Integrated catchment management : Upper Denmark Catchment

The project mapped the landforms and land management units on cleared parts of the catchment ; defined the extent of, processes causing and options for solving the salinity problem in the Upper Denmark Catchment; developed a catchment management plan that would reverse the increasing soil and stream salinity trend within the catchment; encouraged and assisted the landholders to adopt the plan; and applied the results of the study to other areas

Critical light instability in CB/DIO processed PBDTTT-EFT:PC<inf>71</inf>BM organic photovoltaic devices

Organic photovoltaic (OPV) devices often undergo ‘burn-in’ during the early stages of operation, this period describing the relatively rapid drop in power output before stabilising. For normal and inverted PBDTTT-EFT:PC71BM OPVs prepared according to current protocols, we identify a critical and severe light-induced burn-in phase that reduces power conversion efficiency by at least 60% after 24 hours simulated AM1.5 illumination. Such losses result primarily from a reduction in photocurrent, and for inverted devices we correlate this process in-situ with the simultaneous emergence of space-chare effects on the μs timescale. The effects of burn in are also found to reduce the lifetime of photogenerated charge carriers, as determine by in-situ transient photovoltage measurements. To identify the underlying mechanisms of this instability, a range of techniques are employed ex-situ to separate bulk- and electrode-specific degradation processes. We find that whilst the active layer nanostructure and kinetics of free charge generation remain unchanged, partial photobleaching (6% of film O.D.) of PBDTTT-EFT:PC71BM occurs alongside an increase in the ground state bleach decay time of PBDTTT-EFT. We hypothesise that this latter observation may reflect relaxation from excited states on PBDTTT-EFT that do not undergo dissociation into free charges. Owing to the poor lifetime of the reference PBDTTT-EFT:PC71BM OPVs, the fabrication protocol is modified to identify routes for stability enhancement in this initially promising solar cell blend.The authors would like to thank SABIC for partially funding this research. PEH, EC, RHF and NCG thank the EPSRC for funding through the Supergen Supersolar Consortium (EP/J017361/1). PEH also thanks CKIK for additional funding. KD thanks the Gates Cambridge Scholarship fund. MAJ thanks Nyak Technology Ltd for PhD scholarship funding. AJP thanks David Lidzey (University of Sheffield) for use of a sample chamber for X-ray scattering measurements and Adam Brown (University of Cambridge) for UPS measurements.This is the final version of the article. It first appeared from Elsevier via http://dx.doi.org/10.1016/j.orgel.2015.12.02

Identification of antisense nucleic acid hybridization sites in mRNA molecules with self-quenching fluorescent reporter molecules

We describe a physical mRNA mapping strategy employing fluorescent self-quenching reporter molecules (SQRMs) that facilitates the identification of mRNA sequence accessible for hybridization with antisense nucleic acids in vitro and in vivo, real time. SQRMs are 20–30 base oligodeoxynucleotides with 5–6 bp complementary ends to which a 5′ fluorophore and 3′ quenching group are attached. Alone, the SQRM complementary ends form a stem that holds the fluorophore and quencher in contact. When the SQRM forms base pairs with its target, the structure separates the fluorophore from the quencher. This event can be reported by fluorescence emission when the fluorophore is excited. The stem–loop of the SQRM suggests that SQRM be made to target natural stem–loop structures formed during mRNA synthesis. The general utility of this method is demonstrated by SQRM identification of targetable sequence within c-myb and bcl-6 mRNA. Corresponding antisense oligonucleotides reduce these gene products in cells

Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering

Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics.S.L. thanks AGS(O) Scholarship support from A*STAR Singapore. J.W. acknowledges financial support from MOE Tier 3 grant (MOE2014-T3-1-004). This work was supported by the Engineering and Physical Sciences Research Council, U.K. (Grant numbers EP/M005143/1 and EP/G060738/1). D.H.P.T. and N.D.M.H. acknowledge the Winton Programme for the Physics of Sustainability. K.C. and J.M.H. acknowledge support from a Rutherford Discovery Fellowship to J.M.H

Best practices for measuring emerging light-emitting diode technologies

The arrival of light-emitting diodes based on new materials is posing challenges for the characterization and comparison of devices in a trusted and consistent manner. Here we provide some advice and guidelines that we hope will benefit the community

Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix

10.1021/jz502615eJournal of Physical Chemistry Letters63446-45

Tuneable Singlet Exciton Fission and Triplet-Triplet Annihilation in an Orthogonal Pentacene Dimer

