Recent Advances in Tunable Metasurfaces and Their Application in Optics.

Metasurfaces can be opportunely and specifically designed to manipulate electromagnetic wavefronts. In recent years, a large variety of metasurface-based optical devices such as planar lenses, beam deflectors, polarization converters, and so on have been designed and fabricated. Of particular interest are tunable metasurfaces, which allow the modulation of the optical response of a metasurface; for instance, the variation in the focal length of a converging metalens. Response tunability can be achieved through external sources that modify the permittivity of the materials constituting the nanoatoms, the substrate, or both. The modulation sources can be classified into electromagnetic fields, thermal sources, mechanical stressors, and electrical bias. Beside this, we will consider optical modulation and multiple approach tuning strategies. A great variety of tunable materials have been used in metasurface engineering, such as transparent conductive oxides, ferroelectrics, phase change materials, liquid crystals, and semiconductors. The possibility of tuning the optical properties of these metamaterials is very important for several applications spanning from basic optics to applied optics for communications, depth sensing, holographic displays, and biochemical sensors. In this review, we summarize the recent progress on electro-optical magnetic, mechanical, and thermal tuning of metasurfaces actually fabricated and experimentally tested in recent years. At the end of the review, a short section on possible future perspectives and applications is included.

Exciplex Formation in Lipid-bound Escherichia coli Flavohemoglobin.

Flavohemoglobins have the particular capability of binding unsaturated and cyclopropanated fatty acids as free acids or phospholipids. Fatty acid binding to the ferric heme results in a weak but direct bonding interaction. Ferrous and ferric protein, in presence or absence of a bound lipid molecule, have been characterized by transient absorption spectroscopy. Measurements have been also carried out both on the ferrous deoxygenated and on the CO bound protein to investigate possible long-range interaction between the lipid acyl chain moiety and the ferrous heme. After excitation of the deoxygenated derivatives the relaxation process reveals a slow dynamics (350 ps) in lipid-bound protein but is not observed in the lipid-free protein. The latter feature and the presence of an extra contribution in the absorption spectrum, indicates that the interaction of iron heme with the acyl chain moiety occurs only in the excited electronic state and not in the ground electronic state. Data analysis highlights the formation of a charge-transfer complex in which the iron ion of the lipid-bound protein in the expanded electronic excited state, possibly represented by a high spin Fe III intermediate, is able to bind to the sixth coordination ligand placed at a distance of at 3.5 Šfrom the iron. A very small nanosecond geminate rebinding is observed for CO adduct in lipid-free but not in the lipid-bound protein. The presence of the lipid thus appears to inhibit the mobility of CO in the heme pocket.

Time- and Temperature-Dependent Luminescence of Manganese Ions in Ceramic Magnesium Aluminum Spinels.

Samples of magnesium aluminum spinel ceramics doped with manganese ions were prepared by a high-temperature solid-state reaction method; their potential as red-emitting phosphors was analyzed using a time-resolved luminescence spectroscopy technique, from room temperature to 10 K. It was found that in the red spectral range, the luminescence spectra of manganese ions in the MgAl2O4 spinel showed a narrow band peaking at 651 nm due to the emission of Mn4+ and a broader emission band in the region of 675 ÷ 720 nm; the ratio of intensities for these bands depends on the synthesis conditions. By applying a special multi-step annealing procedure, the MgAl2O4:Mn4+ phosphor containing only tetravalent manganese ions, Mn4+, was synthesized. Broad-band far-red emission observed from MgAl2O4:Mn and Mg1.25Al1.75O3.75F0.25:Mn phosphors, prepared by a conventional method of a solid-state reaction, was interpreted as coming from Mn3+ ions.

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules.

