Triangular Magnet Emergent from Noncentrosymmetric Sr0.94Mn0.86Te1.14O6 Single Crystals.

We report the successful growth of high-quality single crystals of Sr0.94Mn0.86Te1.14O6 (SMTO) using a self-flux method. The structural, electronic, and magnetic properties of SMTO are investigated by neutron powder diffraction (NPD), single-crystal X-ray diffraction (SCXRD), thermodynamic, and nuclear magnetic resonance techniques in conjunction with density functional theory calculations. NPD unambiguously determined octahedral (trigonal antiprismatic) coordination for all cations with the chiral space group P312 (no. 149), which is further confirmed by SCXRD data. The Mn and Te elements occupy distinct Wyckoff sites, and minor anti-site defects were observed in both sites. X-ray photoelectron spectroscopy reveals the existence of mixed valence states of Mn in SMTO. The magnetic susceptibility and specific heat data evidence a weak antiferromagnetic order at TN = 6.6 K. The estimated Curie-Weiss temperature θCW = -21 K indicates antiferromagnetic interaction between Mn ions. Furthermore, both the magnetic entropy and the 125Te nuclear spin-lattice relaxation rate showcase that short-range spin correlations persist well above the Néel temperature. Our work demonstrates that Sr0.94(2)Mn0.86(3)Te1.14(3)O6 single crystals realize a noncentrosymmetric triangular antiferromagnet.

Synergistic dynamics of photoionization and photoinduced electron transfer probed by laser flash photolysis and ultrafast fluorescence spectroscopy.

Photoionization (PI) and photoinduced electron transfer (PET) dynamics of coumarin 450 (C450) in micelles were investigated in the time domains of micro to femtoseconds using steady-state and time-resolved absorption and fluorescence spectroscopy. The PI of C450 occurs inside the micelles leads to the formation of C450 cation radical (CR) and hydrated electron, which is characterized by the respective transient absorption. The PI of C450 is monophotonic in nature and the yield is dependent on the charge of the micelles. The observation of amine CR in the transient absorption confirms the PET from amine to the excited state of C450 in micelles, which results in the quenching of both fluorescence intensity and lifetime. The decrease in femtosecond fluorescent decay of C450 and the absence of transient C450 radical anion in the presence of amine implies that the concerted ultrafast PET promoted PI and PET to the C450 CR-electron pair. The decrease in the time constant for the formation of relaxed state in the presence of amines is due to the ultrafast PET to the C450 CR-electron pair, which prevents the formation of a relaxed state through recombination at a longer time scale. In the present investigation, the recombination dynamics of the CR-electron pair is justified as one of the origins of the slow solvation in micelles. The influence of amine concentration on the decay of C450 CR indicates ET reaction between C450 CR and amine, which is further confirmed by the bleach recovery of C450 ground state in the presence of amine.

Internet of Things-Enabled Aggregation-Induced Emission Probe for Cu2+ Ions: Comprehensive Investigations and Three-Dimensional Printed Portable Device Design.

Herein, we have developed a novel aggregation-induced emission (AIE) probe and three-dimensional (3D) printed portable device for copper (Cu2+) sensing in an aqueous medium. A ubiquitous synthetic route has been employed to devise the anthracene-conjugated imidazo[1,5-a]pyridine (TL19) probe as a unique anchor for Cu2+ ions. The TL19 is meticulously characterized through pivotal spectroscopic techniques, and the satisfactory results were obtained. The solvatochromic analysis and density functional theory calculations cohesively reveal that the TL19 exhibits the intramolecular charge transfer transition upon photoexcitation. Intriguingly, the TL19 exhibits spherically shaped nanoaggregates and enhanced fluorescence in DMSO/water (10:90) mixtures. This fluorescent nanoaggregate instantaneously responded toward the detection of Cu2+ via a deaggregation mechanism. The detection limit is found to be 9 pM in an aqueous medium. Further, the detection of Cu2+ in the HeLa cells has also been achieved due to bright green fluorescence, photostability, and biocompatibility nature of TL19 aggregates. On the other hand, an internet of things (IoT)-embedded 3D printed portable device is constructed for the detection of Cu2+ ions in real water samples. The Cu2+ detection is achieved through an IoT device, and results were acknowledged through an android application in 3.32 s round-trip time. Thus, the IoT-enabled AIE probe could be a prospective device for Cu2+ detection in a constrained environment.

