Photochemical & Photobiological Sciences最新文献

The modeling of the bioluminescent system of fireflies is key to understand the binding mode of the oxyluciferin/luciferase complex and its photophysical properties with the aim of developing high-efficiency devices and techniques. In this work, we present the OLUFF force field, which is able to describe the interactions to sample the conformational space of the four possible oxyluciferin emitters in both ground and excited state. This force field has been parameterized to reproduce quantum mechanical (QM) energies and geometrical parameters. Moreover, it has been validated by comparing probability distribution functions, minimized structures, infrared spectra and normal mode analysis obtained from OLUFF-based molecular dynamic (MD) simulations with their QM counterparts. Additionally, ground state simulations have also been performed using the general amber force field (GAFF) and compared with the OLUFF. It has been demonstrated that the OLUFF not only reproduces well the QM properties, but also improves the results from the GAFF.

Basic concepts and theoretical foundations of broken symmetry (BS) and post BS methods for strongly correlated electron systems (SCES) such as electron-transfer (ET) diradical, multi-center polyradicals with spin frustration are described systematically to elucidate structures, bonding and reactivity of the high-valent transition metal oxo bonds in metalloenzymes: photosystem II (PSII) and cytochrome c oxidase (CcO). BS hybrid DFT (HDFT) and DLPNO coupled-cluster (CC) SD(T₀) computations are performed to elucidate electronic and spin states of CaMn₄O_x cluster in the key step for oxygen evolution, namely S₄ [S₃ with Mn(IV) = O + Tyr161-O radical] state of PSII and P_M [Fe(IV) = O + HO-Cu(II) + Tyr161-O radical] step for oxygen reduction in CcO. The cycle of water oxidation catalyzed by the CaMn₄O_x cluster in PSII and the cycle of oxygen reduction catalyzed by the Cu_A-Fe_a-Fe_a3-Cu_B cluster in CcO are examined on the theoretical grounds, elucidating similar concerted and/or stepwise proton transfer coupled electron transfer (PT-ET) processes for the four-electron oxidation in PSII and four-electron reduction in CcO. Interplay between theory and experiments have revealed that three electrons in the metal sites and one electron in tyrosine radical site are characteristic for PT-ET in these biological redox reaction systems, indicating no necessity of harmful Mn(V) = O and Fe(V) = O bonds with strong oxyl-radical character. Implications of the computational results are discussed in relation to design of artificial systems consisted of earth abundant transition metals for water oxidation.

In response to the existing issues of cumbersome and time-consuming detection processes and limited application scope in current pesticide residue detection, this paper designed a novel flexible substrate for surface-enhanced Raman spectroscopy (SERS) by combining flower-like silver nanoparticles prepared by chemical reduction technology with a flexible sponge. The flexible substrate exhibits excellent SERS enhancement effects, with a minimum detection limit of 10^-12 mol/L for the probe molecule rhodamine 6G (R6G) and an average enhancement factor of 6.63 × 10⁵. For the commonly used pesticide thiram, the minimum detection limit is 0.1 mg/L, which is significantly lower than the maximum residue limits set by China and the USA for thiram. Further experiments confirmed the substrate's excellent uniformity and stability, and the use of finite difference time domain (FDTD) software revealed that the model combining flower-like silver nanoparticles with a sponge exhibited higher electromagnetic field intensity compared to the model without the sponge, resulting in abundant "hot spots". Additionally, the sparrow search algorithm (SSA) was used to optimize the backpropagation (BP) neural network for predicting the concentration of thiram pesticide. The experimental results indicated that the SSA-BP algorithm achieved a determination coefficient (R²) of 0.99974 and root mean square error (RMSE) of 300.321, demonstrating good network performance and meeting the requirements of actual detection needs.