We report fast and highly efficient intramolecular singlet exciton fission in a pentacene dimer, consisting of two covalently attached, nearly orthogonal pentacene units. Fission to triplet excitons from this ground state geometry occurs within 1 ps in isolated molecules in solution and dispersed solid matrices. The process exhibits a sensitivity to environmental polarity and competes with geometric relaxation in the singlet state, while subsequent triplet decay is strongly dependent on conformational freedom. The near orthogonal arrangement of the pentacene units is unlike any structure currently proposed for efficient singlet exciton fission and may lead to new molecular design rules.JW acknowledges financial support from Singapore MOE Tier 3 grant (MOE2014-T3-1-004). SL thanks AGS Scholarship support from the A*STAR Singapore. The work was supported by the EPSRC (grant number EP/G060738/1). We acknowledge the use of the Darwin Supercomputer of the University of Cambridge High 18 Performance Computing Service (http://www.hpc.cam.ac.uk/) and the EPSRC UK National Service for Computational Chemistry Software (NSCCS) at Imperial College London in carrying out this work.This is the final version of the article. It first appeared from Wiley via http://dx.doi.org/10.1002/adfm.20150153

Efficient singlet exciton fission in pentacene prepared from a soluble precursor

Carrier multiplication using singlet exciton fission (SF) to generate a pair of spin-triplet excitons from a single optical excitation has been highlighted as a promising approach to boost the photocurrent in photovoltaics (PVs) thereby allowing PV operation beyond the Shockley-Queisser limit. The applicability of many efficient fission materials, however, is limited due to their poor solubility. For instance, while acene-based organics such as pentacene (Pc) show high SF yields (up to 200%), the plain acene backbone renders the organic molecule insoluble in common organic solvents. Previous approaches adding solubilizing side groups such as bis(tri-$\textit{iso}$-propylsilylethynyl) to the Pc core resulted in low vertical carrier mobilities due to reduction of the transfer integrals via steric hindrance, which prevented high efficiencies in PVs. Here we show how to achieve good solubility while retaining the advantages of molecular Pc by using a soluble precursor route. The precursor fully converts into molecular Pc through thermal removal of the solubilizing side groups upon annealing above 150 °C in the solid state. The annealed precursor shows small differences in the crystallinity compared to evaporated thin films of Pc, indicating that the Pc adopts the bulk rather than surface polytype. Furthermore, we identify identical SF properties such as sub-100 fs fission time and equally long triplet lifetimes in both samples.M.T. thanks the Gates Cambridge Trust and the Winton Programme for the Physics of Sustainability for funding. A.H.K. acknowledges the Cambridge Nehru Bursary, the Cambridge Bombay Society, a Trinity-Henry Barlow- and Haidar Scholarship as well as Rana Denim Pvt. Ltd. for financial support. K.B. and J.N. would like to thank Dr. Tom Arnold and Jakub Rozboril for assistance during the beam time at Diamond Light Source. Financial support for K.B. from Diamond Light Source, Swiss Light Source, and the German Research Foundation (Grant No. BR 4869/1-1) is gratefully acknowledged. M.L.B. is a research fellow of Christ’s College, Cambridge. This work was supported by the Engineering and Physical Sciences Research Council (Grant Nos. EP/M005143/1, EP/G060738/1 and Cambridge NanoDTC EP/G037221/1, EP/L015978/1)

Understanding the chemical mechanism behind photoinduced enhanced Raman spectroscopy

Photoinduced enhanced Raman spectroscopy (PIERS) is a new surface enhanced Raman spectroscopy (SERS) modality with a 680% Raman signal enhancement of adsorbed analytes over that of SERS. Despite the explosion in recent demonstrations, the PIERS mechanism remains undetermined. Using X-ray and time-resolved optical spectroscopies, electron microscopy, cyclic voltammetry, and density functional theory simulations, we elucidate the atomic-scale mechanism behind PIERS. Stable PIERS substrates were fabricated using self-organized arrays of TiO2 nanotubes with controlled oxygen vacancy doping and size-controlled silver nanoparticles. The key source of PIERS vs SERS enhancement is an increase in the Raman polarizability of the adsorbed analyte upon photoinduced charge transfer. A balance between improved crystallinity, which enhances charge transfer due to higher electron mobility but decreases light absorption, and increased oxygen vacancy defect concentration, which increases light absorption, is critical. This work enables the rational design of PIERS substrates for sensing