Structural Determination of Lysine-Linked Cisplatin Complexes via IRMPD Action Spectroscopy: NNs and NO- Binding Modes of Lysine to Platinum Coexist.

Despite its success as an anticancer drug, cisplatin suffers from resistance and produces side effects. To overcome these limitations, amino-acid-linked cisplatin analogues have been investigated. Lysine-linked cisplatin, Lysplatin, (Lys)PtCl2, exhibited outstanding reactivity toward DNA and RNA that differs from that of cisplatin. To gain insight into its differing reactivity, the structure of Lysplatin is examined here using infrared multiple photon dissociation (IRMPD) action spectroscopy. To probe the influence of the local chemical environment on structure, the deprotonated and sodium-cationized Lysplatin complexes are examined. Electronic structure calculations are performed to explore possible modes of binding of Lys to Pt, their relative stabilities, and to predict their infrared spectra. Comparisons of the measured IRMPD and predicted IR spectra elucidate the structures contributing to the experimental spectra. Coexistence of two modes of binding of Lys to Pt is found where Lys binds via the backbone and side-chain amino nitrogen atoms, NNs, or to the backbone amino and carboxylate oxygen atoms, NO-. Glycine-linked cisplatin and arginine-linked cisplatin complexes have previously been found to bind only via the NO- binding mode. Present results suggest that the NNs binding conformers may be key to the outstanding reactivity of Lysplatin toward DNA and RNA.

5-Halogenation of Uridine Suppresses Protonation-Induced Tautomerization and Enhances Glycosidic Bond Stability of Protonated Uridine: Investigations via IRMPD Action Spectroscopy, ER-CID Experiments, and Theoretical Calculations.

Uridine (Urd), a canonical nucleoside of RNA, is the most commonly modified nucleoside among those that occur naturally. Uridine has also been an important target for the development of modified nucleoside analogues for pharmaceutical applications. In this work, the effects of 5-halogenation of uracil on the structures and glycosidic bond stabilities of protonated uridine nucleoside analogues are examined using tandem mass spectrometry and computational methods. Infrared multiple photon dissociation (IRMPD) action spectroscopy experiments and theoretical calculations are performed to probe the structural influences of these modifications. Energy-resolved collision-induced dissociation experiments along with survival yield analyses are performed to probe glycosidic bond stability. The measured IRMPD spectra are compared to linear IR spectra predicted for the stable low-energy conformations of these species computed at the B3LYP/6-311+G(d,p) level of theory to determine the conformations experimentally populated. Spectral signatures in the IR fingerprint and hydrogen-stretching regions allow the 2,4-dihydroxy protonated tautomers (T) and O4- and O2-protonated conformers to be readily differentiated. Comparisons between the measured and predicted spectra indicate that parallel to findings for uridine, both T and O4-protonated conformers of the 5-halouridine nucleoside analogues are populated, whereas O2-protonated conformers are not. Variations in yields of the spectral signatures characteristic of the T and O4-protonated conformers indicate that the extent of protonation-induced tautomerization is suppressed as the size of the halogen substituent increases. Trends in the energy-dependence of the survival yield curves find that 5-halogenation strengthens the glycosidic bond and that the enhancement in stability increases with the size of the halogen substituent.

Nocturnal lighting in animal research should be replicable and reflect relevant ecological conditions.

In nature, light is a key driver of animal behaviour and physiology. When studying captive or laboratory animals, researchers usually expose animals to a period of darkness, to mimic night. However, 'darkness' is often poorly quantified and its importance is generally underappreciated in animal research. Even small differences in nocturnal light conditions can influence biology. When light levels during the dark phase are not reported accurately, experiments can be impossible to replicate and compare. Furthermore, when nocturnal light levels are unrealistically dark or bright, the research is less ecologically relevant. Such issues are exacerbated by huge differences in the sensitivity of different light meters, which are not always described in study methods. We argue that nocturnal light levels need to be reported clearly and precisely, particularly in studies of animals housed indoors (e.g. '<0.03 lux' rather than '0 lux' or 'dark'), and that these light levels should reflect conditions that the animal would experience in a natural context.

Towards Insect-Friendly Road Lighting-A Transdisciplinary Multi-Stakeholder Approach Involving Citizen Scientists.

