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Coupling between molecular vibrations leads to collective vibrational states with spectral features sensitive to local molecular order. This provides spectroscopic access to the low-frequency intermolecular energy landscape. In its nanospectroscopic implementation, this technique of vibrational coupling nanocrystallography (VCNC) offers information on molecular disorder and domain formation with nanometer spatial resolution. However, deriving local molecular order relies on prior knowledge of the transition dipole magnitude and crystal structure of the underlying ordered phase. Here we develop a quantitative model for VCNC by relating nano-FTIR collective vibrational spectra to the molecular crystal structure from X-ray crystallography. We experimentally validate our approach at the example of a metal organic porphyrin complex with a carbonyl ligand as the probe vibration. This framework establishes VCNC as a powerful tool for measuring low-energy molecular interactions, wave function delocalization, nanoscale disorder, and domain formation in a wide range of molecular systems.

Wisconsin Ginseng (WG) is a unique product primarily grown around Marathon, Wis. Its limited production area and specialized growing conditions give it certain marketing and 'rural development' advantages, although these [...]

Glut Cooperative, a worker-owned food cooperative in Mt. Rainier, Md., is located within a food desert and near several other food deserts in Prince George's County, Maryland, and Washington, D.C. [...]

Scholars of cooperative topics are praising a new book about the history of African Americans and their involvement in cooperatives: Collective Courage: A History of African-American Cooperative Economic Thought and [...]

Background: Patient involvement in decision-making plays a prominent role in improving the quality of healthcare. Despite this, shared decision-making is not routinely implemented. However, electronic assessment tools that capture patients’ history, symptoms, opinions and values prior to their medical appointment are used by healthcare professionals during patient consultations to facilitate shared decision-making.Objective: To assess the effectiveness of electronic assessment tools to improve the shared decision-making process.Method: A systematic review was conducted following PRISMA guidelines. Published literature was searched on MEDLINE, EMBASE and PsycINFO to identify potentially relevant studies. Data were extracted and analysed narratively.Results: Seventeen articles, representing 4004 participants, were included in this review. The main findings were significant improvement in patient–provider communication and provider management of patient condition in the intervention group compared to the control group. In contrast, patient–provider satisfaction and time efficiency were assessed by relatively few included studies, and the effects of these outcomes were inconclusive.Conclusion: This review found that communication and healthcare professional’s management of a patient’s condition improves because of the use of electronic questionnaires. This is encouraging because the process of shared decision-making is reliant on high-quality communication between healthcare professionals and patients.Implications: We found that this intervention is especially important for people with chronic diseases, as they need to establish a long-term relationship with their healthcare provider and agree to a treatment plan that aligns with their values. More rigorous research with validated instruments is required.

Pelvic organ prolapse is the descent of one or more pelvic organs, (including the bladder, uterus and rectum) from their normal anatomical position into the vaginal canal. Many patients with pelvic organ prolapse can be managed conservatively in the community with the use of supervised pelvic floor muscle training and/or vaginal pessaries. This article explains how to assess and conservatively treat pelvic organ prolapse, with particular focus on how to fit and manage vaginal pessaries.

The Council on Food, Agriculture and (Resource Economics (C-FARE) held a conference in Washington, D.C., on Aug. 4 titled: 'Agricultural Cooperatives: Economics, Opportunities and Structure in a New Era of [...]

When Tillamook County Creamery Association voted in 2004 to ban use of synthetic bovine growth hormone (rBGH) by its producer-members, it triggered a conflict within its membership and with Monsanto [...]

The long, historic trend in U.S. agricultural development has been toward ever-fewer, larger farms--a process some have likened to being on a treadmill. Cycle after cycle, fewer farmers on larger [...]

Agricultural cooperatives have a long history of helping farmers achieve their goals. For generations, they have enabled U.S. farmers to address recurring concerns: low crop and livestock prices, the high [...]

Press coverage of member reaction to recent closings of several local grain elevators by South Dakota Wheat Growers (SDWG) underscores one of many dilemmas faced by cooperatives in maintaining business [...]

AbstractResearch on presidential power delineates between a modern era of relative autonomy and an earlier period of congressional dominance. What drove this change? Unlike prior arguments about presidential entrepreneurship and the rise of the United States as a global power, we attribute the emergence of the modern presidency partially to an institutional change—the adoption of direct election of senators that culminated in the 17th Amendment. With direct election, senators were selected by individual voters rather than state legislators. These senators answered to a new principal—the general public—that was (in the aggregate) less informed and less interested in foreign policy. As a result, senators had less incentive to constrain presidential foreign policy preferences. We find evidence for this shift in the relationship between the piecemeal adoption of direct election and senate votes to delegate foreign policy authority to the executive. The implication is that the direct election of senators played an underappreciated role in the emergence of the modern presidency.