The comprehensive characterization of Intramolecular Charge Transfer (ICT) stemming in push-pull molecules with a delocalized π-system of electrons is noteworthy for a bespoke design of organic materials, spanning widespread applications from photovoltaics to nanomedicine imaging devices. Photo-induced ICT is characterized by structural reorganizations, which allows the molecule to adapt to the new electronic density distribution. Herein, we discuss recent photophysical advances combined with recent progresses in the computational chemistry of photoactive molecular ensembles. We focus the discussion on femtosecond Transient Absorption Spectroscopy (TAS) enabling us to follow the transition from a Locally Excited (LE) state to the ICT and to understand how the environment polarity influences radiative and non-radiative decay mechanisms. In many cases, the charge transfer transition is accompanied by structural rearrangements, such as the twisting or molecule planarization. The possibility of an accurate prediction of the charge-transfer occurring in complex molecules and molecular materials represents an enormous advantage in guiding new molecular and materials design. We briefly report on recent advances in ultrafast multidimensional spectroscopy, in particular, Two-Dimensional Electronic Spectroscopy (2DES), in unraveling the ICT nature of push-pull molecular systems. A theoretical description at the atomistic level of photo-induced molecular transitions can predict with reasonable accuracy the properties of photoactive molecules. In this framework, the review includes a discussion on the advances from simulation and modeling, which have provided, over the years, significant information on photoexcitation, emission, charge-transport, and decay pathways. Density Functional Theory (DFT) coupled with the Time-Dependent (TD) framework can describe electronic properties and dynamics for a limited system size. More recently, Machine Learning (ML) or deep learning approaches, as well as free-energy simulations containing excited state potentials, can speed up the calculations with transferable accuracy to more complex molecules with extended system size. A perspective on combining ultrafast spectroscopy with molecular simulations is foreseen for optimizing the design of photoactive compounds with tunable properties.

Dioxin and Related Compound Detection: Perspectives for Optical Monitoring.

Dioxins and related compounds are environmental xenobiotics that are dangerous to human life, due to the accumulation and persistence in the environment and in the food chain. Cancer, reproductive and developmental issues, and damage to the immune system and endocrine system are only a few examples of the impact of such substances in everyday life. For these reasons, it is fundamental to detect and monitor these molecules in biological samples. The consolidated technique for analytical evaluation is gas chromatography combined with high-resolution mass spectrometry. Nowadays, the development of mid-infrared optical components like broadband laser sources, optical frequency combs, high performance Fourier-transform infrared spectroscopy, and plasmonic sensors open the way to new techniques for detection and real time monitoring of these organic pollutants in gaseous or liquid phase, with sufficient sensitivity and selectivity, and in short time periods. In this review, we report the latest techniques for the detection of dioxins, furans and related compounds based on optical and spectroscopic methods, looking at future perspectives.

Inhaled loxapine for agitation in patients with personality disorder: an initial approach.

Inhaled Loxapine (IL) has demonstrated efficacy in the treatment of agitation in schizophrenic and bipolar patients, although data in patients with Personality Disorder (PD) are scarce. To evaluate the effectiveness and safety of IL in the treatment of agitation in PD, data from 41 patients who presented at our unit with acute agitation and were treated with 9.1 mg of IL were collected retrospectively. The results showed that IL significantly decreased agitation within 10 minutes and its effect was greater at 20 minutes (Positive and Negative Syndrome Scale-excited component: from 22.78 ±â€¯4.39 at baseline to 11.14 ±â€¯4.17 at 20 minutes; p < 0.001; Agitation and Calmness Evaluation Scale: from 1.80 ±â€¯0.49 at baseline to 4.53 ±â€¯1.05 at 20 minutes; p < 0.01) without any severe adverse reactions registered. IL led to fast, safe and well-tolerated control of agitation in patients with PD.

TCDD Toxicity Mediated by Epigenetic Mechanisms.