(1) The project "Tatort Streetlight" implements an insect-friendly road light design in a four year before-after, control-impact (BACI) approach involving citizen scientists. It will broaden the stakeholder interests from solely anthropogenic perspectives to include the welfare of insects and ecosystems. Motivated by the detrimental impacts of road lighting systems on insects, the project aims to find solutions to reduce the insect attraction and habitat fragmentation resulting from roadway illumination. (2) The citizen science approach invites stakeholders to take part and join forces for the development of a sustainable and environmentally friendly road lighting solution. Here, we describe the project strategy, stakeholder participation and motivation, and how the effects of the alternative road luminaire and lighting design can be evaluated. (3) The study compares the changes in (a) insect behavior, (b) night sky brightness, and (c) stakeholder participation and awareness. For this purpose, different experimental areas and stakeholders in four communities in Germany are identified. (4) The project transfers knowledge of adverse effects of improperly managed road illumination and interacts with various stakeholders to develop a new road lighting system that will consider the well-being of street users, local residents, and insects.

1-Alkyl-3-methylimidazolium cation binding preferences in hexafluorophosphate ionic liquid clusters determined using competitive TCID measurements and theoretical calculations.

Ionic liquids (ILs) exhibit unique properties that have led to their development and widespread use for a variety of applications. Development efforts have generally focused on achieving desired macroscopic properties via tuning of the IL through variation of the cations and anions. Both the macroscopic and microscopic properties of an IL influence its tunability and thus feasibility of use for selected applications. Works geared toward a microscopic understanding of the nature and strength of the intrinsic cation-anion interactions of ILs have been limited to date. Specifically, the intrinsic strength of the cation-anion interactions in ILs is largely unknown. In previous work, we employed threshold collision-induced dissociation (TCID) approaches supported and enhanced by electronic structure calculations to determine the bond dissociation energies (BDEs) and characterize the nature of the cation-anion interactions in a series of four 2 : 1 clusters of 1-alkyl-3-methylimidazolium cations with the hexafluorophosphate anion, [2Cnmim:PF6]+. To examine the effects of the 1-alkyl chain on the structure and energetics of binding, the cation was varied over the series: 1-ethyl-3-methylimidazolium, [C2mim]+, 1-butyl-3-methylimidazolium, [C4mim]+, 1-hexyl-3-methylimidazolium, [C6mim]+, and 1-octyl-3-methylimidazolium, [C8mim]+. The variation in the strength of binding among these [2Cnmim:PF6]+ clusters was found to be similar in magnitude to the average experimental uncertainty in the measurements. To definitively establish an absolute order of binding among these [2Cnmim:PF6]+ clusters, we extend this work again using TCID and electronic structure theory approaches to include competitive binding studies of three mixed 2 : 1 clusters of 1-alkyl-3-methylimidazolium cations and the hexafluorophosphate anion, [Cn-2mim:PF6:Cnmim]+ for n = 4, 6, and 8. The absolute BDEs of these mixed [Cn-2mim:PF6:Cnmim]+ clusters as well as the absolute difference in the strength of the intrinsic binding interactions as a function of the cation are determined with significantly improved precision. By combining the thermochemical results of the previous independent and present competitive measurements, the BDEs of the [2Cnmim:PF6]+ clusters are both more accurately and more precisely determined. Comparisons are made to results for the analogous [2Cnmim:BF4]+ and [Cn-2mim:BF4:Cnmim]+ clusters previously examined to elucidate the effects of the [PF6]- and [BF4]- anions on the binding.

Structural determination of arginine-linked cisplatin complexes via IRMPD action spectroscopy: arginine binds to platinum via NO- binding mode.