The study aimed to assess the impact of combining potassium iodide (KI) with methylene blue (MB) in antimicrobial photodynamic therapy (aPDT) within an oral biofilm formed in situ. A single-phase, 14 days in situ study involved 21 volunteers, who wore a palatal appliance with 8 bovine dentin slabs. These slabs were exposed to a 20% sucrose solution 8 times a day, simulating a high cariogenic challenge. Following the intraoral phase, the biofilms formed on the slabs were randomly assigned to the treatments: C (0.9% NaCl); CHX (0.2% chlorhexidine); KI (75 mM KI); MBKI (0.005% MB + 75 mM KI); L (0.9% NaCl + red laser 660 nm, 18 J, 180 s); LMB (0.005% MB + laser); LKI (75 mM KI + laser); LMBKI (0.005% MB + 75 mM KI + laser). The treated biofilms were collected, diluted, and incubated to assess cell viability (CFU/mL) for total microorganisms, total lactobacilli, total streptococci, and mutans streptococci. Data were subjected to analysis using the Friedman test, followed by the Dunn test (α = 0.05). LMBKI group exhibited a noteworthy decrease in the viability of all microorganisms in comparison to groups C, KI, MBKI, MB, L, LMB, and LKI (p < 0.0001), and demonstrated a comparable reduction to the CHX group (p > 0.99). The combination of KI with MB in aPDT may be advocated as a non-invasive technique for diminishing the viability of polymicrobial oral biofilms, thereby aiding in the management of dental diseases.

Increasing solar ultraviolet radiation (UVR) can raise human exposure to UVR and adversely affect the environment. Precise measurements of ground-level solar UVR and long-term data series are crucial for evaluating time trends in UVR. This study focuses on spectrally resolved data from a UVR measuring station in Dortmund, Germany (51.5° N, 7.5° E, 130 m a.s.l.). After a strict quality assessment, UV data, such as the daily maximum UV Index (UVI_max) and daily erythemal radiant exposure (H_er,day) values, were analyzed concerning monthly and annual distribution, frequency, occurrence of highest values and their influencing factors. An advanced linear trend model with a flexible covariance matrix was utilized and applied to monthly mean values. Missing values were estimated by a validated imputation method. Findings were compared to those from a station in Uccle, Belgium (50.8° N, 4.3° E, 100 m a.s.l.). Parameters possibly influencing trends in both UVR and global radiation, such as ozone and sunshine duration, were additionally evaluated. The 1997-2022 trend results show a statistically significant increase in monthly mean of H_er,day (4.9% p. decade) and UVI_max (3.2% p. decade) in Dortmund and H_er,day (7.5% p. decade) and UVI_max (5.8% p. decade) in Uccle. Total column ozone shows a slight decrease in the summer months. Global radiation increases similarly to the UV data, and sunshine duration in Dortmund increases about twice as much as global radiation, suggesting a strong influence of change in cloud cover. To address health-related consequences effectively, future adaptation and prevention strategies to climate change must consider the observed trends.

This experiment investigated the effects of an ecologically relevant level of dim light at night (dLAN) on behavior, physiology and fat metabolism associated gene expressions in central and peripheral tissues of adult male zebra finches that were hatched and raised in 12:12 h LD cycle (Ev, day = 150 ± 5 lx; Ev, night = 0 lx) at 22 ± 2 °C temperature. Half of the birds (n = 8) were maintained on LD cycle and temperature, as before (control), to the other half of birds the 12 h dark period was dimly illuminated at ~ 5 lx (dim light at night, dLAN; Ev, day = 150 ± 5 lx; Ev, night =  ~ 5 lx) for 6 weeks. The exposure to dLAN altered the 24 h activity and feeding patterns with enhanced activity and feeding at night. Birds under dLAN fattened and gained weight, and had higher night glucose levels. Concurrently, a negative effect of dLAN was found on mRNA expression of ppar-alpha and cd36 genes involved in the fat metabolism in the hypothalamus, intestine, liver and muscle. These results suggest a more global effect of dLAN exposure on obesity and perhaps long-term health risks due to obesity-related complications to diurnal animals including humans inhabiting an urbanized environment.

Control of biological activity with light is a fascinating idea. "Caged" compounds, molecules modified with photolabile protecting group, are one of the instruments for this purpose. Adrenergic receptors are essential regulators of neuronal, endocrine, cardiovascular, vegetative, and metabolic functions. These receptors are largely used as pharmacologic targets. Photolabile "caged" analogs of adrenergic receptor agonists has been reported more than 30 years ago. We report that the photolysis of epinephrine analogs, apart from liberation of the epinephrine, is accompanied by a formation of significant amount of adrenochrome, a compound with neuro- and cardiotoxic effect.