Fluorescence and quantum mechanical approach on the interaction of amides and their role on the stability and coexistence of the rotamer conformations of L-tryptophan in aqueous solution.

Photophysical investigation on the fluorescence decay characteristics of L-tryptophan and a derivative N-acetyl-L-tryptophanamide (NATA) with alkyl amides were carried out in water. L-tryptophan exists in the zwitterionic form and exhibits a biexponential lifetime which is correlated to the existence of rotamer structures. Addition of formamide (F) and dimethylformamide (DMF) results in a decrease in the fluorescence lifetime and its proportion of the most stable structure of L-tryptophan wherein acetamide (ACM) results in an increase of the same. Interestingly, all the amides result in the formation of the lifetime of the rotamer whose lifetime doesn't exist initially and the lifetime and its distribution increases irrespective of the nature of amide. The interaction between L-tryptophan and amide is attributed to hydrogen-bonding such that these interactions influence the relative proportion of the existence of individual rotamers in the presence of amides.Strikingly, in the case of NATA that does not exhibit rotamer structures; the fluorescence lifetime is quenched in the presence of F, whereas ACM and DMF result in a larger fold of enhancement resulting in two different lifetimes. The variation in the fluorescence lifetime and amplitude of the various conformers of L-tryptophan and of NATA is completely governed by the concentration of the amides in solution such that the microenvironment surrounding the fluorophores are completely reorganised. The hydrogen-bonding functional groups in amides that are responsible for the coexistence of rotamers are elucidated and well supported by quantum mechanical (QM) studies. Time-correlated single-photon counting(TCSPC) technique is used as a probe as well as marker in establishing the variation in the lifetime properties of L-tryptophan and NATA with non-fluorescent hydrogen-bonding solutes in water which promotes this as fascinating field of research in the context of fluorescence properties of a complicated amino acid-like tryptophan.

Photochemically Synthesized Ruthenium Nanoparticle-Decorated Carbon-Dot Nanochains: An Efficient Catalyst for Synergistic Redox Reactions.

Ruthenium nanoparticle (NP)-decorated carbon dots (Ru/C-dots) were fabricated as a potential catalyst in the application of both oxidation and reduction. The photochemical method was used to synthesize Ru/C-dot nanohybrids. The as-prepared Ru/C-dots exhibited a core-shell-based nanochain structure, in which the spherical nature of C-dots further evolved to a layer structure to homogeneously encapsulate Ru NPs. Such Ru/C-dots have excellent catalytic properties, which were demonstrated in the oxidation of flavonoids and concomitantly reduction of inorganic complex and organic dyes, each yielding a high catalytic rate constant. We also proposed an appropriate catalytic mechanism for each reaction. Higher catalytic activity was achieved by the synergistic effect of the encapsulated Ru NPs and the C-dots layer. Further, this nanohybrid was successfully applied to inspect a real aqueous sample. We anticipated that Ru/C-dots nanohybrid may open up a broad platform for the design of efficient multifunctional catalysts.

Ligusticum Striatum-Derived Carbon Dots as Nanocarriers to Deliver Methotrexate for Effective Therapy of Cancer Cells.

Ligusticum striatum herb-derived carbon dots (C-dots) were adopted as a drug carrier to deliver methotrexate (MTX). MTX is a folate antagonist drug for chemotherapy of cancer. The MTX was conjugated with C-dots to form the MTX/C-dot complex through non-covalent bonding. The efficiency of drug loading and release of MTX/C-dots was evaluated, showing a high drug loading (85.9%) capability of C-dots. The MTX/C-dots exhibited pH-dependent MTX release behavior in which high efficiency (∼69%) was obtained at pH 5.0 with respect to the value of ∼47% at pH 7.4. The cell viabilities of MTX/C-dots and bare C-dots were evaluated in HeLa and human normal fibroblasts (NHF) cells. The C-dots possess less toxicity, whereas MTX/C-dots showed high cytotoxicity compared to that of bare MTX in HeLa cells. The content of the folate receptor is higher (1.56 times) in HeLa cells than that of NHF cells such that a dense binding between the MTX and folate receptor reduces the cell viability. This finding confirms that the MTX/C-dots had a higher cellular uptake, signifying the excellent drug carrier property of C-dots. In addition, the fluorescence bioimaging measurements were examined in HeLa cells to demonstrate the drug delivery efficacy of MTX/C-dots by using confocal fluorescence microscopy. Accordingly, the MTX/C-dots demonstrate their potential in the bioimaging and drug delivery system resulting from fascinating features including photoluminescence, good biocompatibility, and proficient cellular uptake and drug release. It is believed that the MTX/C-dot nanocarrier might hold great potential for cancer chemotherapeutic applications.