Cisplatin, (NH3)2PtCl2, has been known as a successful metal-based anticancer drug for more than half a century. Its analogue, Argplatin, arginine-linked cisplatin, (Arg)PtCl2, is being investigated because it exhibits reactivity towards DNA and RNA that differs from that of cisplatin. In order to understand the basis for its altered reactivity, the deprotonated and sodium cationized forms of Argplatin, [(Arg-H)PtCl2]- and [(Arg)PtCl2 + Na]+, are examined by infrared multiple photon dissociation (IRMPD) action spectroscopy in the IR fingerprint and hydrogen-stretching regions. Complementary electronic structure calculations are performed using density functional theory approaches to characterize the stable structures of these complexes and to predict their infrared spectra. Comparison of the theoretical IR spectra predicted for various stable conformations of these Argplatin complexes to their measured IRMPD spectra enables determination of the binding mode(s) of Arg to the Pt metal center to be identified. Arginine is found to bind to Pt in a bidentate fashion to the backbone amino nitrogen and carboxylate oxygen atoms in both the [(Arg-H)PtCl2]- and [(Arg)PtCl2 + Na]+ complexes, the NO- binding mode. The neutral side chain of Arg also interacts with the Pt center to achieve additional stabilization in the [(Arg-H)PtCl2]- complex. In contrast, Na+ binds to both chlorido ligands in the [(Arg)PtCl2 + Na]+ complex and the protonated side chain of Arg is stabilized via hydrogen-bonding interactions with the carboxylate moiety. These findings are consistent with condensed-phase results, indicating that the NO- binding mode of arginine to Pt is preserved in the electrospray ionization process even under variable pH and ionic strength.

Influence of 5-Methylation and the 2'- and 3'-Hydroxy Substituents on the Base Pairing Energies of Protonated Cytidine Nucleoside Analogue Base Pairs: Implications for the Stabilities of i-Motif Structures.

Repetitive nucleic acid sequences, which occur in abundance throughout the mammalian genome, are of enormous research interest due to their potential to adopt fascinating and unusual molecular structures such as the i-motif. In remarkable contrast to the DNA double helix, i-motif conformations are stabilized by protonated cytosine base pairs, (Cyt)H+(Cyt), that are centrally located in the core of the i-motif and intercalated vertically in an antiparallel fashion. An in-depth understanding of how modifications influence the stability of i-motif conformations is a prerequisite to understanding their biological functions and the development of effective means of tuning their stability for specific medical and technological applications. Here, the influence of the 2'- and 3'-hydroxy substituents of the sugar moieties and 5-methylation of the cytosine nucleobases on the base-pairing interactions of protonated cytidine nucleoside analogue base pairs, (xCyd)H+(xCyd), are examined by complementary threshold collision-induced dissociation techniques and computational methods. The xCyd nucleosides examined include the canonical DNA and RNA cytidine nucleosides, 2'-deoxycytidine (dCyd) and cytidine (Cyd), as well as several modified cytidine nucleoside analogues, 2',3'-dideoxycytidine (ddCyd), 5-methyl-2'-deoxycytidine (m5dCyd), and 5-methylcytidine (m5Cyd). Comparisons among these model base pairs indicate that the 2'- and 3'-hydroxy substituents of the sugar moieties have very little influence on the strength of the base-pairing interactions, whereas 5-methylation of the cytosine nucleobases is found to enhance the strength of the base-pairing interactions. The increase in stability resulting from 5-methylation is only modest but is more than twice as large for the DNA than RNA protonated cytidine base pair. Overall, present results suggest that canonical DNA i-motif conformations should be more stable than analogous RNA i-motif conformations and that 5-methylation of cytosine residues, a significant epigenetic marker, provides greater stabilization to DNA than RNA i-motif conformations.

Impact of Different Wavelengths of Artificial Light at Night on Phototaxis in Aquatic Insects.

The use of artificial light at night (ALAN) is increasing exponentially worldwide and there is growing evidence that ALAN contributes to the decline of insect populations. One of the most conspicuous ecological effects is the strong attraction of ALAN to flying insects. In several studies, light sources with strong short-wavelength emissions have been shown to attract the highest numbers of flying insects. Furthermore, flying stages of aquatic insects are reported to be more vulnerable to ALAN than flying stages of terrestrial insects. This is concerning because freshwater habitats are likely affected by ALAN that originates from human activity centers, which are typically close to sources of freshwater. However, the effects of ALAN on aquatic insects, which spend their larval phase (amphibiotic insects) or their whole life cycle (fully aquatic insects) in freshwaters, are entirely understudied. Here, we investigated the phototaxis of aquatic insects to ALAN at different wavelengths and intensities. We used floating light traps and compared four, near-monochromatic, lights (blue, green, red, and yellow) at two different photopic light intensities in a ditch system, which was not exposed to ALAN previously. Similar to flying stages of (aquatic and terrestrial) insects, we found a strong positive phototaxis of aquatic life stages. However, in contrast to the flying stages, there is no clear preference for short-wavelength light. Overall, responsivity to wavelengths in the center of the visible range (green, yellow; 500-600 nm) was significant for all orders of aquatic insects studied, and the nymphs of Ephemeroptera did not respond to blue light at all. This is likely an adaption to how light is attenuated in freshwater systems, where not only the water itself but also a variety of optical constituents act as a color filter, often like in our case filtering out short-wavelength light. Therefore, insects living in freshwater bodies often live in longer wavelength-dominated environments and might therefore be especially sensitive to green/yellow light. In conclusion, the different spectral sensitivities of both aquatic and flying insects should be taken into account when planning lighting near freshwater.

