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Prehension, the act of reaching to grasp an object, is central to the human experience. We use it to feed ourselves, groom ourselves, and manipulate objects and tools in our environment. Such behaviors are impaired by many sensorimotor disorders, yet our current understanding of their neural control is far from complete. Current technologies for investigating human reach-to-grasp movements often utilize motion tracking systems that can be expensive, require the attachment of markers or sensors to the hands, impede natural movement and sensory feedback, and provide kinematic output that can be difficult to interpret. While generally effective for studying the stereotypical reach-to-grasp movements of healthy sighted adults, many of these technologies face additional limitations when attempting to study the unpredictable and idiosyncratic reach-to-grasp movements of young infants, unsighted adults, and patients with neurological disorders. Thus, we present a novel, inexpensive, and highly reliable yet flexible protocol for quantifying the temporal and kinematic structure of idiosyncratic reach-to-grasp movements in humans. High speed video cameras capture multiple views of the reach-to-grasp movement. Frame-by-frame video analysis is then used to document the timing and magnitude of pre-defined behavioral events such as movement start, collection, maximum height, peak aperture, first contact, and final grasp. The temporal structure of the movement is reconstructed by documenting the relative frame number of each event while the kinematic structure of the hand is quantified using the ruler or measure function in photo editing software to calibrate 2 dimensional linear distances between two body parts or between a body part and the target. Frame-by-frame video analysis can provide a quantitative and comprehensive description of idiosyncratic reach-to-grasp movements and will enable researchers to expand their area of investigation to include a greater range of naturalistic prehensile behaviors, guided by a wider variety of sensory modalities, in both healthy and clinical populations.

Epstein-Barr virus (EBV) causes infectious mononucleosis and can lead to lymphoproliferative diseases. We evaluated the effects of valganciclovir on oral EBV shedding in a randomized, double-blind, placebo-controlled study. Twenty-six men received oral valganciclovir or daily placebo for 8 weeks, followed by a 2-week "washout period" and then 8 weeks of the alternative treatment. Valganciclovir reduced the proportion of days with EBV detected from 61.3% to 17.8% (relative risk, 0.28; 95% confidence interval [CI], .21-.41; P < .001), and quantity of virus detected by 0.77 logs (95% CI, .62-.91 logs; P < .001). Further investigations into the impact of valganciclovir on EBV-associated diseases are needed.

Mice are adept in the use of their hands for activities such as feeding, which has led to their use in investigations of the neural basis of skilled-movements. We describe the syntactic organization of pasta-eating and the structure of hand movements used for pasta manipulation by the head-fixed mouse. An ethogram of mice consuming pieces of spaghetti reveals that they eat in bite/chew bouts. A bout begins with pasta lifted to the mouth and then manipulated with hand movements into a preferred orientation for biting. Manipulation involves many hand release-reach movements, each with a similar structure. A hand is advanced from a digit closed and flexed (collect) position to a digit extended and open position (overgrasp) and then to a digit closed and flexed (grasp) position. Reach distance, hand shaping, and grasp patterns featuring precision grasps or whole hand grasps are related. To bite, mice display hand preference and asymmetric grasps; one hand (guide grasp) directs food into the mouth and the other stabilizes the pasta for biting. When chewing after biting, the hands hold the pasta in a symmetric resting position. Pasta-eating is organized and features structured hand movements and so lends itself to the neural investigation of skilled-movements.

Neurospora fungi harbor a group of meiotic drive elements known as Spore killers (Sk). Spore killer-2 (Sk-2) and Spore killer-3 (Sk-3) are two Sk elements that map to a region of suppressed recombination. Although this recombination block is limited to crosses between Sk and Sk-sensitive (SkS) strains, its existence has hindered Sk characterization. Here we report the circumvention of this obstacle by combining a classical genetic screen with next-generation sequencing technology and three-point crossing assays. This approach has allowed us to identify a novel locus called rfk-1, mutation of which disrupts spore killing by Sk-2. We have mapped rfk-1 to a 45-kb region near the right border of the Sk-2 element, a location that also harbors an 11-kb insertion (Sk-2INS1) and part of a >220-kb inversion (Sk-2INV1). These are the first two chromosome rearrangements to be formally identified in a Neurospora Sk element, providing evidence that they are at least partially responsible for Sk-based recombination suppression. Additionally, the proximity of these chromosome rearrangements to rfk-1 (a critical component of the spore-killing mechanism) suggests that they have played a key role in the evolution of meiotic drive in Neurospora.

