Merging molecular catalysts and metal-organic frameworks for photocatalytic fuel production.

In the effort to generate sustainable clean energy from abundant resources such as water and carbon dioxide, solar fuel production-the combination of solar-light harvesting and the generation of efficient chemical energy carriers-by artificial molecular photosystems is very attractive. Molecular constituents that display attractive features for chemical energy conversion (such as high product selectivity and atom economy) have been developed, and their interfacing with host materials has enabled recyclability, controlled site positioning, as well as access to fundamental insights into the catalytic mechanism and environment-governed selectivity. Among the wide variety of supports, metal-organic frameworks (MOFs) possess valuable characteristics (such as their porosity and versatility) that can influence the reaction environment and material architecture in a unique fashion. Here we highlight the various existing synthetic strategies to graft molecular complexes such as catalysts and photosensitizers onto MOFs for solar fuel production. The opportunities and limitations of one-pot and stepwise approaches are critically assessed, and the resulting materials are discussed based on their photocatalytic performances and the practical applicability of selected examples.

Cultivar × Management Interaction to Reduce Lodging and Improve Grain Yield of Irrigated Spring Wheat: Optimising Plant Growth Regulator Use, N Application Timing, Row Spacing and Sowing Date.

Severe lodging of irrigated spring-wheat in sub-tropical Australia has previously caused yield loss of between 1.7 and 4.6 t ha-1 (20-60% of potential yield). In response, agronomic management options were assessed for their ability to reduce lodging and increase grain yield, namely plant growth regulators (PGRs), timing of nitrogen (N) application, row spacing and sowing date, in combination with long and short duration cultivars across 15 irrigated environments from 2012 to 2016. Our study identified significant interaction between genotype, environment and agronomic management (G × E × M) for grain yield and lodging, although some combinations of agronomic techniques were broadly applicable across cultivars. PGR application improved grain yield of most cultivars in well-irrigated fields that had more than 120 kg ha-1 N (mineral N + fertiliser N) at sowing, with yield gains of up to 0.5 t ha-1 observed in both lodged and non-lodged fields. However, PGRs had little effect on grain yield when soil + fertiliser N at sowing was less than 80 kg ha-1 N. In-crop N application (compared to sowing N application) often improved grain yield of short duration, lodging resistant cultivars, but reduced the yield of long-duration, lodging susceptible cultivars in some environments. Narrow row spacing of 19 cm had the highest grain yield across cultivars in low lodging environments. At a severely lodged environment, narrow rows were the highest yielding for five out of six cultivars when PGRs were used, but was the highest yielding for only half of the tested cultivars when PGRs were not used. Cultivar × sowing date interaction for grain yield was also associated with the occurrence of lodging. Neither early nor late sowing had a consistent yield benefit across a range of cultivars, as lodging severity varied between sowing date depending on the timing of storm-induced lodging events. Lodging resistant long-duration cultivars had more stable grain yield across environments and increased grain yield in response to early sowing. Further research is needed to determine the optimum management strategy for new cultivars, because farmers do not always choose the most lodging resistant cultivars for reasons of cultivar disease resistance, grain quality and seed availability.

Review: High-throughput phenotyping to enhance the use of crop genetic resources.

Improved genetic, genomic and statistical technologies have increased the capacity to enrich breeding populations for key alleles underpinning adaptation and continued genetic gain. In turn, directed genomic selection together with increased heritability will reduce genetic variance to narrow the genetic base in many crop breeding programs. Diverse genetic resources (GR), including wild and weedy relatives, landraces and reconstituted synthetics, have potential to contribute novel alleles for key traits. Targeted trait identification may also identify genetic diversity in addressing new challenges including the need for modified root architecture, greater nutrient-use efficiency, and adaptation to warmer air and soil temperatures forecast with climate change. Yet while core collections and other GR sources have historically been invaluable for major gene control of disease and subsoil constraints, the mining of genetically (and phenotypically) complex traits in GR remains a significant challenge owing to reduced fertility, limited seed quantities and poor adaptation through linkage drag with undesirable alleles. High-throughput field phenomics (HTFP) offers the opportunity to capture phenotypically complex variation underpinning adaptation in traditional phenotypic selection or statistics-based breeding programs. Targeted HTFP will permit the reliable phenotyping of greater numbers of GR-derived breeding lines using smaller plot sizes and at earlier stages of population development to reduce the duration of breeding cycles and the loss of potentially important alleles with linkage drag. Two key opportunities are highlighted for use of HTFP in selection among GR-derived wheat breeding lines for greater biomass and stomatal conductance through canopy temperature.

Flexible metal-organic frameworks.