Nature and strength of intrinsic cation-anion interactions of 1-alkyl-3-methylimidazolium hexafluorophosphate clusters.

Imidazolium-based cations and the hexafluorophosphate anion are among the most commonly used ionic liquids (ILs). Yet, the nature and strength of the intrinsic cation-anion interactions, and how they influence the macroscopic properties of these ILs are still not well understood. Threshold collision-induced dissociation is utilized to determine the bond dissociation energies (BDEs) of the 2 : 1 clusters of 1-alkyl-3-methylimidazolium cations and the hexafluorophosphate anion, [2Cnmim:PF6]+. The cation, [Cnmim]+, is varied across the series, 1-ethyl-3-methylimidazolium [C2mim]+, 1-butyl-3-methylimidazolium [C4mim]+, 1-hexyl-3-methylimidazolium [C6mim]+, 1-octyl-3-methylimidazolium [C8mim]+, to examine the structural and energetic effects of the size of the 1-alkyl substituent of the cation on the binding to [PF6]-. Complementary electronic structure methods are employed for the [Cnmim]+ cations, (Cnmim:PF6) ion pairs, and [2Cnmim:PF6]+ clusters to elucidate details of the cation-anion interactions and their impact on structure and energetics. Multiple levels of theory are benchmarked with the measured BDEs including B3LYP, B3LYP-GD3BJ, and M06-2X each with the 6-311+G(d,p) basis set for geometry optimizations and frequency analyses and the 6-311+G(2d,2p) basis set for energetic determinations. The modest structural variation among the [Cnmim]+ cations produces only minor structural changes and variation in the measured BDEs of the [2Cnmim:PF6]+ clusters. Present results are compared to those previously reported for the analogous 1-alkyl-3-methylimidazolium tetrafluoroborate IL clusters to compare the effects of these anions on the nature and strength of the intrinsic binding interactions.

Absolute Trends and Accurate and Precise Gas-Phase Binding Energies of 1-Alkyl-3-Methylimidazolium Tetrafluoroborate Ionic Liquid Clusters from Combined Independent and Competitive TCID Measurements.

Ionic liquid (IL) development efforts have focused on achieving desired properties via tuning of the IL through variation of the cations and anions. However, works geared toward a microscopic understanding of the nature and strength of the intrinsic cation-anion interactions of ILs have been rather limited such that the intrinsic strength of the cation-anion interactions in ILs is largely unknown. In previous work, we employed threshold collision-induced dissociation approaches supported and enhanced by electronic structure calculations to characterize the nature of the cation-anion interactions in and determine the bond dissociation energies (BDEs) of a series of four 2:1 clusters of 1-alkyl-3-methylimidazolium cations and tetrafluoroborate anions, [2Cnmim:BF4]+. The cation was varied over the series: 1-ethyl-3-methylimidazolium, [C2mim]+, 1-butyl-3-methylimidazolium, [C4mim]+, 1-hexyl-3-methylimidazolium, [C6mim]+, and 1-octyl-3-methylimidazolium, [C8mim]+, to determine the structural and energetic effects of the size of the 1-alkyl substituent on the binding. The variation in the strength of binding determined for these [2Cnmim:BF4]+ clusters was found to be similar in magnitude to the average experimental uncertainty in these determinations. To definitively establish an absolute order of binding among these [2Cnmim:BF4]+ clusters, we extend this work here to include competitive binding studies of three mixed 2:1 clusters of 1-alkyl-3-methylimidazolium cations and tetrafluoroborate anions, [Cn-2mim:BF4:Cnmim]+ for n = 4, 6, and 8. Importantly, the results of the present work simultaneously provide the absolute BDEs of these mixed [Cn-2mim:BF4:Cnmim]+ clusters and the absolute relative order of the intrinsic binding interactions as a function of the cation with significantly improved precision. Further, by combining the thermochemical results of the previous and present studies, the BDEs of the [2Cnmim:BF4]+ clusters are more accurately and precisely determined.