During the past several (decades, the number of U.S. farms has declined while the size of remaining farms (measured by acreage and volume of output) has increased, although there has [...]

During the past several decades, U.S. farm numbers have increased in two farm categories: those with annual sales of less than $2,500 and those with sales of more than $1 [...]

[ILLUSTRATION OMITTED] During the past decade, understanding the multifunctional nature of agriculture has emerged in scientific and farm policy debates. New language and new terms are emerging. Talk about MFA [...]

Menopause is the cessation of menstruation; it typically occurs at around 51 years of age. The postmenopausal phase of life is linked to a variety of health conditions, including osteoporosis, cardiovascular disease and cognitive decline. Beyond symptom control, hormonal replacement therapy (HRT) reduces the incidence of chronic health conditions. Some unfounded concerns and misunderstanding about the risks of HRT contribute to a low uptake of HRT, currently around 10% of menopausal women. This article highlights the symptoms of menopause and treatment options available. As the majority of menopause management occurs in primary care, a good understanding of the risks and benefits is paramount when guiding patients to make informed decisions about the treatment options.

We use the two-photon excited fluorescence method to determine the two-photon absorption (2PA) cross sections of three series of (fluorenyl benzothiazole) gold(I) complexes in the visible wavelength range from 570 to 700 nm. We compare the effect of ancillary ligand substitutions on the 2PA magnitudes and find that the ancillary ligand does not drastically affect either the magnitude or the shape of 2PA. Even so, moderate 2PA cross sections were measured that ranged from 10 to 1000 s of GM (Göppert–Mayer, =10^−50cm^4s/photon), making these types of complexes nonlinear optical materials for two-photon absorbing applications.

Author's note: An earlier version of this paper was published by the author in 1986, during a period of intense merger, consolidation and acquisition activity by cooperatives and other businesses. [...]

Shame on you and the SKEPTICAL INQUIRER for touting the IPCC's Fourth Assessment Report as science. Scientists do not prove theories right or wrong by assessing and evaluating published research [...]

When cooperatives are in their early formative stages, they can often resemble social movements. Social movements are a kind of group action, composed of individuals with common interests, seeking to [...]

Order, disorder, and domains affect many of the functional properties in self-assembled monolayers (SAMs). However, carrier transport, wettability, and chemical reactivity are often associated with collective effects, where conventional imaging techniques have limited sensitivity to the underlying intermolecular coupling. Here we demonstrate vibrational excitons as a molecular ruler of intermolecular wave function delocalization and nanodomain size in SAMs. In the model system of a 4-nitrothiophenol (4-NTP) SAM on gold, we resolve coupling-induced peak shifts of the nitro symmetric stretch mode with full spatio-spectral infrared scattering scanning near-field optical microscopy. From modeling of the underlying 2D Hamiltonian, we infer domain sizes and their distribution ranging from 3 to 12 nm across a field of view on the micrometer scale. This approach of vibrational exciton nanoimaging is generally applicable to study structural phases and domains in SAMs and other molecular interfaces.

Gynaecological cancers are malignancies involving the female genital tract, of which there are five types: ovarian, uterine, cervical, vaginal and vulval cancer. Every year in the UK, more than 21 000 women are diagnosed with a gynaecological cancer and there are 8000 deaths. The NHS is aiming for earlier diagnosis, and campaigns from various UK cancer groups are hoping to increase awareness among women. This article will discuss the epidemiology, risk factors and clinical features of gynaecological cancers and provide a summary of investigation and management in primary and secondary care.