Advances in flexible and functional metal-organic frameworks (MOFs), also called soft porous crystals, are reviewed by covering the literature of the five years period 2009-2013 with reference to the early pertinent work since the late 1990s. Flexible MOFs combine the crystalline order of the underlying coordination network with cooperative structural transformability. These materials can respond to physical and chemical stimuli of various kinds in a tunable fashion by molecular design, which does not exist for other known solid-state materials. Among the fascinating properties are so-called breathing and swelling phenomena as a function of host-guest interactions. Phase transitions are triggered by guest adsorption/desorption, photochemical, thermal, and mechanical stimuli. Other important flexible properties of MOFs, such as linker rotation and sub-net sliding, which are not necessarily accompanied by crystallographic phase transitions, are briefly mentioned as well. Emphasis is given on reviewing the recent progress in application of in situ characterization techniques and the results of theoretical approaches to characterize and understand the breathing mechanisms and phase transitions. The flexible MOF systems, which are discussed, are categorized by the type of metal-nodes involved and how their coordination chemistry with the linker molecules controls the framework dynamics. Aspects of tailoring the flexible and responsive properties by the mixed component solid-solution concept are included, and as well examples of possible applications of flexible metal-organic frameworks for separation, catalysis, sensing, and biomedicine.

Co3O4/ZnO nanocomposites: from plasma synthesis to gas sensing applications.

Herein, we describe the design, fabrication and gas sensing tests of p-Co(3)O(4)/n-ZnO nanocomposites. Specifically, arrays of (001) oriented ZnO nanoparticles were grown on alumina substrates by plasma enhanced-chemical vapor deposition (PECVD) and used as templates for the subsequent PECVD of Co(3)O(4) nanograins. Structural, morphological and compositional analyses evidenced the successful formation of pure and high-area nanocomposites with a tailored overdispersion of Co(3)O(4) particles on ZnO and an intimate contact between the two oxides. Preliminary functional tests for the detection of flammable/toxic analytes (CH(3)COCH(3), CH(3)CH(2)OH, NO(2)) indicated promising sensing responses and the possibility of discriminating between reducing and oxidizing species as a function of the operating temperature.

MOF-on-MOF heteroepitaxy: perfectly oriented [Zn2(ndc)2(dabco)]n grown on [Cu2(ndc)2(dabco)]n thin films.

We report the successful heteroepitaxial growth of perfectly oriented hybrid MOF thin films. By employing step-by-step liquid-phase epitaxy (LPE), [Zn(2)(ndc)(2)(dabco)](n) was grown on [Cu(2)(ndc)(2)(dabco)](n), thus demonstrating that the MOF-on-MOF deposition scheme developed for powdered microcrystalline MOF materials can also be applied in connection with LPE for MOF thin films or multilayers. The deposition was monitored by surface plasmon resonance (SPR) spectroscopy, the resulting MOF heterostructures were characterized using IR spectroscopy and different types of X-ray diffraction (XRD)-based techniques. The results suggest that the LPE method is a promising way to fabricate and grow MOF heterostructures, and also demonstrates the potential of [Cu(2)(ndc)(2)(dabco)](n) MOF thin films as substrates for the LPE-based growth of different MOFs on top.

MOF thin films: existing and future applications.

The applications and potentials of thin film coatings of metal-organic frameworks (MOFs) supported on various substrates are discussed in this critical review. Because the demand for fabricating such porous coatings is rather obvious, in the past years several synthesis schemes have been developed for the preparation of thin porous MOF films. Interestingly, although this is an emerging field seeing a rapid development a number of different applications on MOF films were either already demonstrated or have been proposed. This review focuses on the fabrication of continuous, thin porous films, either supported on solid substrates or as free-standing membranes. The availability of such two-dimensional types of porous coatings opened the door for a number of new perspectives for functionalizing surfaces. Also for the porous materials themselves, the availability of a solid support to which the MOF-films are rigidly (in a mechanical sense) anchored provides access to applications not available for the typical MOF powders with particle sizes of a few µm. We will also address some of the potential and applications of thin films in different fields like luminescence, QCM-based sensors, optoelectronics, gas separation and catalysis. A separate chapter has been devoted to the delamination of MOF thin films and discusses the potential to use them as free-standing membranes or as nano-containers. The review also demonstrates the possibility of using MOF thin films as model systems for detailed studies on MOF-related phenomena, e.g. adsorption and diffusion of small molecules into MOFs as well as the formation mechanism of MOFs (101 references).

Characterization of interfacial water in MOF-5 (Zn4(O)(BDC)3)--a combined spectroscopic and theoretical study.