Human herpesvirus 8 (HHV-8) replication increases the risk of Kaposi sarcoma (KS). Highly-active antiretroviral therapy (HAART) reduces the incidence of KS, and regimens that contain protease inhibitors (PIs) may be particularly effective.To determine whether PI-based HAART regimens may more effectively inhibit HHV-8 shedding compared to regimens without PIs.Prospective, observational study of 142 HIV-1 and HHV-8 co-infected men conducted in Seattle, Washington. Quantitative HHV-8 PCR testing was performed on daily swabs of the oropharynx, the primary site of HHV-8 replication. Associations between antiretroviral regimen and detection of HHV-8 DNA in swabs were evaluated using generalized estimating equations.HHV-8 DNA was detected in 3016 (26%) of 11,608 specimens collected. PI-based HAART was associated with a statistically significantly lower frequency of detection (RR 0.2; 95% CI 0.1-0.5) compared to ART-naïve persons, whereas HAART without a PI was not (RR 0.7; 95% CI 0.4-1.3). Compared to ART-naïve persons, there was also a trend toward lower quantities of HHV-8 detected during treatment with HAART regimens that contained a PI. These associations between PIs and measures of HHV-8 shedding could not be attributed to use of nelfinavir, which inhibits HHV-8 replication in vitro, and were independent of CD4 count and HIV plasma viral load (VL).HAART regimens that contain PIs appear to decrease HHV-8 shedding compared to NNRTIs. Further study of PI-based HAART is warranted to determine the optimal regimens for prevention and treatment of KS.

The primary purpose of this study was to explore the unique impact of individual differences (e.g. gender, managerial experience), social culture, ethical leadership, and ethical climate on the manner in which individuals analyse and interpret an organisational scenario. Furthermore, we sought to explore whether the manner in which a scenario is initially interpreted by respondents (i.e. as a legal issue, ethical issue, and/or ethical dilemma) influenced subsequent recognition of the relevant stakeholders involved and the identification of intra- and extra-organisational variables significant to the scenario depicted. Data for this study were anonymously collected from professional samples in Russia (Moscow region) and in New Zealand. Findings show a strong effect of social culture (i.e. working in New Zealand or working in Russia) on the manner in which respondents characterised the scenario, on the experience of ethical climate and ethical leadership in their organisations, and on the ability to identify intra- and extra-organisational variables responsible for the situation presented in the scenario, above and beyond other individual and contextual factors.

This paper addresses the definition and the operational use of intuitions in philosophical methods in the form of a research study encompassing several regions of the globe, involving 282 philosophers from a wide array of academic backgrounds and areas of specialisation. The authors tested whether philosophers agree on the conceptual definition and the operational use of intuitions, and investigated whether specific demographic variables and philosophical specialisation influence how philosophers define and use intuitions. The results obtained point to a number of significant findings, including that philosophers distinguish between intuitions used to formulate (discovery) and to test (justification) philosophical theory. The survey results suggest that strategies implemented to characterise philosophical intuition are not well motivated since, even though philosophers do not agree on a single account of intuition, they fail to capture a preferred usage of intuitions as aspects of discovery. The quantitative summary of survey findings informs the debate on this topic, and advances more defined routes for subsequent approaches to the study of intuitions.