Dioxins are highly toxic and persistent halogenated organic pollutants belonging to two families i.e., Polychlorinated Dibenzo-p-Dioxins (PCDDs) and Polychlorinated Dibenzo Furans (PCDFs). They can cause cancer, reproductive and developmental issues, damage to the immune system, and can deeply interfere with the endocrine system. Dioxins toxicity is mediated by the Aryl-hydrocarbon Receptor (AhR) which mediates the cellular metabolic adaptation to these planar aromatic xenobiotics through the classical transcriptional regulation pathway, including AhR binding of ligand in the cytosol, translocation of the receptor to the nucleus, dimerization with the AhR nuclear translocator, and the binding of this heterodimeric transcription factor to dioxin-responsive elements which regulate the expression of genes involved in xenobiotic metabolism. 2,3,7,8-TCDD is the most toxic among dioxins showing the highest affinity toward the AhR receptor. Beside this classical and well-studied pathway, a number of papers are dealing with the role of epigenetic mechanisms in the response to environmental xenobiotics. In this review, we report on the potential role of epigenetic mechanisms in dioxins-induced cellular response by inspecting recent literature and focusing our attention on epigenetic mechanisms induced by the most toxic 2,3,7,8-TCDD.

Cold-Adaptation Signatures in the Ligand Rebinding Kinetics to the Truncated Hemoglobin of the Antarctic Bacterium Pseudoalteromonas haloplanktis TAC125.

Cold-adapted organisms have evolved proteins endowed with higher flexibility and lower stability in comparison to their thermophilic homologues, resulting in enhanced reaction rates at low temperatures. In this context, protein-bound water molecules were suggested to play a major role, and their weaker interactions at protein active sites have been associated with cold adaptation. In this work, we tested this hypothesis on truncated hemoglobins (a family of microbial heme-proteins of yet-unclear function) applying molecular dynamics simulations and ligand-rebinding kinetics on a protein from the Antarctic bacterium Pseudoalteromonas haloplanktis TAC125 in comparison with its thermophilic Thermobifida fusca homologue. The CO rebinding kinetics of the former highlight several geminate phases, with an unusually long-lived geminate intermediate. An articulated tunnel with at least two distinct docking sites was identified by analysis of molecular dynamics simulations and was suggested to be at the origin of the unusual geminate rebinding phase. Water molecules are present in the distal pocket, but their stabilization by TrpG8, TyrB10, and HisCD1 is much weaker than in thermophilic Thermobifida fusca truncated hemoglobin, resulting in a faster geminate rebinding. Our results support the hypothesis that weaker water-molecule interactions at the reaction site are associated with cold adaptation.

A Comprehensive Characterization of a 10 at.% Yb:YSAG Laser Ceramic Sample.

We report a comprehensive characterization of a 10 at.% Yb3+-doped YSAG (Yb:Y3ScxAl(5-x)O12, x = 1.5) ceramic, including microstructural, spectroscopic and laser properties. Moreover, we illustrate and discuss the fabrication technique. Yb3+ in YSAG features a broader absorption and emission band than in traditional YAG, which is advantageous for laser applications (i.e., tunable laser sources, ultrafast pulse generation). Pumping in a quasi continuous wave regime at 936 nm, the ceramic has shown good laser performance as the maximum output power was 6.3 W with a corresponding slope efficiency (ηs) of 67.8%. In continuous wave regime instead, the maximum output power was 5 W with ηs = 52.7%. The laser emission wavelengths in free running were λL = 1051 nm and λL = 1031 nm, depending on the output coupler transmission. Finally, by a tunable cavity we obtained laser emission spanning from 991.5 to 1073 nm, i.e., 81.5 nm, which is the broadest tuning range ever reported for this material, to the best of our knowledge.

Photophysical properties and excited state dynamics of 4,7-dithien-2-yl-2,1,3-benzothiadiazole.