In this article we report the detection and characterization of adsorbed interfacial water within the cages of the metal-organic framework MOF-5 (Zn(4)O(BDC)(3)) by terahertz time-domain spectroscopy (THz TDS) in the frequency range from 5 to 46 cm(-1). The experimental spectra suggest a coupling of the intermolecular motions of the water molecules adsorbed to the collective vibrations of the network at 4 wt% hydration. This finding is supported by the results of MD simulations. When increasing the water content to 8 wt% we observed a non reversible decomposition of MOF-5.

Redox chemistry of Cu colloids probed by adsorbed CO: an in situ attenuated total reflection Fourier transform infrared study.

The IR spectroscopic investigation of both the adsorption of carbon monoxide and the interaction of oxygen and CO on the surface of copper colloids is described for the first time. The copper colloids were produced by pyrolysis of [Cu(OCH(Me)CH(2)NMe(2))(2)] in hot n-hexadecylamine. Upon contact to synthetic air Cu/Cu(x)O core-shell particles are formed. The treatment of these particles with CO results in the reestablishment of pure Cu(0) particles. These results demonstrate that small molecules penetrate the ligand shell of the nanoparticles and reversibly adsorb at the surface without affecting the particle morphology and size distribution.

Fabrication of self-assembled monolayers exhibiting a thiol-terminated surface.

We compare two different strategies for fabricating self-assembled monolayers (SAMs) exhibiting a thiol-terminated organic surface, which recently has attracted considerable interest with regard to the binding of metal, and in particular gold particles, to these organic surfaces. Results obtained by IR spectroscopy and scanning tunneling microscopy (STM) reveal that the straightforward approach, namely, using the corresponding organodithiols, typically leads to the formation of disordered, ill-defined surfaces. We demonstrate that high-quality organothiolate adlayers exhibiting an SH-terminated surface can be prepared using dithiols where one of the thiol groups is protected by a thioester group. After formation of the organothiolate adlayer, the protecting group can be removed by immersion into NaOH solution. IR spectra recorded for the deprotected organothiolate adlayer reveal the presence of a highly oriented organothiolate adlayer.

The effects of age, sex, and shoulder dominance on range of motion of the shoulder.

To determine the effects of age, sex, and arm dominance on shoulder range of motion, we measured active and passive forward elevation, abduction, internal and external rotation at 90 degrees of abduction, external rotation with the arm adducted, and extension bilaterally in 280 subjects ranging in age from 4 to 70 years. Linear regression analyses were performed for all motions except forward elevation. This motion, which showed a nonlinear pattern of decline with age, was evaluated with 3-way analysis of variance. Shoulder range of motion decreased with age for all measured motions with the exception of internal rotation, which increased with age. Female subjects had a significantly greater range of motion than male subjects for all motions measured. Dominant arms displayed significantly greater external rotation than nondominant, regardless of whether the arm was abducted or adducted at the time of measurement. However, nondominant shoulders demonstrated significantly greater internal rotation and extension than dominant. No significant differences were found between dominant and nondominant sides for forward elevation or abduction.

Transfusion-associated falciparum malaria successfully treated with red blood cell exchange transfusion.

Falciparum malaria is frequently associated with significant morbidity and mortality. The use of exchange transfusion as a therapeutic modality for severe cases of malaria has been described previously. We describe a case of a 49 year-old African American gentleman with a history of hemoglobin-SC disease who presented with a severe case of Plasmodium falciparum malaria 3 weeks after having received an infected blood transfusion. His peripheral smear showed the presence of numerous intraerythrocytic ring forms and "banana-shaped" gametocytes with a high-grade parasitemia, estimated at 18%. He was treated with antimalarial chemotherapy and also underwent a 12-unit red blood cell exchange transfusion, decreasing his parasite load to < 1%, as determined on repeat smear. It is prudent to be aware of the efficacy of this adjunctive treatment, especially with ever-increasing travel and a resultant increase in the prevalence of tropical diseases in the United States.

MR observations of postraumatic osteolysis of the distal clavicle after traumatic separation of the acromioclavicular joint.