Objective: To determine whether rapidly cleared episodes of herpes simplex virus (HSV) reactivation occur in HIV-infected adults. Methods: Twenty HSV-2―seropositive, HIV-seropositive adults, including 9 (45%) who were also HSV-1 seropositive, collected oral and anogenital swabs for HSV DNA polymerase chain reaction 4 times a day for 60 days. Samples were positive for HSV if we detected ≥150 copies of HSV DNA/mL of specimen. Results: Median HSV shedding episode duration was 7.5 (range 4-253) hours for oral and 11 (range 4-328) hours for anogenital reactivation. Thirty-five percent of oral and 29% of anogenital reactivations lasted ≤6 hours, and 59% of oral and 53% of anogenital reactivations lasted ≤12 hours. Seven of 9 participants who shed orally and 10 of 15 who shed anogenitally had ≥1 reactivation lasting ≤6 hours. The median maximum level of HSV DNA detected in an episode increased with episode duration for both oral and anogenital episodes. Concurrent oral and anogenital shedding occurred more frequently than expected: oral HSV shedding was detected on 17% of time points with anogenital but 1% of time points without anogenital, shedding (P < 0.001). Conclusions: Rapidly cleared episodes of oral and anogenital HSV shedding occur in HIV-infected persons, supporting the hypothesis that frequent anogenital mucosal immune activation caused by HSV-2 is present in HIV coinfected persons, potentially contributing to HIV infectiousness.

Manned rotorcraft are often employed in harsh environments and difficult terrain that are inaccessible to other craft. Conversely, robotic rotorcraft are operated in controlled settings, often at safe, high altitudes. Missions such as cargo delivery, medevac and fire fighting are unachievable because of unpredictable adverse environmental conditions. To enable UAVs to perform these missions, the effects of obscurants on UAV sensor suites and algorithms must be clearly understood. This paper explores the use of a laser range finder to accomplish landing zone identification in unknown, unstructured environments. The ability to detect a landing zone in environments obscured by smoke is investigated. This is accomplished using a design methodology of testing and evaluating in a controlled environment followed by verification and validation in the field. This methodology establishes a concrete understanding of the sensor performance, thereby removing ambiguities in field tests.

The effect of highly active antiretroviral therapy (HAART) on control of herpes simplex virus (HSV) in human immunodeficiency virus (HIV) type 1– infected subjects is not known. Among 28 HAART-treated and 49 untreated subjects with HIV-1 and HSV-2 infections mucosal HSV shedding (median 18% and 29% of days positive for HSV DNA respectively; P = .08) and HSV DNA level (median 56250 and 50000 copies/mL respectively; P = .20) were similar. Treated subjects reported significantly fewer days with HSV lesions compared with untreated subjects (2.8% vs. 11.3% of days respectively; P = .001). Thus mucosal HSV shedding and HSV-2 reactivation were still frequent among treated subjects even though HAART was associated with fewer days with HSV lesions. (authors)

Trains of repetitive transcranial magnetic stimulation (TMS) at 10-30 Hz and intensities of 90-120% motor threshold were delivered through a figure of eight coil over the motor cortex while normal subjects made either rapid, self-terminated (ballistic) wrist movements or maintained the position of their wrist at a fixed angle. Movement kinematics and EMG activity in antagonistic forearm muscles were analysed. In the ballistic task, repetitive TMS had little effect on the velocity or acceleration of the initial segment of the movement, although it induced large terminal oscillations (tremor) around the target position at frequencies between 4.4 and 7.2 Hz. The likelihood that tremor would occur increased with increasing stimulus intensities or frequencies. It was maximal with stimulation over the forearm area, and decreased with stimulation over the leg area, or over parietal sites; there was no tremor during stimulation of cervical nerve roots. The frequency of the induced tremor was independent of the rate of stimulation and did not depend on the presence of excitatory and inhibitory motor responses to the stimulus. Stimulation could also induce tremor of the same frequency in the fixed task, but only during co-contraction of forearm muscles. The amplitude of tremor was proportional to the level of co-contraction. Clinically, the tremor induced by repetitive TMS appeared very similar to cerebellar tremors. In order to confirm this we investigated two cerebellar patients, one with autosomal dominant cerebellar ataxia and the other with multiple sclerosis. Both of them had a terminal tremor of 6-7 Hz in the wrist movement task. In the holding task, the amplitude of their postural tremor increased with the level of co-contraction in forearm muscles. Since the frequency of repetitive TMS-induced tremor was independent of stimulus parameters, we conclude that it represents some intrinsic property of the CNS. We suggest that the tremor is caused by disruption of cortical processes involved in terminating a voluntary movement or maintaining a posture. Similarities to cerebellar patients suggest that repetitive TMS may cause tremor by interfering with adaptive cerebellar afferent inflow to motor cortex. Repetitive TMS-induced tremor, therefore, may represent a model of some forms of cerebellar tremor in man.

