Host Dependency of Boundary between Strong and Weak Crystal Field Strength of Cr3+ Luminescence.

Cr3+ doped near-infrared phosphors hold significant applications and generate considerable research interest. The critical parameter for assessing the strength of the crystal field for Cr3+ in the Tanabe-Sugano diagram is the boundary value of Dq/B, representing the ratio of crystal field splitting to the Racah parameter B. Nevertheless, there are conflicting values for this parameter, as reported in various studies, such as 2.1, 2.2, and 2.3 for C/B = 4.5-4.8. Moreover, some Cr3+ doped phosphors with wide-band emissions exhibit a Dq/B value that falls within the region of a contradictory strong field. In this study, we numerically determine the boundary value of Dq/B, which distinguishes between strong and weak fields. The results then demonstrate a dependence on the host material and are correlated with the values of Racah parameters B and C. This work resolves the inconsistency between the boundary values of Dq/B and the emission profile of Cr3+, providing researchers with a more profound comprehension of Cr3+ luminescence.

Invited review: integration of technologies and systems for precision animal agriculture-a case study on precision dairy farming.

Precision livestock farming (PLF) offers a strategic solution to enhance the management capacity of large animal groups, while simultaneously improving profitability, efficiency, and minimizing environmental impacts associated with livestock production systems. Additionally, PLF contributes to optimizing the ability to manage and monitor animal welfare while providing solutions to global grand challenges posed by the growing demand for animal products and ensuring global food security. By enabling a return to the "per animal" approach by harnessing technological advancements, PLF enables cost-effective, individualized care for animals through enhanced monitoring and control capabilities within complex farming systems. Meeting the nutritional requirements of a global population exponentially approaching ten billion people will likely require the density of animal proteins for decades to come. The development and application of digital technologies are critical to facilitate the responsible and sustainable intensification of livestock production over the next several decades to maximize the potential benefits of PLF. Real-time continuous monitoring of each animal is expected to enable more precise and accurate tracking and management of health and well-being. Importantly, the digitalization of agriculture is expected to provide collateral benefits of ensuring auditability in value chains while assuaging concerns associated with labor shortages. Despite notable advances in PLF technology adoption, a number of critical concerns currently limit the viability of these state-of-the-art technologies. The potential benefits of PLF for livestock management systems which are enabled by autonomous continuous monitoring and environmental control can be rapidly enhanced through an Internet of Things approach to monitoring and (where appropriate) closed-loop management. In this paper, we analyze the multilayered network of sensors, actuators, communication, networking, and analytics currently used in PLF, focusing on dairy farming as an illustrative example. We explore the current state-of-the-art, identify key shortcomings, and propose potential solutions to bridge the gap between technology and animal agriculture. Additionally, we examine the potential implications of advancements in communication, robotics, and artificial intelligence on the health, security, and welfare of animals.

Precision technologies are revolutionizing animal agriculture by enhancing the management of animal welfare and productivity. To fully realize the potential benefits of precision livestock farming (PLF), the development and application of digital technologies are needed to facilitate the responsible and sustainable intensification of livestock production over the next several decades. Importantly, the digitalization of agriculture is expected to provide collateral benefits of ensuring audibility in value chains while assuaging concerns associated with labor shortages. In this paper, we analyze the multilayered network of sensors, actuators, communication, and analytics currently in use in PLF. We analyze the various aspects of sensing, communication, networking, and intelligence on the farm leveraging dairy farms as an example system. We also discuss the potential implications of advancements in communication, robotics, and artificial intelligence on the security and welfare of animals.

Short-Term Adaptation of Dairy Cattle Production Parameters to Individualized Changes in Dietary Top Dress.