AbstractAgronomic crops engineered with resistance to 2,4-D or dicamba have been commercialized and widely adopted throughout the United States. Because of this, increased use of these herbicides in time and space has increased damage to sensitive crops. From 2014 to 2016, cucumber and cantaloupe studies were conducted in Tifton, GA, to demonstrate how auxinic herbicides (namely, 2,4-D or dicamba), herbicide rate (1/75 or 1/250 field use), and application timing (26, 16, and 7 d before harvest [DBH] of cucumber; 54, 31, and 18 DBH of cantaloupe) influenced crop injury, growth, yield, and herbicide residue accumulation in marketable fruit. Greater visual injury, reductions in vine growth, and yield loss were observed at higher rates when herbicides were applied during early-season vegetative growth compared with late-season with fruit development. Dicamba was more injurious in cucumber, whereas cantaloupe responded similarly to both herbicides. For cucumber, total fruit number and relative weights were reduced (16% to 19%) when either herbicide was applied at the 1/75 rate 26 DBH. Cantaloupe fruit weight was also reduced 21% and 10% when either herbicide was applied at the 1/75 rate 54 or 31 DBH, respectively. Residue analysis noted applications made closer to harvest were more likely to be detectable in fruit than earlier applications. In cucumber, dicamba was detected at both rates when applied 7 DBH, whereas in cantaloupe, it was detected at both rates when applied 18 or 31 DBH in 2016 and at the 1/75 rate applied 18 or 31 DBH in 2014. Detectable amounts of 2,4-D were not observed in cucumber but were detected in cantaloupe when applied at either rate 18 or 31 DBH. Although early-season injury will more likely reduce cucumber or cantaloupe yields, the quantity of herbicide residue detected will be most influenced by the time interval between the off-target incident and sampling.

Editor's Note: USDA/RBS Research Report 192, 'Problems and Issues Facing Farmer Cooperatives,' examines more fully the various survey responses discussed in this article. It should be available by late June [...]

While most common‐space estimations rely upon members who served in both the House and Senate as “bridges” to scale the remaining members, this assumes that these “bridge members” do not change their preferences when they change chambers. Such an assumption conflicts with standard notions of representation, that is, that legislators’ votes reflect (at least to some degree) the wishes of their constituents. We examine the constancy of this common‐space voting assumption by focusing on a subset of House members who move to the Senate: those who come from statewide House districts. Using these members as the bridge actors—and thus bridging by constituency explicitly—in a one‐dimensional item response theory model, we find that the standard assumption of chamber switchers in common‐space estimations is technically, but immaterially, false. While there are statistically distinguishable differences in House and Senate voting records for chamber switchers, they are not sufficiently large to meaningfully undermine bridging.

Five Pt(II) complexes bearing a 3,6-di-tert-butyl-1,8-bis(1H-imidazol-1-yl)-9H-carbazole (BIMCA) backbone and different isonitrile ancillary ligands were synthesized and photophysically characterized. The solid-state structures were determined by X-ray crystallography, all of which showed a distorted-square-planar geometry where isonitrile moieties protrude from the Pt–carbazole plane. In the solid state, these complexes show biexponential phosphorescence with lifetimes up to 25 ms and quantum yields ranging from 5% to 22%. In solution, these complexes are weakly emissive with a nanosecond-scale lifetime. Density functional theory calculations indicate that the highest occupied Kohn–Sham orbital (HOMO) and the lowest unoccupied Kohn–Sham orbital (LUMO) reside primarily on the MeBIMCA ligand.

A phone call handled poorly on a hectic day at the co-op, or even an invoice mistake on a good day, may have the same kind of impact on an [...]

Four new laterally asymmetric dinuclear gold(I) complexes made from a new chromophoric ligand (Au-DiBTF0–3) have been characterized. Changing the organic ancillary ligand from a phosphine ((Au-DiBTF0(PMe3) and Au-DiBTF1(PCy3)) to an N-heterocyclic carbene (Au-DiBTF2) with an alkynyl linking moiety or modifying the alkynyl linkage to a triazolyl moiety with the ancillary ligand being an N-heterocyclic carbene (Au-DiBTF3) impacts the ground- and excited-state properties of these systems. All four complexes exhibit structured absorption and emission spectra with weak phosphorescence. A bathochromic shift is observed in both the ground-state absorption and luminescence spectra as the series varies from Au-DiBTF0to Au-DiBTF3. The dinuclear alkynyl complexes (Au-DiBTF0–2) display decreased fluorescence lifetimes and fluorescence quantum yields along with more efficient intersystem crossing when the capping ligand is changed from a trialkylphosphine to an N-heterocyclic carbene. This change results in comparable rates of radiative decay and intersystem crossing and negligible rates of nonradiative decay. Changing the π-bridging moiety (Au-DiBTF3) results in a diminished fluorescence quantum yield, shorter fluorescence lifetime, and increased intersystem quantum yield, resulting in faster intersystem crossing accompanied by slower radiative decay and more efficient nonradiative decay relative to the alkynyl-bridged complexes. Density functional theory calculations are in accord with the observed photophysics, with nearly identical S1-to-T2energy gaps for the dinuclear alkynyl complexes (Au-DiBTF0and -2) and a smaller energy gap for Au-DiBTF3. Experimentally, Au-DiBTF3has the highest rate constant and quantum yield of intersystem crossing of the new gold(I) organometallics.