Systematic functionalization of perfluoroaryl azides with chelating agents capable of complexing transition metals produces a new class of bifunctional photolabile chelating agents (BFPCAs). The strategy to shield the azide functionality from the electronic and steric influence of the electron-rich metal Pd through ester and amide bridges raised CH insertion efficiency to unprecedented levels (>92%) in a model solvent (cyclohexane). In contrast, perfluoroaryl azides attached to chelating agents via hydrazones show no significant CH insertion in cyclohexane upon photolysis. Measurements of the lifetimes of the singlet nitrenes derived from these agents by flash photolysis techniques correlate well with the efficiency of CH insertion by demonstrating longer lifetimes (10−50 times) for singlet nitrenes derived from azidotetrafluorinated esters and amides compared with the related hydrazones, which failed to yield significant CH insertion. A representative BFPCA 12 is chelated to diagnostic radionuclide 99mTc...

Synthesis of a new photo cross-linking agent incorporating chromogenicity, cleavability, and water solubility is described. The high efficiency of nitrene insertion observed upon photolysis of perfluoroaryl azides into organic solvents and proteins is extended to the design and synthesis of new multifunctional cross-linking agents useful for protein–protein interactions. The new cross-linker sulfosuccinimidyl (perfluorobenzamido)-ethyl-1,3′-dithiopropionate (SFAD) 10 was conjugated to IgG and cross-linked to horseradish peroxidase (HRP). The analysis of the cross-linked product using ELISA assays leads to a higher yield of IgG–HRP cross-linked product than that seen with a similar nonfluorinated analog. The efficiency of photo cross-linking by SFAD is also extended to small molecule biotin via CH insertion and checked for the retention of binding affinity of the cross-linked product.

The photoreduction of acetylene is catalyzed by Mo 2 O 4 (dedtc) 2 (dedtc, diethyldithiocarbamate) in the presence of 5–8 nm diameter colloidal TiO 2 . This photocatalytic process exhibits optimum activity at pH 6 and a loading of 30 catalyst molecules per TiO 2 particle. The same catalytic site(s) are responsible for C 2 H 2 reduction to C 2 H 4 and C 2 H 6 and H + reduction to H 2 . The overall photonic efficiency is 1.3% for the transfer of reducing equivalents to products at full lamp intensity, and increases with decreasing intensity. The effects of pH, temperature, intensity and loading on the catalytic process are consistent with a mechanism in which the catalytic site associated with the TiO 2 surface promotes the transfer of H atoms or electrons to the bound substrate. The photocatalytic properties of this neutral molecular complex are compared with those observed for other Mo-containing catalysts.

Synthesis and evaluation of a new class of photochemically activated heterobifunctional chelating agents for protein modification is described. Selective functionalization of perfluoroaryl azides by versatile phosphorus hydrazide ligating systems 2 and 3 for the complexation of transition metals and analogous radiometals form the basis for these new agents. The utility of the photogenerated precursors from these bifunctional agents to form covalent attachments is demonstrated through examination of C-H bond insertion on cyclohexane. Representative amide-coupled phosphorus hydrazides 5 and 6 provide78% insertion of the probe into unactivated C-H bonds of cyclohexane with short photolysis times. Photoconjugation of the photoactivable heterobifunctional chelating agent 6 and its Pd metalated analog 7 with HSA is also evaluated. The uncomplexed chelate appears to add to HSA with high efficiency, consistent with the observed 82% bond insertion into model solvents. Covalent attachment of 7, evaluated through the use of (109)Pd, was estimated to be between 49% and 74% with the uncertainty arising because of prephotolysis association of the (109)Pd complex with HSA. The application of in situ (19)F NMR to distinguish between bond insertion and noninsertion processes is demonstrated. These results suggest that functionalized perfluoroaryl azido phosphorus hydrazides may find utility as heterobifunctional photolabeling agents for attaching radionuclides to proteins and antibodies.