Immediate and short-term changes in diet composition can support individualized, real-time interventions in precision dairy production systems, and might increase feed efficiency (FE) of dairy cattle in the short-term. The objective of this study was to determine immediate and short-term effects of changes in diet composition on production parameters of dairy cattle fed varying amounts of top dressed commodities. A 4 × 4 replicated Latin square design was used to evaluate responses of twenty-four Holstein cows fed either no top dress (Control) or increasing amounts of: corn grain (CG), soybean meal (SBM), or chopped mixed grass hay (GH) top dressed on a total mixed ration (TMR) over four, 9-day periods. Throughout each period, top dressed commodities were incrementally increased, providing 0% to 20% of calculated net energy of lactation (NEL) intake. Measured production responses were analyzed for each 9-d period using a mixed-effects model considering two different time ranges. Samples collected from d 3 and 4 and from d 7 and 8 of each period were averaged and used to reflect "immediate" vs. "short-term" responses, respectively. In the immediate response time frame, control fed cows had lower milk yield, milk fat yield, and milk true protein yield than CG and SBM supplemented animals but similar responses to GH supplemented animals. Milk fat and protein percentages were not affected by top dress type in the immediate term. In the short-term response time-frame, GH supplemented animals had lower DMI and milk fat yield than all other groups. Control and GH supplemented cows had lower milk yield than CG and SBM fed cows. In the immediate response time frame, FE of SBM supplemented cows was superior to other groups. In the short-term time frame, FE of GH and SBM groups was improved over the control group. Results suggest that lactating dairy cows show rapid performance responses to small (<20% NEL) changes in dietary composition, which may be leveraged within automated precision feeding systems to optimize efficiency of production. Before this potential can be realized, further research is needed to examine integration of such strategies into automatic feeding systems and downstream impacts on individual animal FE and farm profitability.

pH-Selective Cytotoxicity of pHLIP-Antimicrobial Peptide Conjugates.

Positively charged antimicrobial peptides have become promising agents for the treatment of cancer by inducing apoptosis though their preferential binding and disruption of negatively charged membranes, such as the mitochondrial membrane. (KLAKLAK)2 is such a peptide but due to its polarity, it cannot cross the cellular membrane and therefore relies on the use of a delivery agent. For targeted delivery, previous studies have relied on cell penetrating peptides, nanoparticles or specific biomarkers. Herein, we investigated the first use of pHLIP to selectively target and directly translocate (KLAKLAK)2 into the cytoplasm of breast cancer cells, based on the acidic tumor micro-environment. With the goal of identifying a lead conjugate with optimized selective cytotoxicity towards cancer cells, we analyzed a family of (KLAKLAK)2 analogs with varying size, polarity and charge. We present a highly efficacious pHLIP conjugate that selectively induces concentration- and pH-dependent toxicity in breast cancer cells.

Trends in Atomic Parameters for Crystals and Free Ions across the Lanthanide Series: The Case of LaCl3:Ln(3+).

Analyses of the crystal field energy levels of the series LaCl3:Ln(3+) using a semiempirical Hamiltonian shows that only five ions (Pr, Nd, Pm, Dy, Ho) meet the criteria to avoid overfitting of the atomic part. A new parameter (SNES) has been introduced to represent the strength of the normalized electrostatic repulsion for these ions. This parameter varies linearly (R(2)adj = 0.9994, N = 5) with the reciprocal of the radius of the tripositive lanthanide ion, as expected from the form of repulsive Coulomb interaction. The Slater parameters from the crystal field analyses, F(k)(corr) (i.e., corrected for the effects of the two-particle component of the three-body operator associated with the T(2) parameter), exhibit an exponential variation with the number of electrons, n, in 4f(n). This is explained by reference to the radial part of a hydrogen-like wave function. The ratio of F(k)(corr) with the ab initio free ion Slater parameter F(k)(ab initio) varies linearly with n. Fitted parameters F(k)(corr: free ion) from the free ion data for Pr(3+) and Nd(3+) show that the corresponding ab initio values are between 14 and 27% too high. The spin-orbit coupling constant from crystal field analyses (ζ4f) exhibits a quartic variation with atomic number, and the ratio ζ4f/ζ4f(ab initio) follows an exponential growth model with n. The results serve to confirm the hypothesis that smooth trends can be observed across the Ln(3+) series for the fitted parameters despite the fact that the majority of experimental data is lacking.

Efficient doping and energy transfer from ZnO to Eu3+ ions in Eu(3+)-doped ZnO nanocrystals.