The relationships between the photophysics and structural properties of 4,7-dithien-2-yl-2,1,3-benzothiadiazole as a function of solvent polarity are investigated both experimentally and by computational methods. Stationary fluorescence measurements are consistent with a model envisaging the presence of three types of conformers in equilibrium in the ground state. They are characterized by different relative orientations of the thiophene rings. Due to a low rotational barrier, the sample in solution is characterized by a distribution of relative internal orientations. By applying the Kawski method, we evaluate the average dipole moment of ground and excited states of the three types of conformers. The ground state dipole moments are small and similar for the three types of conformers. On the contrary, dipole moments differ substantially in the excited state. X-ray diffraction of a single crystal confirms the presence of an orientational disorder of thiophene rings. Transient absorption UV-visible spectroscopy experiments allows the identification of the main mechanisms responsible for the large Stokes shift observed in this push-pull molecule. Time dependent spectra provide a picture of the relaxation processes occurring after excitation: the primary step is an internal charge transfer assisted by thiophene ring planarization which occurs on a time scale ranging from 0.88 to 1.3 picoseconds depending on solvent polarity. Moreover, time-resolved fluorescence measurements are consistent with a mechanism involving planarization accompanied by a stabilization of the charge transfer state as observed in polar solvents. In the latter, longer fluorescence lifetimes are observed along with a quantum yield decrease due to the activation of specific non-radiative relaxation channels. The photophysical behavior of 4,7-dithien-2-yl-2,1,3-benzothiadiazole in a solid matrix of polymethyl methacrylate is similar to that observed in solution, but the overall non-radiative process rate is slow with respect to that in the liquid phase. As a consequence, the radiative processes are enhanced giving rise to a fluorescence quantum yield of 90%. Such behavior is consistent with the proposed relaxation model.

Use of nalmefene in patients with comorbid borderline personality disorder and alcohol use disorder: a preliminary report.

Comorbidity between borderline personality disorder (BPD) and alcohol use disorder (AUD) is high and relevant as alcohol consumption seems to worsen BPD symptomatology. One of the newest treatments for AUD, nalmefene, may be useful to improve BPD symptoms not only indirectly by reducing alcohol consumption but also directly by acting on the opioid system as this system has been related to specific BPD symptoms. This open-label study aimed at evaluating the efficacy of an 8-week nalmefene treatment in reducing alcohol consumption in individuals with BPD and comorbid AUD. A secondary objective was to assess its efficacy in improving general BPD symptomatology and specific behaviors (self injury and binge eating). Eighteen out of the 25 patients with BPD and comorbid AUD enrolled in the study completed all the assessment points. After 8 weeks, a significant reduction was observed in alcohol consumption, BPD global symptomatology, self-injurious behavior, and binge eating. No serious adverse effects were reported; however, five participants experienced mild side effects, resulting in withdrawal from the study in two cases. According to our results, nalmefene may be a safe and effective drug for treating patients with BPD and comorbid AUD. Controlled clinical trials are needed to support our findings.

Enhanced energy transport in genetically engineered excitonic networks.

One of the challenges for achieving efficient exciton transport in solar energy conversion systems is precise structural control of the light-harvesting building blocks. Here, we create a tunable material consisting of a connected chromophore network on an ordered biological virus template. Using genetic engineering, we establish a link between the inter-chromophoric distances and emerging transport properties. The combination of spectroscopy measurements and dynamic modelling enables us to elucidate quantum coherent and classical incoherent energy transport at room temperature. Through genetic modifications, we obtain a significant enhancement of exciton diffusion length of about 68% in an intermediate quantum-classical regime.

Subdiffraction localization of a nanostructured photosensitizer in bacterial cells.

Antibacterial treatments based on photosensitized production of reactive oxygen species is a promising approach to address local microbial infections. Given the small size of bacterial cells, identification of the sites of binding of the photosensitizing molecules is a difficult issue to address with conventional microscopy. We show that the excited state properties of the naturally occurring photosensitizer hypericin can be exploited to perform STED microscopy on bacteria incubated with the complex between hypericin and apomyoglobin, a self-assembled nanostructure that confers very good bioavailability to the photosensitizer. Hypericin fluorescence is mostly localized at the bacterial wall, and accumulates at the polar regions of the cell and at sites of cell wall growth. While these features are shared by Gram-negative and Gram-positive bacteria, only the latter are effectively photoinactivated by light exposure.