The synthesis and biological activity of functionalized lisinopril, a potent angiotensin converting enzyme (ACE) inhibitor is described. Selective functionalization of lisinopril is achieved at the secondary amino position by a photochemical method, whereas esterfication of the carboxylic groups and modification at the primary amino group is achieved by chemical methods. Autoradiographic investigations using competitive 125 I radioactive binding assays with the modified lisinopril reveal that the terminal amino group modification enhanced the binding to ACE, whereas the secondary amino group functionalization did not differ significantly from the binding properties of native lisinopril. However, esterification of the carboxyl groups reduced the inhibitory potentency from n M to μ M . These results suggest that lisinopril can be derivatized with preservation of inhibition potency toward ACE. These modifications may find utility in the development of photoaffinity labeling agents for ACE or to incorporate bifunctional chelating agents carrying diagnostic radiometals for the development of cardiac imaging agents.

The competitive photocatalytic reduction of H + and C 2 H 2 at catalytic sites formed when Mo 2 S 4 (S 2 C 2 H 4 ) 2− 2 is photoreduced on colloidal TiO 2 in the presence of a sacrificial electron donor was studied. Comparisons of the total number of electrons transferred to both substrates as a function of pH suggest that the substrates compete for a common catalytic site. Based on analogies with homogeneous solution studies, a mechanism involving an Mo(IV) dimeric species as the catalytic site is suggested. The efficiency for conversion of incident light to reduced products increases with decreasing light intensity and maximizes at about seven electrons transferred per 100 photons absorbed.

The photocatalytic of molecular hydrogen from aqueous suspensions of colloidal TiO2 loaded with MoS2−4 and Mo2S4(S2C2H4)2−2 was studied as a function of pH, loading and light intensity. The efficiency of these systems, in which polyvinyl alcohol and ethylenediamine tetraacetic acid (EDTA) were utilized as sacrificial electron donors, was compared with the well-studied systems utilizing platinum as an electron transfer catalyst. Optimum loading levels were 20 ions per particle for tetrathiomolybdate and 6 ions per particle for the thio dimer. Both of the Mo-S systems were only about 40% as efficient as platinum. Quantum yields of molecular hydrogen approximately doubled as the intensity was decreased by a factor of 10 and increased about twofold when the more efficient hole scavenger, EDTA, was added to the mixture. The highest yield obtained, in terms of the percentage utilization of the photoproduced electrons, was 11.5% compared with 28.2% for platinum. Except for differences in optimum loading levels, both catalysts gave similar results.

BACKGROUND: Human herpesvirus-8 (HHV-8) replication is critical in the induction and maintenance of Kaposi sarcoma, primary effusion lymphoma, and some cases of Castleman disease. In vitro and observational studies suggest that ganciclovir inhibits HHV-8 replication, but no randomized clinical trials have been conducted. METHODS: A total of 26 men infected with HHV-8 were randomized to receive 8 weeks of valganciclovir administered orally (900 mg once per day) or 8 weeks of placebo administered orally. After a 2-week washout period, participants in each group received the study drug they had not yet taken (either valganciclovir or placebo), for 8 additional weeks. Oral swab samples were collected daily during the study, and HHV-8 and CMV DNA were quantified by real-time PCR. RESULTS: A total of 16 human immunodeficiency virus (HIV)-positive men and 10 HIV-negative men enrolled in and completed the study. Of the 3,439 swab samples that participants had been expected to provide, 3029 (88%) were available for analysis. HHV-8 was detected on 44% of swabs collected from participants who were receiving placebo, compared with 23% of swabs collected from participants who were receiving valganciclovir (relative risk [RR], 0.54 [95% confidence interval {CI}, 0.33-0.90]; P = .02). Valganciclovir reduced oropharyngeal shedding of cytomegalovirus by 80% (RR, 0.20 [95% CI, 0.08-0.48]; P < .001). Shedding of HHV-8 and shedding of cytomegalovirus were independent. Hematologic, renal, or hepatic toxicities were no more common among participants who received the active drug, compared with those who received placebo, though participants who received valganciclovir reported more days of diarrhea. CONCLUSIONS: Valganciclovir administered orally once per day is well tolerated and significantly reduces the frequency and quantity of HHV-8 replication.