Successful doping of Eu3+ ions into ZnO nanocrystals has been realized by using a low temperature wet chemical doping technique. The substitution of Eu3+ for Zn2+ is shown to be dominant in the Eu-doped ZnO nanocrystals by analyzing the X-ray diffraction patterns, transmission electron microscopy images, Raman and selectively excited photoluminescence spectra. Measurement of the luminescence from the samples shows that the excited ZnO transfers the excited energy efficiently to the doped Eu3+ ions, giving rise to efficient emission at red spectral region. The red emission quantum yield is measured to be 31% at room temperature. The temperature dependence of photoluminescence and the photoluminescence excitation spectra have also been investigated, showing strong energy coupling between the ZnO host and Eu3+ ions through free and bound excitons. The result indicates that Eu3+ ion-doped ZnO nanocrystals are promising light-conversion materials and have potential application in highly distinguishable emissive flat panel display and LED backlights.

Speciated isotope dilution analysis of Cr(III) and Cr(VI) in water by ICP-DRC-MS.

An isotope dilution method has been developed for the speciation analysis of chromium in natural waters which accounts for species interconversions without the requirement of a separation instrument connected to the mass spectrometer. The method involves (i) in-situ spiking of the sample with isotopically enriched chromium species; (ii) separation of chromium species by precipitation with iron hydroxide; (iii) careful measurement of isotope ratios using an inductively coupled plasma mass spectrometer (ICP-MS) with a dynamic reaction cell (DRC) to remove isobaric polyatomic interferences. The method detection limits are 0.4 microg L(-1) for Cr(III) and 0.04 microg L(-1) for Cr(VI). The method is demonstrated for the speciation of Cr(III) and Cr(VI) in local nullah and synthetically spiked water samples. The percentage of conversion from Cr(III) to Cr(VI) increased from 5.9% to 9.3% with increase of the concentration of Cr(VI) and Cr(III) from 1 to 100 microg L(-1), while the reverse conversion from Cr(VI) to Cr(III) was observed within a range between 0.9% and 1.9%. The equilibrium constant for the conversion was found to be independent of the initial concentrations of Cr(III) and Cr(VI) and in the range of 1.0 (at pH 3) to 1.8 (at pH 10). The precision of the method is better than that of the DPC method for Cr(VI) analysis, with the added bonuses of freedom from interferences and simultaneous Cr(III) determination.

Immunization of puppies in the presence of maternally derived antibodies against canine distemper virus.

Vaccination of dams with modified-live canine distemper virus (CDV) vaccines will elicit high concentrations of colostral antibody, that although vital for protection of the pup during the first weeks of life, can interfere with active vaccination against the virus. In the present study, 12 pups, 7-9 weeks of age, with maternally derived immunity to CDV, were vaccinated with a canarypox-vectored CDV vaccine. These pups were protected against intravenous challenge with CDV. Three littermate pups that were unvaccinated all developed clinical signs of infection after challenge, and two of these control pups died.

Synthesis and luminescence of nano-insulators doped with lanthanide ions.

This paper reviews the syntheses, particle-size measurements and various aspects of the optical spectra of lanthanide ion doped insulating nanomaterials, with the focus upon the sesquioxides, and it contrasts their behaviour with bulk materials.

2-year study of chemical composition of bulk deposition in a south China coastal city: comparison with east Asian cities.

Using the emission strengths of the precursor gases, the nature of soil in China, the ventilation power and half value rainout region length, the nss-SO42-, NO3-, Ca2+, and NH4+ concentrations, and pH of rainwater at Hong Kong and other cities of China and Japan are compared and rationalized. The chemical composition of Hong Kong bulk deposition from 1998 to 2000 is taken from our collection and analysis of 156 daily samples. The volume-weighted average (VWA) pH is 4.2 over the whole study period. Nonsea salt- (nss-) sulfate is the most abundant species in the samples, and the pH mostly depended upon the concentrations of the major species nss-SO42, NO3-, Ca2+, and NH4+. All species concentrations show higher levels in the cold season (especially NO3- and Ca2+), which indicates the dominant dilution effects in the warm season due to heavy rainfall and the influence of the continental outflow of pollutants during the cold season. For Hong Kong bulk deposition, the VWA pH is slightly lower in the cold season, and there is a slight decrease in VWA pH over the period from 1994 to 2000. The impact of acid rain in Hong Kong is briefly discussed.

O-(2-[18F]fluoroethyl)-L-tyrosine PET for monitoring the effects of convection-enhanced delivery of paclitaxel in patients with recurrent glioblastoma.