Role of local structure and dynamics of small ligand migration in proteins: a study of a mutated truncated hemoprotein from Thermobifida fusca by time resolved MIR spectroscopy.

Carbon monoxide recombination dynamics in a mutant of the truncated hemoglobin from Thermobida fusca (3F-Tf-trHb) has been analyzed by means of ultrafast Visible-pump/MidIR-probe spectroscopy and compared with that of the wild-type protein. In 3F-Tf-trHb, three topologically relevant amino acids, responsible for the ligand stabilization through the formation of a H-bond network (TyrB10 TyrCD1 and TrpG8), have been replaced by Phe residues. X-ray diffraction data show that Phe residues in positions B10 and G8 maintain the same rotameric arrangements as Tyr and Trp in the wild-type protein, while Phe in position CD1 displays significant rotameric heterogeneity. Photodissociation of the ligand has been induced by exciting the sample with 550 nm pump pulses and the CO rebinding has been monitored in two mid-IR regions respectively corresponding to the ν(CO) stretching vibration of the iron-bound CO (1880-1980 cm(-1)) and of the dissociated free CO (2050-2200 cm(-1)). In both the mutant and wild-type protein, a significant amount of geminate CO rebinding is observed on a subnanosecond time scale. Despite the absence of the distal pocket hydrogen-bonding network, the kinetics of geminate rebinding in 3F-Tf-trHb is very similar to the wild-type, showing how the reactivity of dissociated CO toward the heme is primarily regulated by the effective volume and flexibility of the distal pocket and by caging effects exerted on the free CO on the analyzed time scale.

Characteristic vibrational frequencies of toxic polychlorinated dibenzo-dioxins and -furans.

The possibility to monitor in real-time the emission of dioxins produced by incineration of waste or by industrial processes is nowadays a necessity considering the high toxicity of these compounds, their persistence in the environment and their ability to bio-accumulate in the food chain. Recently it has been demonstrated the potentiality of detecting dioxins in carbon tetrachloride via MIR Quantum Cascade Lasers. A fundamental step in real time monitoring of dioxins emission is the possibility to recognize the most toxic congeners within complex mixtures and at low concentrations. Taking into account the lack of spectroscopic data about these very toxic environmental pollutants and the necessity to monitor their emissions we have recorded infrared spectra of 13 of the 17 most toxic congeners of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-furans (PCDFs) dissolved in carbon tetrachloride. In this way we have obtained a small database that we have used to test the ability of a linear regression algorithm to recognize each congener and its relative concentration in complex mixtures of these compounds.

Asenapine in the treatment of borderline personality disorder: an atypical antipsychotic alternative.

Many individuals with borderline personality disorder (BPD) receive medical treatment in clinical practice, although to date, there are no drugs specifically available for BPD. The recent Cochrane guideline suggests a benefit from using second-generation antipsychotics such as olanzapine or aripiprazole; nevertheless, side effects limit their use. Asenapine is a novel FDA-approved atypical antipsychotic for schizophrenia and bipolar disorder. However, it has not yet been tested for BPD. The goal of this observational open-label study was to assess the safety, tolerability and efficacy of asenapine in a series of cases of patients with BPD. Twelve individuals with BPD were recruited and treated with asenapine during an 8-week period. Eight individuals completed the study; a significant improvement was observed in the CGI-BPD (P<0.001) and BSL-23 (P<0.048) scales for BPD symptomatology. Besides, there was a significant improvement in the general psychopathology domains (BPRS, P<0.004), whereas no significant differences were observed in depressive symptoms. No serious adverse effects were reported and a significant weight reduction was observed (P=0.002). Asenapine appears to be a safe and effective agent in the treatment of patients with BPD, especially when other alternatives are not tolerated. These preliminary findings should be replicated in a controlled clinical trial.

