning provides a classification accuracy of 97.67 %, with a sensitivity and specificity of 96.07 and 100 %, respectively.