Gas-Phase Binding Energies and Dissociation Dynamics of 1-Alkyl-3-Methylimidazolium Tetrafluoroborate Ionic Liquid Clusters.

Ionic liquids (ILs) have become increasingly popular due to their useful and unique properties, yet there are still many unanswered questions regarding their fundamental interactions. In particular, details regarding the nature and strength of the intrinsic cation-anion interactions and how they influence the macroscopic properties of ILs are still largely unknown. Elucidating the molecular-level details of these interactions is essential to the development of better models for describing ILs and enabling the purposeful design of ILs with properties tailored for specific applications. Current uses of ILs are widespread and diverse and include applications for energy storage, electrochemistry, designer/green solvents, separations, and space propulsion. To advance the understanding of the energetics, conformations, and dynamics of gas-phase IL clustering relevant to space propulsion, threshold collision-induced dissociation approaches are used to measure the bond dissociation energies (BDEs) of the 2:1 clusters of 1-alkyl-3-methylimidazolium cations and tetrafluoroborate, [2Cnmim:BF4]+. The cation, [Cnmim]+, is varied across the series, 1-ethyl-3-methylimidazolium [C2mim]+, 1-butyl-3-methylimidazolium [C4mim]+, 1-hexyl-3-methylimidazolium [C6mim]+, and 1-octyl-3-methylimidazolium [C8mim]+, to examine the structural and energetic effects of the size of the 1-alkyl substituent on binding. Complementary electronic structure calculations are performed to determine the structures and energetics of the [Cnmim]+ and [BF4]- ions and their binding preferences in the (Cnmim:BF4) ion pairs and [2Cnmim:BF4]+ clusters. Several levels of theory, B3LYP, B3LYP-GD3BJ, and M06-2X, using the 6-311+G(d,p) basis set for geometry optimizations and frequency analyses and the 6-311+G(2d,2p) basis set for energetics, are benchmarked to examine their abilities to properly describe the nature of the binding interactions and to reproduce the measured BDEs. The modest structural variation among these [Cnmim]+ cations produces only minor structural changes and variation in the measured BDEs of the [2Cnmim:BF4]+ clusters. Present findings indicate that the dominant cation-anion interactions involve the 3-methylimidazolium moieties and that these clusters are sufficiently small that differences in packing effects associated with the variable length of the 1-alkyl substituents are not yet significant.

Experimental light at night has a negative long-term impact on macro-moth populations.

Van Grunsven et al. experimentally test the long-term effects of artificial light on natural moth populations. In the initial two years there was no effect on populations, but in the latter three years population sizes were reduced compared with the dark controls. This shows that artificial light negatively affects moth populations.

Structures and Relative Glycosidic Bond Stabilities of Protonated 2'-Fluoro-Substituted Purine Nucleosides.

The 2'-substituent is the primary distinguishing feature between DNA and RNA nucleosides. Modifications to this critical position, both naturally occurring and synthetic, can produce biologically valuable nucleoside analogues. The unique properties of fluorine make it particularly interesting and medically useful as a synthetic nucleoside modification. In this work, the effects of 2'-fluoro modification on the protonated gas-phase purine nucleosides are examined using complementary tandem mass spectrometry and computational methods. Direct comparisons are made with previous studies on related nucleosides. Infrared multiple photon dissociation action spectroscopy performed in both the fingerprint and hydrogen-stretching regions allows for the determination of the experimentally populated conformations. The populated conformers of protonated 2'-fluoro-2'-deoxyadenosine, [Adofl+H]+, and 2'-fluoro-2'-deoxyguanosine, [Guofl+H]+, are highly parallel to their respective canonical DNA and RNA counterparts. Both N3 and N1 protonation sites are accessed by [Adofl+H]+, stabilizing syn and anti nucleobase orientations, respectively. N7 protonation and anti nucleobase orientation dominates in [Guofl+H]+. Spectroscopically observable intramolecular hydrogen-bonding interactions with fluorine allow more definitive sugar puckering determinations than possible for the canonical systems. [Adofl+H]+ adopts C2'-endo sugar puckering, whereas [Guofl+H]+ adopts both C2'-endo and C3'-endo sugar puckering. Energy-resolved collision-induced dissociation experiments with survival yield analyses provide relative glycosidic bond stabilities. The N-glycosidic bond stabilities of the protonated 2'-fluoro-substituted purine nucleosides are found to exceed those of their canonical analogues. Further, the N-glycosidic bond stability is found to increase with increasing electronegativity of the 2'-substituent, i.e., H < OH < F. The N-glycosidic bond stability is also greater for the adenine nucleoside analogues than the guanine nucleoside analogues.