In this paper, we introduce a new apparatus to evaluate communications performance, which combines both active and passive measurements. This approach is very suited for moving networks (NEMO) in ITS environments, as we will show in a detailed scenario and experiment. The experiment uses the currently available NEPL implementation of NEMO based on the GNU/Linux operating system to demonstrate the actual feasibility of the scenario. Then the hybrid measurements approach makes it possible for us to thoroughly analyze the outcomes, be they achievements or failures, of this very architecture.

To test the hypothesis that there is no difference between adults with Class I crowded (CICR), Class III (CIII), and Class I normal (CIN) occlusions with respect to (1) arch widths, (2) width of the maxillary and mandibular arches, (3) gender dimorphism within groups, and (4) gender comparisons.Samples of 39 CICR subjects, 40 CIII subjects, and 40 CIN subjects were studied. All subjects were white Americans with no history of orthodontic treatment. An analysis of variance and Duncan's test statistically compared the groups and genders.The CICR group had mean maxillary and mandibular intermolar and alveolar arch widths significantly smaller than the CIN group. The CIII group had mean maxillary intermolar and alveolar arch widths significantly smaller than the CIN group. Mean maxillary and mandibular intercanine arch widths were similar in the three groups. The CICR and CIN groups had similar mean maxillary/mandibular intermolar and alveolar differences significantly larger than the negative differences observed in the CIII group. Gender dimorphisms were identical in the CIII and CIN groups. The CICR group differed by not having a gender dimorphism in the maxillary alveolar width and having a gender dimorphism in the mandibular intercanine width. Gender comparisons between groups were similar in intercanine widths but differed in other widths.The hypothesis was rejected by the findings of this study.

Functionalization of perfluoro aryl azides by bifunctional chelating agents (BFCAs) capable of forming high specific activity complexes with (99m)Tc (for gamma-imaging) and (188)Re (for radiotherapy) is described. The synthesis of multidonor BFCAs containing N(2)S(2), N(4), and N(3)S donor groups containing imidazole, pyridine, and pyrazine functionalities that may be important for tuning the pharmacokinetic parameters is also described. Functionalization of perfluoro aryl azides at various sites on BFCAs yields novel bifunctional photolabile chelating agents (BFPCAs) that are useful for covalent attachment to biomolecules. A representative Re-BFPCA 8a in a model solvent, diethylamine, proceeded to give a high yield of intermolecular NH insertion product without the decomplexation of the metal ion from 8a. All products originated from the photolysis of 8a in diethylamine are characterized by analytical techniques, and a plausible mechanism of formation of different photolytic products is suggested. The high yield of intermolecular NH insertion of Re-BFPCA 8a is extended to labeling of human serum albumin (HSA) and Fab fragments under aqueous conditions. The photolabeling technology developed here offers a new way to attach diagnostically and therapeutically useful radiotracers (e.g., (99m)Tc, (188)Re) to Fab fragments for potential noninvasive imaging and therapy of cancer.

This report discusses activities and progress that has occurred since initiation of this project on September 1, 1989. We have synthesized ethyl N,N{prime}-bis(benzoylmercaptoacetyl)-2,3-diaminopropanoate, a ligand to be used as a bifunctional chelating agent (BFCA), to form {sup 186}Re or {sup 188}Re ({sup 186}Re/{sup 188}Re) complexes. {sup 186}Re/{sup 188}Re, in reducing media, reacts with this ligand to form {sup 186}Re/{sup 188}Re-CO{sub 2}DADS chelates that will be used to formulate new radiolabeled photoaffinity labels (RPALs). Initial steps have been taken to synthesize R-As-dithiol compounds. This approach will be used to produce {sup 77}As-RPALs or covalently link {sup 77}As directly to monoclonal antibodies (MAbs). The R group will contain a group that can be used for conjugation reactions. Spectral and photochemical properties of various types of photoaffinity labels (PALs) have been studied. Acrylo-azido compounds and 9-azido acridine have been studied as well as several other photoprobes. The binding characteristics of the azido-based PALs to HSA have been studied and progress has been made on developing techniques for efficiently separating of non-covalently sound PALs. The Nd-YAG laser was purchased and arrived in 1990. It has been assembled and tested and is now operational.