Fluorescence coupled with electrochemical approach at the bulk and the interface region of hydrogen-bonding self assemblies of urea derivatives with DDP dye in aqueous solution.

Photophysical and electrochemical techniques were employed to hydrogen-bonding self assemblies forming solutes (Urea, Dimethylurea and Tetramethylurea) in the presence of 4-dicyanomethylene 2, 6-dimethyl-4H-pyran (DDP) dye. Addition of urea derivatives to DDP dye (Intramolecular Charge Transfer (ICT)) results in a fluorescence enhancement accompanied with a significant shift. Fluorescence lifetime behavior exhibits a tri-exponential decay with a large variation in the fluorescence lifetime and relative amplitude distribution. The coexistence of three different fluorescence lifetime components of DDP with urea derivatives signifies the existence of heterogeneous micro environment. The dye is surrounded by varying proportion of solute and water molecules are established from fluorescence lifetime studies. Urea derivatives govern the excited state characteristics of DDP dye resulting in the formation and promotion of different microenvironment which are clearly distinguishable. The existence of multi environment attributed to urea-water structural behaviour is authenticated by electrochemical impedance spectral studies (EIS). A large variation in the contour pattern, shape and intensity in 3D fluorescence contour spectra of dye with urea validate the existence of dye in a heterogeneous micro environment. The hydrophobicity of urea derivatives along with the hydrogen-bonding properties of urea-water and urea-urea influence the photophysical and electrochemical nature of dye is emphasized.

Recent Advances in Functionalized Carbon Dots toward the Design of Efficient Materials for Sensing and Catalysis Applications.

Since the past decade, enormous research efforts have been devoted to the detection/degradation and quantification of environmental toxic pollutants and biologically important molecules due to their ubiquitous necessity in the fields of environmental protection and human health. These fields of sensor and catalysis are advanced to a new era after emerging of nanomaterials, especially, carbon nanomaterials including graphene, carbon nanotube, carbon dots (C-dots), etc. Among them, the C-dots in the carbon family are rapidly boosted in the aspect of synthesis and application due to their superior properties of chemical and photostability, highly fluorescent with tunable, non/low-toxicity, and biocompatibility. The C-dot-based functional materials have shown great potential in sensor and catalysis fields for the detection/degradation of environmental pollutants. The major advantage of C-dots is that they can be easily prepared from numerous biomass/waste materials which are inexpensive and environment-friendly and are suitable for a developing trend of sustainable materials. This review is devoted to the recent development (since 2017) in the synthesis of biomass- and chemical-derived C-dots as well as diverse functionalization of C-dots. Their capability as a sensor and catalyst and respective mechanism are summarized. The future perspectives of C-dots are also discussed.

Pyrene-Based Chemosensor for Picric Acid-Fundamentals to Smartphone Device Design.

Developing a fluorescent probe for the selective and sensitive detection of explosives is a topic of continuous research interest. Additionally, underlying the principles behind the detection mechanism is indeed providing substantial information about the design of an efficient fluorescence probe. In this context, a pyrene-tethered 1-(pyridin-2-yl)imidazo[1,5-a]pyridine-based fluorescent probe (TL18) was developed and employed as a fluorescent chemosensor for nitro explosives. The molecular structure of TL18 was well-characterized by NMR and EI-MS spectrometric techniques. UV-visible absorption, steady-state, and time-resolved fluorescence spectroscopic techniques have been employed to explicate the photophysical properties of TL18. The fluorescent nature of the TL18 probe was explored for detection of nitro explosives. Intriguingly, the TL18 probe was selectively responsive to picric acid over other explosives. The quantitative analysis of the fluorescence titration studies of TL18 with picric acid proved that the probe achieved a detection limit of 63 nM. Further, DFT and QTAIM studies were used to establish the nature of the sensing mechanism of TL18. The hydrogen-bonding interactions are the reason for the imperative sensing property of TL18 for picric acid. Thus, our experimental and theoretical studies provide an adequate and appropriate prerequisite for an efficient fluorescent probe. Furthermore, a smartphone-interfaced portable fluorimeter module is developed to facilitate sensitive and real-time sensing of picric acid. This portable module was capable of detecting picric acid down to 99 nM. Eventually, these studies will have a significant impact on development and application of a new class of chemosensors for detection of explosives.