Recurrent urinary tract infection (UTI) is a common, and burdensome, condition that accounts for up to 3% of GP appointments per year. It affects over half of women in their lifetime, disproportionately affecting post-menopausal women. Most presentations of recurrent UTI will be to GPs, so for them to recognise and manage recurrent UTI, and when to refer to secondary care is important. This article outlines the microbial and non-microbial prophylaxis and management options available to GPs for recurrent UTI in non-pregnant women. The article will highlight when to refer patients to secondary care for further management.

Urinary incontinence is the involuntary loss of urine. It is a common ailment that affects up to 50% of women within their lifetime, and has a detrimental effect on quality of life. There are many effective treatments, including conservative and medical management, available in the community before referral to secondary care. It is essential that GPs have a good understanding of the assessment, primary management and indications for onward referral of this common complaint that has a significant impact on quality of life.

Conventional assessment of overactive bladder syndrome uses invasive pressure-measuring catheters to detect bladder contractions (urodynamics). We hypothesised that bladder shape changes detected and measured using transabdominal ultrasound scan could provide a non-invasive and clinically useful alternative investigation of bladder contractions. This feasibility study evaluated a novel transabdominal ultrasound scan bladder shape test during conventional urodynamics and physiological bladder filling. The aim was to initially evaluate and refine a non-invasive approach for detecting and quantifying bladder shape changes associated with involuntary bladder contractions. To develop measurement techniques and characterise bladder shape changes during bladder filling, healthy female volunteers (n=20) and women with overactive bladder symptoms who had previously undergone urodynamics (n=30) completed symptom questionnaires and bladder diaries. The bladder shape test protocol included consumption of 1 l water before undergoing serial transabdominal ultrasound scan imaging of the bladder during physiological bladder filling and during episodes of urgency. In a further group of women with overactive bladder (n=22), serial transabdominal ultrasound scan images were captured during urodynamics so that shape changes occurring with bladder contractions could be characterised. In both healthy volunteers and women with overactive bladder, the transverse view of the bladder provided the most reliable plane to characterise and measure bladder shape changes. A sphericity index derived from the ratio between maximum inscribed and minimum circumscribed ellipses (πac2(inner)/πac2(outer)) offered a reliable and reproducible measurement system. Of participants undergoing transabdominal ultrasound scan during urodynamics, there were significant measurable differences in sphericity index between patients with bladder contractions (n=12) and patients with acontractile bladders (p< 0.001). Bladder shape changes detected during physiological filling and urodynamics have provided preliminary evidence to support further research into bladder shape test as a non-invasive diagnostic tool to identify involuntary bladder contractions in patients with overactive bladder syndrome.

Several letters to the editor are presented in response to previous articles, including "More Employees Should Have a Say in ESOPs," in the August 15, 1988 issue, "Beijing Opens the Door to Bubble Gum and Band-Aids," in the August 8, 1988 issue, and "Where Water is Money in the Bank," in the August 15, 1988 issue.

There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention in this field, and in most cases, sterically driven approaches are used to optimize their lifetimes. This study presents a series of three-coordinate copper(I) complexes (Cu1–Cu3) where the excited-state lifetime is extended by triplet–triplet energy transfer. The heteroleptic compounds feature a cyclohexyl-substituted β-diketiminate (CyNacNacMe) paired with aryl isocyanide ligands, giving the general formula Cu(CyNacNacMe)(CN-Ar) (CN-dmp = 2,6-dimethylphenyl isocyanide for Cu1; CN-pyr = 1-pyrenyl isocyanide for Cu2; CN-dmp-pyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide for Cu3). The nature, energies, and dynamics of the low-energy triplet excited states are assessed with a combination of photoluminescence measurements at room temperature and 77 K, ultrafast transient absorption (UFTA) spectroscopy, and DFT calculations. The complexes with the pyrene-decorated isocyanides (Cu2and Cu3) exhibit extended excited-state lifetimes resulting from triplet–triplet energy transfer (TTET) between the short-lived charge-transfer excited state (3CT) and the long-lived pyrene-centered triplet state (3pyr). This TTET process is irreversible in Cu3, producing exclusively the 3pyr state, and in Cu2, the 3CT and 3pyr states are nearly isoenergetic, enabling reversible TTET and long-lived 3CT luminescence. The improved photophysical properties in Cu2and Cu3result in improvements in activity for both photocatalytic stilbene E/Zisomerization via triplet energy transfer and photoredox transformations involving hydrodebromination and C–O bond activation. These results illustrate that the extended excited-state lifetimes achieved through TTET result in newly conceived photosynthetically relevant earth-abundant transition metal complexes.