The June 1975 meteoroid storm detected on the moon by the Apollo seismometers was the largest ever observed. Reexamination of radio data taken at that time showed that the storm also produced pronounced disturbances on Earth, which were recorded as unique phase anomalies on very low frequency (VLF) radio propagation paths in the low terrestrial ionosphere. Persistent effects were observed for the major storm period (20 to 30 June 1975), including reductions in the diurnal phase variation, advances in the nighttime and daytime phase levels, and reductions in the sunset phase delay rate. Large nighttime phase advances, lasting a few hours, were detected on some days at all VLF transmissions, and for the shorter propagation path they were comparable to solar Lyman alpha daytime ionization. Ion production rates attributable to the meteor storm were estimated to be about 0.6 to 3.0 ions per centimeter cubed per second at the E and D regions, respectively. The storm was a sporadic one with a radiant (that is, the point of apparent origin in the sky) located in the Southern Hemisphere, with a right ascension 1 to 2 hours larger than the sun's right ascension.

The method of flash photolysis was used to identify the transient absorption spectrum and to characterize the decay kinetics of the indole triplet of human serum albumin. This protein was studied because it contains a single indole side chain which is deeply buried in an expandable oily region and because the phosphorescence of the homologous indole in bovine serum albumin could not be detected at ambient temperatures. The transient was identified on the following basis: (i) its triplet-triplet absorption spectrum was similar to those previously reported for indole and tryptophan; (ii) it was quenched by small quantities of oxygen; and (iii) it was photobleached by 370- to 700-nm light. In a nitrogen-saturated solution at room temperature, the indole triplet decays exponentially for more than a factor of 10 with a lifetime of 0.5 msec. These observations suggest that, because of its exponential decay and relatively long lifetime, the triplet will be more valuable than the indole singlet as an intrinsic reporter group for the study of the structure and dynamics of proteins in solution.

The total rate constant for H-atom reactions with cysteine and penicillamine has been determined at pH 1 and pH 6 utilizing a photolytic source of H-atoms. The effect of COOH dissociation is to increase k/sub cysteine/ by 1.3 and k/sub penicillamine/ by 1.75. This effect is of the same magnitude as that observed for nonsulfhydryl amino acids. At higher pH values, dissociation of NH$sub 3$$sup +$ causes further enhancement of the rate for penicillamine. The mechanism of H-atom reactions with these amino acids appears to be independent of pH in the range of 1 to 6. (auth)

k4 ks two mechanisms: (a) H + RSH- Hs + RS, and b) H + RSH H2S + R. The rate constant for reaction 4 is influenced by the presence of functional groups within the molecule. It is also found that reaction 4 is the predominant mechanism for hydrogen atom reaction with primary sulfhydryl compounds while reaction 5 is most important for secondary and tertiary SH groups. The relationship of these results to observed

The rates of hydrated electron reactions with cysteamine, cysteine, thioglycol, α-mercaptopropionic acid, β-mercaptopropionic acid, and penicillamine have been studied in the pH 1-3 region. Hydrogen yields, which are a function of pH in this region, were used to monitor the competition between H+ and RSH for hydrated electrons. Corrections were applied to the observed rate constants to account for dissociation of the COOH group and the ionic strength effect on hydrated electron reactions. In the cases of cysteine and penicillamine, the rate constants for reaction with protonated amino acids at infinite dilution were greater by a factor of 3-5 than those for reaction with the zwitterion. Uncharged species show no pH dependence of the rate constant within this region. All rate constants measured were of comparable magnitude and approached the diffusion controlled limit.