Catalytic Activity of Bimetallic (Ruthenium/Palladium) Nano-alloy Decorated Porous Carbons Toward Reduction of Toxic Compounds.

Chicken feather-derived high-surface-area porous activated carbon (CFAC) material was prepared using chemical activation. A new composite composed of Ru-Pd nanoparticles supported on CFAC (Ru-Pd@CFAC) has been prepared by microwave-thermal reduction in the presence of the support. Characterization by XRD, Raman, BET, FE-SEM/TEM, FT-IR, TGA, XPS, HAADF-STEM-EDS, H2 -chemisorption, H2 -TPR, and ICP-AES was used to analyze the catalyst. This catalyst is found to be efficient for the reduction of hexavalent chromium (CrVI ), potassium ferricyanide (K3 [Fe(CN)6 ]), 4-nitrophenol (4-NP), and pendimethalin (PDM), at room temperature, and remains stable, even after several repeated runs. Moreover, it showed excellent catalytic activity compared with the monometallic counterparts.

Pyrene-based prospective biomaterial: In vitro bioimaging, protein binding studies and detection of bilirubin and Fe3.

Herein, we have meticulously derived the nanosized fluorescent aggregates from pyrene Schiff base (PS) in DMSO:water (10:90) ratio. The aggregation property of PS molecule was characterized by SEM and TEM measurements, revealed the aggregated particles are in spherical shape with ~3 nm in size. Moreover, aggregates exhibit a high fluorescence quantum yield (48%) which was effectively used for the in vitro bioimaging of two different cancer cells such as A549 and MCF-7 cells in which it exhibiting excellent biocompatibility. Further, it was estimated the capability of twofold acridine orange/ethidium bromide (AO/EB) staining to identify the apoptotic associated changes in cancer cells. Additionally, the aggregates were successfully demonstrated as a luminescent probe for the perceptive biomolecule detection of bilirubin. On the other hand, the PS molecule was successfully utilized for protein binding and metal ion sensing studies. The interaction of bovine serum albumin (BSA) with PS molecule in DMSO was using fluorescence spectroscopic method and nature of interaction was also confirmed through molecular docking analysis. The PS molecule also acts as an excellent sensor for biologically important Fe3+ ion with detection limit of 336 nM. Overall, PS molecule can be a prospective material in biological field both in solution as well as aggregated forms.

Highly sensitive fluorogenic sensing of L-Cysteine in live cells using gelatin-stabilized gold nanoparticles decorated graphene nanosheets.

A highly sensitive and selective fluorogenic sensing of L-Cysteine (L-Cys) was implemented based on gelatin stabilized gold nanoparticles decorated reduced graphene oxide (rGO/Au) nanohybrid. The rGO/Au nanohybrid was prepared by the one-pot hydrothermal method and well characterized by different physiochemical techniques. The nanohybrid exhibits a weak fluorescence of rGO due to the energy transfer from the rGO to Au NPs. The rGO/Au nanohybrid shows enhanced fluorescence activity due to the restoration of quenched fluorescence of rGO/Au nanohybrid in presence of L-Cys. The rGO/Au nanohybrid exhibits much lower detection limit of 0.51 nM for L-Cys with higher selectivity. The fluorescence sensing mechanism arose from the fluorescence recovery due to the stronger interaction between Au NPs and L-Cys, and consequently, the energy transfer was prevented between rGO and Au NPs. The practicability of rGO/Au sensor was implemented by invitro bioimaging measurements in Colo-205 (colorectal adenocarcinoma) and MKN-45 (gastric carcinoma) cancer live cells with excellent biocompatibility.