PURPOSE: Convection-enhanced delivery (CED) of paclitaxel is a new locoregional approach for patients with recurrent glioblastoma. The aim of this study was to evaluate O-(2-[(18)F]fluoroethyl)-L-tyrosine (FET) positron emission tomography (PET) in monitoring the effects of this type of direct drug delivery. METHODS: Eight patients with recurrent glioblastoma underwent CED of paclitaxel, which was infused over stereotactically placed catheters into the tumour. FET PET and MRI were performed before and 4 weeks after therapy and then at 3-month intervals to document follow-up. For quantitative evaluation, SUV(max)(tumour)/SUV(mean)(background) ratios were calculated. RESULTS: At baseline all tumours showed gadolinium enhancement and high FET uptake (SUV(max)/BG 3.2+/-0.8). Four weeks after CED, a statistically significant decrease in FET uptake was seen (SUV(max)/BG-17%; p<0.01). During follow-up, no recurrence was observed within the CED area. Two out of eight patients with extended tumours died 4 and 5 months after treatment, most probably from local complications. Temporarily stable disease with stable FET uptake was observed in six of eight patients; this was followed by progression and increasing FET uptake ratios (+46%) distant from the CED area in five of the six patients 3-13 months after CED. One patient still presents stable FET uptake 10 months after CED. MRI showed unchanged/increasing contrast enhancement and oedema without ability to reliably assess disease progression. CONCLUSION: FET PET is a valuable tool in monitoring the effects of CED of paclitaxel. In long-term follow-up, stable or decreasing FET uptake, even in contrast-enhancing lesions, is suggestive of reactive changes, whereas increasing ratios appear always to be indicative of recurrence. Therefore, FET PET is more reliable than MRI in differentiating stable disease from tumour regrowth.

Acute radiation toxicity assessment of a 3-D conformal head and neck radiation treatment technique.

Patients undergoing radiation treatment for head and neck cancer have many critical structures within or adjacent to the treatment area. Avoiding these critical structures is more efficient and easier using 3-D conformal planning. At Sir Charles Gairdner Hospital an investigation into the acute radiation toxicity was undertaken when the head and neck treatment technique was changed from the conventional 2-D plan to the conformal 3-D plan. Although the primary target volume (PTV), fraction size and overall dose remain the same for the two techniques, differing beam configurations mean that treatment fields enter and exit through different parts of the head and neck. Ten patients were initially assessed to gain a baseline appearance of their head and neck region, and then graded weekly according to the toxicity criteria during treatment and at 4, 8 and 12 weeks after treatment. The results of the assessment indicate that there is no increase in toxicity as a result of treating using the conformal head and neck technique.

Prospective documentation and analysis of the pre- and early clinical management in severe head injury in southern Bavaria at a population based level.

Treatment of patients suffering from severe head injury is so far restricted to general procedures, whereas specific pharmacological agents of neuroprotection including hypothermia have not been found to improve the outcome in clinical trials. Albeit effective, symptomatic measures of the preclinical rescue of patients (i.e. stabilization or reestablishment of the circulatory and respiratory system) or of the early clinical care (e.g. prompt diagnosis and treatment of an intracranial space occupying mass, maintenance of a competent circulatory and respiratory system, and others) by and large constitute the current treatment based on considerable organizational and logistical efforts. These and other components of the head injury treatment are certainly worthwhile of a systematic analysis as to their efficacy or remaining deficiencies, respectively. Deficits could be associated with delays of providing preclinical rescue procedures (e.g. until intubation of the patient or administration of fluid). Delays could also be associated in the hospital with the diagnostic establishment of intracranial lesions requiring prompt neurosurgical intervention. By support of the Federal Ministry of Education and Research and under the auspices of the Forschungsverbund Neurotraumatology, University of Munich, a prospective system analysis was carried out on major aspects of the pre- and early clinical management at a population based level in patients with traumatic brain injury. Documentation of pertinent data was made from August 1998 to July 1999 covering a catchment area of Southern Bavaria (5.6 mio inhabitants). Altogether 528 cases identified to suffer from severe head injury (GCS < or = 8 or deteriorating to that level within 48 hrs) were enrolled following admission to the hospital and establishment of the diagnosis. Further, patients dying on the scene or during transport to the hospital were also documented, particularly as to the frequency of severe head injury as underlying cause of mortality. The analysis included also cases with additional peripheral trauma (polytrauma). The efficacy of the logistics and organization of the management was studied by documentation of prognosis-relevant time intervals, as for example until arrival of the rescue squad at the scene of an accident, until intubation and administration of fluid, or upon hospital admission until establishment of the CT-diagnosis and commencement of surgery or transfer to the intensive care unit, respectively. The severity of cases studied in the present analysis is evident from a mortality of far above 40% of cases admitted to the hospital, which was increased by about 20% when including prehospital mortality. The outcome data notwithstanding, the emerging results demonstrate a high efficacy of the pre- and early clinical management, as indicated by a prompt arrival of the rescue squad at the scene, a competent prehospital and early clinical management and care, indicative of a low rate of avoidable complications. It is tentatively concluded on the basis of these findings that the patient prognosis is increasingly determined by the manifestations of primary brain damage vs. the development of secondary complications.