Is prehospital blood transfusion effective and safe in haemorrhagic trauma patients? A systematic review and meta-analysis.

BACKGROUND: Life-threatening haemorrhage accounts for 40% mortality in trauma patients worldwide. After bleeding control is achieved, circulating volume must be restored. Early in-hospital transfusion of blood components is already proven effective, but the scientific proof for the effectiveness of prehospital blood-component transfusion (PHBT) in trauma patients is still unclear. OBJECTIVE: To systematically review the evidence for effectiveness and safety of PHBT to haemorrhagic trauma patients. METHODS: CINAHL, Cochrane, EMBASE, and Pubmed were searched in the period from 1988 until August 1, 2018. Meta-analysis was performed for matched trauma patients receiving PHBT with the primary outcomes 24-hour mortality and long-term mortality. Secondary outcome measure was adverse events as a result of PHBT. RESULTS: Trauma patients who received PHBT with simultaneous use of packed red blood cells (pRBCs) and plasma showed a statistically significant reduction in long-term mortality (OR = 0.51; 95% CI, 0.36-0.71; P < 0.0001) but no difference in 24-hour mortality (OR = 0.47, 95% CI, 0.17-1.34; P = 0.16). PHBT with individual use of pRBCs showed no difference in long-term mortality (OR = 1.18; 95% CI, 0.93-1.49; P = 0.17) or 24-hour mortality (OR = 0.92; 95% CI, 0.46-1.85; P = 0.82). In a total of 1341 patients who received PHBT, 14 adverse events were reported 1.04%, 95% CI 0.57-1.75%. CONCLUSIONS: PHBT with simultaneous use of both pRBCs and plasma resulted in a significant reduction in the odds for long-term mortality. However, based on mainly poor quality evidence no hard conclusion can be drawn about a possible survival benefit for haemorrhagic trauma patients receiving PHBT. Overall, PHBT is safe but results of currently ongoing randomised controlled trials have to be awaited to demonstrate a survival benefit. STUDY TYPE: Systematic review and meta-analysis.

Impact of the 2'- and 3'-Sugar Hydroxyl Moieties on Gas-Phase Nucleoside Structure.

Modified nucleosides have been an important target for pharmaceutical development for the treatment of cancer, herpes simplex virus, and the human immunodeficiency virus (HIV). Amongst these nucleoside analogues, those based on 2',3'-dideoxyribose sugars are quite common, particularly in anti-HIV applications. The gas-phase structures of several protonated 2',3'-dideoxyribose nucleosides are examined in this work and compared with those of the analogous protonated DNA, RNA, and arabinose nucleosides to elucidate the influence of the 2'- and combined 2',3'-hydroxyl groups on intrinsic structure. Infrared multiple photon dissociation (IRMPD) action spectra are collected for the protonated 2',3'-dideoxy forms of adenosine, guanosine, cytidine, thymidine and uridine, [ddAdo+H]+, [ddGuo+H]+, [ddCyd+H]+, [ddThd+H]+, and [ddUrd+H]+, in the IR fingerprint and hydrogen-stretching regions. Molecular mechanics conformational searching followed by electronic structure calculations generates low-energy conformers of the protonated 2',3'-dideoxynucleosides and corresponding predicted linear IR spectra to facilitate interpretation of the measured IRMPD action spectra. These experimental IRMPD spectra and theoretical calculations indicate that the absence of the 2'- and 3'-hydroxyls largely preserves the protonation preferences of the canonical forms. The spectra and calculated structures indicate a slight preference for C3'-endo sugar puckering. The presence of the 3'- and further 2'-hydroxyl increases the available intramolecular hydrogen-bonding opportunities and shifts the sugar puckering modes for all nucleosides but the guanosine analogues to a slight preference for C2'-endo over C3'-endo. Graphical Abstract.