Ultra-sensitive DNA sensing of a prostate-specific antigen based on 2D nanosheets in live cells.

Herein, we report ultra-sensitive sensing of a prostate-specific antigen (PSA), which is used as a biomarker to detect prostate cancer, using a molybdenum series (MoO3, MoS2, and MoSe2) of two-dimensional nanosheets (2D NSs). Moreover, the design of a 2D NS-based PSA aptamer sensor system was demonstrated based on a fluorescence turn-on mechanism in the presence of a target. The 2D NSs acted as an excellent sensing platform in which the PSA aptamer was adsorbed on the NSs and subsequent energy transfer between them led to fluorescence quenching of the aptamer. The detection limit of PSA was achieved to be 13 pM for MoO3 NSs, whereas the MoS2 and MoSe2 systems exhibited a detection limit of 72 and 157 pM, respectively. To the best of our knowledge, this is the first report on the ultra-sensitive detection of a 2D NS-based aptamer sensor. The in vitro bioimaging measurements were performed using confocal fluorescence microscopy. Herein, PSA detection was successfully demonstrated in human embryonic kidney 293T (HEK) live cells. Moreover, the MoO3, MoS2, and MoSe2 NSs exhibit excellent biocompatibility and low toxicity; thus, these 2D NSs can be used as a promising sensor platform to detect prostate cancer.

3D Probed Lipid Dynamics in Small Unilamellar Vesicles.

Single-molecule fluorescence correlation spectroscopy overcomes the resolution barrier of optical microscopy (10≈-20 nm) and is utilized to look into lipid dynamics in small unilamellar vesicles (SUVs; diameter < 100 nm). The fluorescence trajectories of lipid-like tracer 1,1'-dioctadecyl-3,3,3',3'-tetramethylindodicarbocyanine (DiD) in the membrane bilayers are acquired at a single-molecule level. The autocorrelation analysis yields the kinetic information on lipid organization, oxygen transport, and lateral diffusion in SUVs' membrane. First, the isomerization feasibility may be restricted by the addition of cholesterols, which form structure conjugation with DiD chromophore. Second, the oxygen transport is prevented from the ultrasmall cluster and cholesterol-rich regions, whereas it can pass through the membrane region with liquid-disordered phase (Ld ) and defects. Third, by analyzing 2D spectra correlating the lipid diffusion coefficient and triplet-state lifetime, the heterogeneity in lipid bilayer can be precisely visualized such as lipid domain with different phases, the defects of lipid packing, and DiD-induced "bouquet" ultrasmall clusters.

Silicon Quantum Dot-Based Fluorescence Turn-On Metal Ion Sensors in Live Cells.

Multiple sensor systems are designed by varying aza-crown ether moiety in silicon quantum dots (SiQDs) for detecting individual Mg(2+), Ca(2+), and Mn(2+) metal ions with significant selectivity and sensitivity. The detection limit of Mg(2+), Ca(2+), and Mn(2+) can reach 1.81, 3.15, and 0.47 µM, respectively. Upon excitation of the SiQDs which are coordinated with aza-crown ethers, the photoinduced electron transfer (PET) takes place from aza-crown ether moiety to the valence band of SiQDs core such that the reduced probability of electron-hole recombination may diminish the subsequent fluorescence. The fluorescence suppression caused by such PET effect will be relieved after selective metal ion is added. The charge-electron binding force between the metal ion and aza-crown ether hinders the PET and thereby restores the fluorescence of SiQDs. The design of sensor system is based on the fluorescence "turn-on" of SiQDs while in search of the appropriate metal ion. For practical application, the sensing capabilities of metal ions in the live cells are performed and the confocal image results reveal their promising applicability as an effective and nontoxic metal ion sensor.

Chemically induced fluorescence switching of carbon-dots and its multiple logic gate implementation.