In vitro assessment of the broad-spectrum ultraviolet protection of sunscreen products.

BACKGROUND: There are considerable data to suggest that protection from solar ultraviolet (UV) radiation will reduce the risk of acute and chronic skin damage in humans. Whereas the sun protection factor (SPF) provides an index of protection against erythemally effective solar UV, largely confined to the UVB (290-320 nm) and short-wavelength UVA (320-340 nm) region, there is currently no agreed-upon method to measure broad-spectrum protection against long-wavelength UVA (340-400 nm). OBJECTIVE: The objective of these studies was to assess the potential of in vitro UV substrate spectrophotometry and subsequent calculation of the "critical wavelength" value as a measure of broad-spectrum UV protection and as a routine, practical procedure for classification of sunscreen products. METHODS: The spectral absorption of 59 commercially available sunscreen products and multiple experimental formulas with one or more UV filters was measured. Sunscreen product, 1 mg/cm(2), was applied to a hydrated synthetic collagen substrate, preirradiated with a solar simulator, and then subjected to UV substrate spectrophotometry. Multiple determinations from 5 independent samples per product were used to calculate the critical wavelength value, defined as the wavelength at which the integral of the spectral absorbance curve reached 90% of the integral from 290 to 400 nm. RESULTS: We found that a recognized long-wave UVA active ingredient such as titanium dioxide, zinc oxide, or avobenzone is a necessary but insufficient product requirement for achieving the highest proposed broad-spectrum classification, that is, critical wavelength of 370 nm or more. Although SPF and critical wavelength are largely independent of each other, UVA absorbance must increase commensurate with SPF to maintain the same critical wavelength value. Substrate spectrophotometry and the calculation of critical wavelength can readily account for sunscreen photostability by UV preirradiation. Finally, there is also a strong positive relationship between critical wavelength and a currently available in vivo measure of UVA protection. CONCLUSION: Determination of critical wavelength by means of UV substrate spectrophotometry provides a rapid, inexpensive, and reliable measure of broad-spectrum protection, which is largely independent of SPF, yet ensures long-wavelength UVA protection commensurate with SPF. The procedure provides a routine, sensitive means of differentiating and classifying sunscreen products and, importantly, obviates the need to subject volunteers to acute exposures of high-dose, nonterrestrial UV, the health risks of which are still poorly understood.

Alterations in extracellular substances during the biofilm development of Pseudomonas aeruginosa on aluminum plates.

The chemical moieties during biofilm formation of Pseudomonas aeruginosa on aluminium plates were examined for a period of 17 days. The effect of fluid shearing upon biofilm formation has also been investigated. The Fourier transform infrared (FTIR) spectrum of the biofilm taken on the fifth day showed significant differences compared with the spectrum of the unattached bacterial cells, indicating that structural changes or modifications of the cell envelope had taken place during the development of the biofilm. Major changes were also observed in the spectrum during the subsequent development of the biofilm from day 5 to day 17. The increasing intensity of a band corresponding to the symmetric stretching mode of the carboxyl group indicated interactions between the carboxyl group and the aluminium surface. Increased bacterial colonization was also observed at the air-water interface of the aluminium plates when compared with the middle and the bottom parts. Changes in FTIR spectra of the biofilm at the bottom, at the middle, and at the air-water interface suggest that the mechanisms of bacterial attachment differed by a -COO(-) interaction at the air-water interface, and by both -COO(-) and NH3(+) groups beneath the water surface.