Effects of experimental light at night on extra-pair paternity in a songbird.

Light pollution is increasing worldwide and significantly affects animal behavior. In birds, these effects include advancement of morning activity and onset of dawn song, which may affect extra-pair paternity. Advanced dawn song of males may stimulate females to engage in extra-pair copulations, and the earlier activity onset may affect the males' mate guarding behavior. Earlier work showed an effect of light at night on extra-pair behavior, but this was in an area with other anthropogenic disturbances. Here, we present a two-year experimental study on effects of light at night on extra-pair paternity of great tits (Parus major). Previously dark natural areas were illuminated with white, red, and green LED lamps and compared to a dark control. In 2014, the proportion of extra-pair young in broods increased with distance to the red and white lamps (i.e., at lower light intensities), but decreased with distance to the poles in the dark control. In 2013, we found no effects on the proportion of extra-pair young. The total number of offspring sired by a male was unaffected by artificial light at night in both years, suggesting that potential changes in female fidelity in pairs breeding close to white and red light did not translate into fitness benefits for the males of these pairs. Artificial light at night might disrupt the natural patterns of extra-pair paternity, possibly negates potential benefits of extra-pair copulations and thus could alter sexual selection processes in wild birds.

Colors of attraction: Modeling insect flight to light behavior.

Light sources attract nocturnal flying insects, but some lamps attract more insects than others. The relation between the properties of a light source and the number of attracted insects is, however, poorly understood. We developed a model to quantify the attractiveness of light sources based on the spectral output. This model is fitted using data from field experiments that compare a large number of different light sources. We validated this model using two additional datasets, one for all insects and one excluding the numerous Diptera. Our model facilitates the development and application of light sources that attract fewer insects without the need for extensive field tests and it can be used to correct for spectral composition when formulating hypotheses on the ecological impact of artificial light. In addition, we present a tool allowing the conversion of the spectral output of light sources to their relative insect attraction based on this model.

A transition to white LED increases ecological impacts of nocturnal illumination on aquatic primary producers in a lowland agricultural drainage ditch.

The increasing use of artificial light at night (ALAN) has led to exposure of freshwater ecosystems to light pollution worldwide. Simultaneously, the spectral composition of nocturnal illumination is changing, following the current shift in outdoor lighting technologies from traditional light sources to light emitting diodes (LED). LEDs emit broad-spectrum white light, with a significant amount of photosynthetically active radiation, and typically a high content of blue light that regulates circadian rhythms in many organisms. While effects of the shift to LED have been investigated in nocturnal animals, its impact on primary producers is unknown. We performed three field experiments in a lowland agricultural drainage ditch to assess the impacts of a transition from high-pressure sodium (HPS) to white LED illumination (color temperature 4000 K) on primary producers in periphyton. In all experiments, we compared biomass and pigment composition of periphyton grown under a natural light regime to that of periphyton exposed to nocturnal HPS or, consecutively, LED light of intensities commonly found in urban waters (approximately 20 lux). Periphyton was collected in time series (1-13 weeks). We found no effect of HPS light on periphyton biomass; however, following a shift to LED the biomass decreased up to 62%. Neither light source had a substantial effect on pigment composition. The contrasting effects of the two light sources on biomass may be explained by differences in their spectral composition, and in particular the blue content. Our results suggest that spectral composition of the light source plays a role in determining the impacts of ALAN on periphyton and that the ongoing transition to LED may increase the ecological impacts of artificial lighting on aquatic primary producers. Reduced biomass in the base of the food web can impact ecosystem functions such as productivity and food supply for higher trophic levels in nocturnally-lit ecosystems.

Slugs (Arionidae) benefit from nocturnal artificial illumination.

Artificial illumination increases around the globe and this has been found to affect many groups of organisms and ecosystems. By manipulating nocturnal illumination using one large experimental field site with 24 streetlights and one dark control, we assessed the impact of artificial illumination on slugs over a period of 4 years. The number of slugs, primarily Arionidae, increased strongly in the illuminated site but not on the dark site. There are several nonexclusive explanations for this effect, including reduced predation and increased food quality in the form of carcasses of insects attracted by the light. As slugs play an important role in ecosystems and are also important pest species, the increase of slugs under artificial illumination cannot only affect ecosystem functioning but also have important economic consequences.