Phthalides represent a notable category of secondary metabolites that are prevalent in various plant species, certain fungi, and liverworts. The significant pharmacological properties of these compounds have led to the synthesis of a novel phthalide derivative. The current study focuses on investigating the binding interactions of a newly synthesized 3-substituted phthalide derivative, specifically 3-((4-chloro-6-methyl pyrimidine-2-yl)amino) isobenzofuran-1(3H)-one (Z11), with double-stranded deoxyribonucleic acid (dsDNA). Research in the pharmaceutical and biological fields aimed at developing more potent DNA-binding agents must take into account the mechanisms by which these newly synthesized compounds interact with DNA. This investigation seeks to explore the binding dynamics between dsDNA and our compound through a variety of analytical techniques, such as electrochemistry, UV spectroscopy, fluorescence spectroscopy, and thermal denaturation. The binding constant (K_b) of Z11 with DNA was determined using both spectroscopic and voltammetric approaches. The research revealed that Z11 employs a groove binding mechanism to associate with dsDNA. To further explore the interactions between Z11 and dsDNA, the study utilized density functional theory (DFT) calculations, molecular docking, and molecular dynamics simulations. These analyses aimed to ascertain the potential for a stable complex formation between Z11 and dsDNA. The results indicate that Z11 is situated within the minor groove of the dsDNA, demonstrating the ability to establish a stable complex. Furthermore, the findings imply that both π-alkyl interactions and hydrogen bonding play significant roles in the stabilization of this complex.

Diurnal preference to eveningness might predispose to depression. There is preliminary evidence of infrared-A (IR-A) induced whole-body hyperthermia (WBH) in the treatment of depression. In this exploratory study with 19 adults, we investigated the effects of a 20-min exposure of water-filtered IR-A (wIRA) to the skin of back and buttock area, without inducing WBH, on mood and assessed the outcome by diurnal preference (#R19047, approval on 7 May 2019). The skin received irradiation with an integrated power of 102.4 W in the wavelength region of 550-1350 nm and a total dose of 123 kJ over the total area of 0.0483 m². The diurnal preference was assessed with a 6-item version of the Morningness-Eveningness Questionnaire (mMEQ). The 40-item Profile of Mood States (POMS) questionnaire was used to assess total mood disturbance (TMD). Core temperature was measured 30 min before, during and 30 min after the irradiation. Skin surface temperature was measured on baseline and every two minutes during the irradiation. The TMD improved immediately after the exposure, and this positive effect lasted for 24 h (p = 0.001) as well as for 2 weeks (p = 0.02). Concerning the diurnal preference, the positive effect on mood was immediate and lasted for 24 h in evening types (p = 0.02) and for 2 weeks in morning types (p = 0.04). During the exposure, core body temperature was constantly lower in morning types compared to evening types. This study gives us new information on the effects of near-infrared radiation, without inducing WBH, through the skin on mood.

Herein, we establish the release of aliphatic acids in water upon excitation of 7-diethylaminothio-4-coumarinyl derivatives encapsulated within the organic host octa acid (OA). The 7-diethylaminothio-4-coumarinyl skeleton, employed here as the trigger, photoreleases caged molecules from the excited triplet state, in contrast to its carbonyl analogue, where the same reaction is known to occur from the excited singlet state. Encapsulation in OA solubilizes molecules in water that are otherwise water-insoluble, and retains the used trigger within itself following the release of the aliphatic acid. Such supramolecular characteristics usher in new features to the photorelease methodology. The thiocarbonyl chromophore extends the absorption of coumarinyl trigger to visible range while enhancing the intersystem crossing (ISC) to the triplet state, making it the reactive state. Despite the non-polar environment within the OA capsules the photocleavage occurs in a heterolytic fashion to release the conjugate base and the used trigger as triplet carbocation in an adiabatic process. Interestingly, the triplet carbocation crosses to the ground singlet surface (closed shell singlet carbocation) with the help of water molecules, possibly aided by C = S chromophore. Utilizing the known excited state dynamics of related thiocoumarinyl and coumarinyl systems, we have identified a few of the important mechanistic features of the photorelease process of 7-diethylaminothio-4-coumarinyl derivatives. Ultrafast excited state dynamic studies and quantum chemical calculations planned should help us better understand the photorelease process so as to effectively exploit the proposed system for potential applications.