Carbon monoxide recombination dynamics in truncated hemoglobins studied with visible-pump midIR-probe spectroscopy.

Carbon monoxide recombination dynamics upon photodissociation with visible light has been characterized by means of ultrafast visible-pump/MidIR probe spectroscopy for the truncated hemoglobins from Thermobifida fusca and Bacillus subtilis. Photodissociation has been induced by exciting the sample at two different wavelengths: 400 nm, corresponding to the heme absorption in the B-band, and 550 nm, in the Q-bands. The bleached iron-CO coordination band located at 1850-1950 cm(-1) and the free CO absorption band in the region 2050-2200 cm(-1) have been observed by probe pulses tuned in the appropriate infrared region. The kinetic traces measured at 1850-1950 cm(-1) reveal multiexponential subnanosecond dynamics that have been interpreted as arising from fast geminate recombination of the photolyzed CO. A compared analysis of the crystal structure of the two proteins reveals a similar structure of their distal heme pocket, which contains conserved polar and aromatic amino acid residues closely interacting with the iron ligand. Although fast geminate recombination is observed in both proteins, several kinetic differences can be evidenced, which can be interpreted in terms of a different structural flexibility of the corresponding heme distal pockets. The analysis of the free CO band-shape and of its dynamic evolution brings out novel features about the nature of the docking site inside the protein cavity.

Mania and depression. Mixed, not stirred.

OBJECTIVE: Current criteria for mixed bipolar episode do not allow an adequate understanding of a vast majority of bipolar patients with mixed (hypo) manic-depressive features, keeping the qualification of "mixed episodes" for bipolar type I only. This study was aimed to test the existence of a bipolar-mixed continuum by comparing the characteristics of three groups classified according to patterns of past and current manic or mixed episodes. METHOD: 134 bipolar I inpatients were divided according to their pattern of excitatory "mixed-like" episodes in three groups: 1) lifetime history of purely manic episodes without mixed features (PMA); 2) lifetime history of both manic and mixed episodes (MIX) and 3) lifetime history exclusively of mixed, but not manic, episodes (PMIX). Differences in clinical and demographic characteristics were analyzed by using chi-square head-to-head for categorical data, one-way ANOVA for continuous variables and Tukey's post-hoc comparison. Logistic regression was used to control for data validity. RESULTS: PMIX had higher rates of depressive predominant polarity and less lifetime history of psychotic symptoms, and had received more antidepressants both lifetime and during 6 months prior to index episode. PMIX had more suicide attempts and Axis I comorbidity than PMA. DISCUSSION: PMIX is likely to have a higher risk for suicide and higher rates of comorbidities; current DSM-IV-TR criteria are not fit for correctly classifying these patients and this may affect treatment appropriateness. The concept of "mixicity" should be extended beyond bipolar I disorder to other bipolar disorder subtypes.

Treatment choice and psychometric characteristics: differences between patients who choose bariatric surgical treatment and those who do not.

BACKGROUND: Among the treatment options offered to patients with severe obesity are surgery and psychotherapy plus dieting. The treatment choice may reflect differences in the psychology of these patients. The objective was to assess the psychopathological differences between patients with obesity who choose surgery and those who choose non-surgical treatment to lose weight. METHODS: 100 patients with obesity (50 in the non-surgical group [NS]; and 50 in the surgical group [S]; 41 women and 9 men in each group) completed the MMPI-2 and the EDI-2; for the latter, data from 21 S and 24 NS women were available. Comparisons were carried out through analysis of variance. RESULTS: The NS group scored higher on the Pa (paranoia) and Pt (psychasthenia) scales of the MMPI-2 compared to the S group. No differences were found on the EDI-2; however, both groups scored higher on the drive-for-thinness and body-dissatisfaction scales, and the NS group scored higher on the bulimia and ineffectiveness scales. CONCLUSION: The MMPI-2 was able to distinguish between the NS and S groups, while the EDI-2 found significant eating-related psychopathology in both.