PURPOSE: The purpose of this work was to characterize the MR features of post-traumatic osteolysis of the distal clavicle in patients who have sustained a previous separation of the ipsilateral acromioclavicular (AC) joint. METHOD: We studied eight male patients (mean age 25 years) with intractable pain in the AC joint after sustaining a traumatic joint separation. With use of the Rockwood classification, the separations were classified as Type 1 in one patient, Type 2 in two patients, and Type 3 in five patients. The MR studies were evaluated for periarticular soft tissue swelling, cortical irregularity defined as thinning or absence of portions of the cortex in the acromial and clavicular articular surfaces, hypertrophic osseous changes, periostitis, bone marrow edema, periarticular cyst-like changes, and joint space widening exceeding 6 mm. Radiographs were evaluated independently of the MR studies. Osteolysis of the distal clavicle was confirmed pathologically in seven patients and with surgery in one patient. RESULTS: The incidence of osteolysis in patients who have had a previous AC joint separation was estimated to be approximately 6%. Observations on MRI included soft tissue swelling, bone marrow edema in the distal clavicle, and cortical irregularity associated with periarticular cyst-like erosions in eight patients, joint space widening in six patients, clavicular periostitis in three patients, and marrow edema in the cromion in five patients. Only one patient had osteophyte formation. Radiographic observations of periarticular soft tissue swelling, osteopenia of the distal clavicle, articular erosions, and joint space widening allowed diagnosis in only four patients prospectively. CONCLUSION: The MR features of posttraumatic osteolysis are characteristic of this process. We advocate the use of MRI in patients with chronic AC joint pain who have had a prior AC joint dislocation, particularly if follow-up radiographs are nonspecific, equivocal, or do not indicate the presence of secondary osteoarthritis.

Arthroscopic distal clavicle resection for isolated atraumatic osteolysis in weight lifters.

Ten consecutive patients with isolated atraumatic osteolysis of the distal clavicle who had failed results with conservative treatment were treated with arthroscopic resection of the involved distal clavicle (average, 4.5 mm). All patients were men with an average age of 30.4 years, had unilateral involvement, and were considered aggressive amateur to elite weight lifters or bodybuilders. Postoperative symptoms consisted of pain at the incision and discomfort from extravasation of the irrigation fluid. At an average followup of 18.7 months, all patients had returned to their sport (average, 3.2 days) and to their preoperative weight training program (average, 9.1 days). They continued to be asymptomatic throughout the follow-up period and were able to increase both their training volume and strength from preoperative levels. Limited arthroscopic resection of the distal clavicle for isolated atraumatic osteolysis is a viable alternative for the weight lifter or bodybuilder. The ability to continue training without significant interruption as well as a more acceptable cosmetic appearance are benefits for these patients. Limited arthroscopic resection of the distal clavicle may be sufficient for this entity in this patient population, rather than the 1 to 2 cm previously reported. A sport-specific functional outcome questionnaire has been developed for this patient population.

Episodic acute hypotonia after Nd:YAG laser capsulotomy--retinal function and choroidal swelling.

In a patient with uveitis who had been treated with Nd:YAG laser capsulotomy after cataract surgery, several episodes of acute hypotonia occurred which were associated with changes in clinical tests of the eye and of visual function. Immunosuppressive and immunomodulating treatment appeared to reverse the changes in intraocular pressure and normalise the test results. The significance of these observations is discussed.

Clinical efficacy of haemorheological treatment using plasma exchange, selective adsorption and membrane differential filtration in maculopathy, retinal vein occlusion and uveal effusion syndrome.

The aim of the study was to test the clinical efficacy of haemorheological treatment with extracorporeal techniques in ocular diseases. We treated patients suffering from maculopathies of different origin: age-related (AMD, n = 17), uveitis-associated (n = 14) and myopia-associated maculopathy (n = 5). We also treated patients with uveal effusion syndrome (n = 3) and central retinal vein occlusion (n = 4) resistant to haemodilution or steroid therapy. The treatment consisted of plasma exchange, selective adsorption with a tryptophan-polyvinylalcohol adsorber and membrane differential filtration. Maculopathy patients underwent two treatments while the other patients received between 1 and 7 treatments. Pulsatile ocular blood flow was measured in 10 patients before and after therapy. The main parameter for evaluating clinical outcome was the change in visual acuity. Severe side-effects did not occur. The rheological parameters including plasma viscosity, whole blood viscosity and erythrocyte aggregation were statistically significantly lowered. Of 36 patients suffering from maculopathy, 25 showed an improvement of at least 1 line of visual acuity after therapy, 7/17 patients in AMD, 6/14 in uveitis and 0/5 in myopia improved 3 lines or more. All patients suffering from retinal vein occlusion improved at least 1 line and two showed an improvement of 3 lines or more. In uveal effusion syndrome, an improvement of 3 lines or more was reached in all patients. Plasma exchange, selective adsorption and membrane differential filtration are effective rheological treatment approaches to improving visual acuity in patients suffering from maculopathy except myopia-associated maculopathy. Efficacy in patients suffering from central retinal vein occlusion and uveal effusion syndrome was proven, even when the patients were resistant to previous haemodilution or steroid therapy. We conclude that a rheological approach should be considered before invasive methods such as laser coagulation, radiation therapy or surgery are applied.