Investigations were carried out on the carbon-dots (C-dots) based fluorescent off - on (Fe(3 + )- S2O3(2-)) and on - off (Zn(2 + )- PO4(3-)) sensors for the detection of metal ions and anions. The sensor system exhibits excellent selectivity and sensitivity towards the detection of biologically important Fe(3 + ), Zn(2 + ) metal ions and S2O3(2-), PO4(3-) anions. It was found that the functional group on the C-dots surface plays crucial role in metal ions and anions detection. Inspired by the sensing results, we demonstrate C-dots based molecular logic gates operation using metal ions and anions as the chemical input. Herein, YES, NOT, OR, XOR and IMPLICATION (IMP) logic gates were constructed based on the selection of metal ions and anions as inputs. This carbon-dots sensor can be utilized as various logic gates at the molecular level and it will show better applicability for the next generation of molecular logic gates. Their promising properties of C-dots may open up a new paradigm for establishing the chemical logic gates via fluorescent chemosensors.

Role of photoionization on the dynamics and mechanism of photoinduced electron transfer reaction of coumarin 307 in micelles.

The dynamics and mechanism of the photoinduced electron transfer (PET) reaction between coumarin 307 (C307) and aromatic amines in micelles have been studied by using steady-state (S-S) and time-resolved (T-R) absorption and fluorescence spectroscopy. Based on the fluorescence quenching time scale, PET in micelles is grouped into two types: (i) ultrafast electron transfer (ET) due to the close contact of the donor and acceptor in micelles and (ii) diffusion averaged dynamic electron transfer (DADET) which is controlled by the diffusion of the reactants in micellar Stern layer and diffusion of the micelles. The DADET does not affect the photoionization and solvation processes whereas ultrafast ET competes with the photoionization and faster than the solvation process. Both ultrafast and DADET shows Marcus inversion in the ET rates at the similar exergonicity and indicates that the role of diffusion and solvent reorganization is negligible toward the activation barrier for the ET reaction in micelles. The activation barrier for the ET reactions in micelles is mainly due to intramolecular reorganization energy. The intramolecular reorganization energy must be higher in CTAB due to the photoionization and subsequent recombination and also involvement of triplet state in the PET. The ET reaction between coumarin radical cation and amine is reported for the first time in the C307-amine systems in micelles which are confirmed by the effect on amine concentration of the decay of coumarin radical cation and the dynamics of the ground-state recovery of C307. A mechanism for the PET reaction between C307-amine systems is proposed in micelles including photoionization, ultrafast and dynamic ET, and solvation dynamics.

Photoionization and time-dependent stokes shift of coumarin 307 in soft matter: solvation and radical-ion pair recombination dynamics.

Photoionization, fluorescence time-dependent Stokes shift (TDSS), and rotational dynamics of coumarin 307 (C307) have been investigated in soft matter system such as micelles using time-resolved transient absorption and fluorescence spectroscopy. Photoionization of C307 leads to the formation of coumarin radical cation and hydrated electron, which were characterized by their respective transient absorption. The photoionization yields are significantly higher in anionic sodium dodecyl sulfate (SDS) micelle than in cationic cetyltrimethylammonium bromide (CTAB) and neutral Triton X-100 (TX-100) micelles, indicating the influence of micellar surface charge on the efficient separation of radical cation-hydrated electron pair. The CTAB micelle favors the recombination of radical cation and hydrated electron leading to the formation of triplet state of C307, which causes a decrease in the photoionization yield. C307 exhibits TDSS in all micelles; the time evolution and the magnitude of the TDSS depend on nature of the micelle. In TX-100 micelles, the decay of the TDSS exhibits ultraslow component (165 ns) and is affected by the presence of electron scavengers. The ultraslow component in TX-100 micelle originates from the recombination of radical cation-hydrated electron, which results in the formation of twisted intramolecular charge transfer (TICT) state; such formation of TICT state was not observed in SDS and CTAB micelles. To the best of our knowledge, this is the first report where the radical-ion pair recombination dynamics is probed using TDSS in combination with time-resolved transient absorption studies. The activation energy for the solvent relaxation and radical-ion pair (solvent separated) recombination process was found to be 6.1 and 3.0 kcal mol(-1), respectively. Temperature effect on TDSS in TX-100 micelles confirmed the increase in the water hydration, and size of the micelle influences the relative contribution of the solvation and radical-ion pair recombination dynamics toward the total TDSS. We propose that TDSS observed in neutral micelles and reported in other biomolecules such as proteins by the 7-amino coumarin probe is not only due to the solvation dynamics alone but also due to the radical-ion pair recombination dynamics.