Fire pumps are perhaps the most critical single piece of fire protection equipment installed at a site. Just like people, fire pumps come in all shapes and sizes. Fire pumps [...]

Gynaecological problems in primary care are common. Some gynaecological conditions present as emergencies, requiring rapid referral to secondary care for review and treatment. GPs are likely to see such patients more often in out-of-hours sessions. This article will consider common gynaecological emergencies including pelvic inflammatory disease, bleeding and pain in early pregnancy, vulval abscess, Bartholin’s cyst abscess and ovarian cyst accidents. The article aims to guide assessment of patients in primary care including information on aetiology, risk factors, clinical features, initial investigations, management and referral.

Bis-cyclometalated iridium complexes with enhanced phosphorescence quantum yields in the red region of the visible spectrum are described. Here, we demonstrate that incorporating strongly π-donating, nitrogen-containing β-ketoiminate (acNac), β-diketiminate (NacNac), and N,N′-diisopropylbenzamidinate (dipba) ancillary ligands can demonstrably perturb the excited-state kinetics, leading to enhanced photoluminescence quantum yields (ΦPL) for red-emitting compounds. A comprehensive study of the quantum yields and lifetimes for these complexes reveals that for the compounds with the highest quantum yields, the radiative rate constant (kr) is significantly higher than that of related complexes, and contributes substantially to the increase in ΦPL. Experimental and computational evidence is consistent with the notion that an increase in spin–orbit coupling, caused by an enhancement of the metal-to-ligand charge transfer (MLCT) character of the excited state via destabilization of the HOMO, is mainly responsible for the faster radiative rates. One of the compounds was shown to be effective as the emissive dopant in an organic light-emitting diode device.

AbstractThe commercial release of crops with engineered resistance to 2,4-D and dicamba will alter the spatial and temporal use of these herbicides. This, in turn, has elicited concerns about off-target injury to sensitive crops. In 2014 and 2015, studies were conducted in Tifton, GA, to describe how herbicide (2,4-D and dicamba), herbicide rate (1/75 and 1/250 field use), and application timing (20, 40, and 60 DAP) influence watermelon injury, vine development, yield, and the accumulation of herbicide residues in marketable fruit. In general, greater visual injury and reductions in vine growth, relative to the non-treated check, were observed when herbicide applications were made before watermelon plants had begun to flower. Although the main effects of herbicide and rate were less influential than the timing of applications with respect to plant development, the 1/75 rates were more injurious than the 1/250 rates; dicamba was more injurious than 2,4-D. In 2014, the 1/75 and 1/250 rates of each herbicide reduced marketable fruit numbers 13 to 20%, but only for the 20 DAP application. The 1/75 rate of each herbicide when applied at either 20 or 40 DAP reduced the number of fruit harvested per plot in 2015. Dicamba residues were detected in marketable fruit when the 1/75 rate in 2014 and 2015 and the 1/250 rate in 2015 was applied to plants at 40 or 60 DAP. Residues of 2,4-D were detected in 2015 when the 1/75 and 1/250 rates were applied at 60 DAP. Across both years, the maximum level of residue detected was 0.030 ppm. While early season injury may reduce watermelon yields, herbicide residue detection is more likely in marketable fruit when an off-target contact incident occurs closer to harvest.

Vasa praevia is described as the unprotected fetal vessels traversing through the placental membranes over the cervical os, below the fetal presenting part and unprotected by placental tissue or the umbilical cord. It is often not detected antenatally and presents with painless bleeding and rapid fetal compromise after spontaneous or artificial rupture of the membranes, which causes trauma to these vessels. It is a rare condition affecting one in 2500 pregnancies and has a reported perinatal mortality rate of up to 60%. More than 80% of cases of vasa praevia have at least one risk factor for the condition and it has been shown that identification of vasa praevia antenatally results in fetal survival rates of up to 97%. Risk factors include placenta praevia, velamentous cord insertion, bi-lobed placenta, succenturiate lobe, assisted reproduction and multiple pregnancy. Screening for vasa praevia with transvaginal ultrasound has been shown to be sensitive and cost effective when used in a targeted population where risk factors are present. Here, we present the antenatal assessment and management of a case of vasa praevia detected during the routine 20-week anatomy scan of a healthy primigravida, which resulted in elective caesarean section delivery of a healthy baby at 36 weeks' gestation. The pathophysiology of vasa praevia is discussed and the methods and role of screening for this rare but serious condition are appraised.